Instruments and Methods for XRF analysis of

Materials of Cultural Interest

Facoltà di Ingegneria Civile ed Industriale

Dipartimento di Ingegneria chimica, materiali, ambiente
Dottorato in Ingegneria dei Materiali, delle Tecnologie e dei Sistemi Industriali
Complessi
Curriculum B, Ingegneria dei Materiali e delle Materie Prime, XXVIII ciclo

Candidato
Claudia Polese
N° matricola 1142373

Tutor Co-tutor
Cecilia Bartùli Marco Ferretti
Sultan B. Dabagov
Dariush Hampai

A/A 2014/2015
Ringraziamenti

Desidero anzitutto ringraziare la Prof.ssa Cecilia Bartúli (DICMA-Sapienza)

per aver accettato di essere la mia tutor, e per tutto il tempo e l’aiuto
dedicatomi; l’Ing. Marco Ferretti (ITABC-CNR) per avermi seguita e con-
sigliata nello svolgimento del mio progetto, fin dall’esame di ammissione al
dottorato; il Prof./Dr. Sultan B. Dabagov e il Dr. Dariush Hampai (LNF-
INFN) per avermi ospitato presso il loro laboratorio negli ultimi tre anni, ed
aiutato ad imparare moltissime cose riguardo l’attivitá sperimentale e non
solo.
Ringrazio inoltre il Dott. Adolfo Esposito, la Dott.ssa Astrik Gorghinian
(LNF-INFN) e il Dott. Francesco Taccetti (Sezione di Firenze e CHNet -
INFN) per il supporto alle mie varie attivitá e missioni.
Rivolgo poi un particolare ringraziamento ai miei ‘compagni di ventura’ il
Dott. Andrea Liedl (Roma3), la Dott.ssa Francesca Casarin ed Emilio Capi-
tolo (LNF-INFN) per il prezioso aiuto e sostegno che mi hanno dimostrato
nel condividere gioie e dolori della vita da dottoranda, e nel supporto con-
creto nello svolgere la mia ricerca.
Ringrazio poi, per i consigli tecnici, messa a disposizione di materiali,
tempo, strumenti e fondi: il Dott. Armando Solé (ESRF), il Dott. Tom
Schoonjans (Diamond Light Source), la Dott.ssa Maria Luisa Grilli e la
dott.ssa Franca Persia (ENEA), la dott.ssa Rosa Maria Villani e la sig.ra
Valeria Sicilia (SAM-IPZS), il Dott. Virgilio Genova (DICMA-Sapienza), il
Dott. Giannantonio Cibin (Diamond Light Source), il Prof. Gabriele Vita-
colonna e il Dott. Gianfranco Marsibilio (Ente Mostra Artigianato Artistico
Abruzzese), la Dott.ssa Lucia Arbace e la Dott.ssa Ernestina Stinziani (So-
printendenza BSAE dell’Abruzzo).
Estendo inoltre i miei ringraziamenti a tutte le fantastiche persone che
ho avuto la fortuna di conoscere sia presso i Laboratori Nazionali di Frascati
che in Facoltá, per le quali non basterebbe sicuramente una pagina sola, e
che in aggiunta alle persone gi sopracitate mi hanno accolto in un modo che
non credevo possibile, sia professionalmente che personalmente.
Vorrei esprimere la mia sincera gratitudine a tutti gli amici e colleghi
che mi sono stati a fianco in questi anni e hanno sopportato i miei sfoghi,
in particolare Luca, Salvatore, Luca, Elisa, Maria Chiara, Lidia, Giuseppe,
Beatrice, Ye, Giuseppe, Maria Paola, Erica, e Valerio.
Desidero infine ringraziare profondamente i miei genitori, senza il cui
sostegno non avrei sicuramente potuto intraprendere la mia avventura.

1
Summary

Introduction 2

1 X-ray Fluorescence Spectrometry 6

1.1 Physics of X-rays emission . . . . . . . . . . . . . . . . . . . . 6
1.2 X-ray fluorescence analysis . . . . . . . . . . . . . . . . . . . . 7
1.2.1 Analysis of Cultural Heritage materials . . . . . . . . 9
1.3 Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.3.1 Sources . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.3.2 Detectors . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.4 Methods of quantitative analysis . . . . . . . . . . . . . . . . 18
1.4.1 The Fundamental Parameters (FP) method . . . . . . 18
1.4.2 PyMCA software . . . . . . . . . . . . . . . . . . . . . 21
1.5 Principles of radiation protection . . . . . . . . . . . . . . . . 29

2 Micro X-ray Fluorescence Spectrometry 31

2.1 X-ray optics . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.2 Polycapillary lenses . . . . . . . . . . . . . . . . . . . . . . . . 34
2.3 µXRF for cultural heritage: state of the art . . . . . . . . . . 41

3 Configuration and test of the latest PyMCA version 44

3.1 Experimental set up . . . . . . . . . . . . . . . . . . . . . . . 44
3.2 Experimental results . . . . . . . . . . . . . . . . . . . . . . . 47
3.2.1 Homogeneous matrices . . . . . . . . . . . . . . . . . . 47
3.2.2 Multilayer samples . . . . . . . . . . . . . . . . . . . . 53

4 Getting in touch with µXRF analysis of Cultural Heritage

materials 57
4.1 In situ investigation of the processional cross by Nicola da
Guardiagrele . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.2 Comparative use of a conventional XRF and a µXRF spec-
trometer: experimental setup . . . . . . . . . . . . . . . . . . 59
4.3 Discussion and interpretation of the results . . . . . . . . . . 62

1
5 Development of a µXRF spectrometer for Cultural Heritage
applications (pHEMIX) 73
5.1 Experimental set up . . . . . . . . . . . . . . . . . . . . . . . 74
5.2 Feasibility study . . . . . . . . . . . . . . . . . . . . . . . . . 76
5.2.1 Experimental results . . . . . . . . . . . . . . . . . . . 77
5.3 Selection and experimental characterization of the system
components . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
5.3.1 Transmission anode X-ray tube . . . . . . . . . . . . . 83
5.3.2 Polycapillary lens . . . . . . . . . . . . . . . . . . . . . 86
5.3.3 Beam filtering . . . . . . . . . . . . . . . . . . . . . . . 91
5.3.4 Detector . . . . . . . . . . . . . . . . . . . . . . . . . . 93
5.4 Experimental validation of the prototype . . . . . . . . . . . . 95
5.4.1 Sensitivity and Limits of Detection . . . . . . . . . . . 97
5.4.2 Low-Z elements detection: He flux tests . . . . . . . . 103
5.4.3 Quantitative analysis . . . . . . . . . . . . . . . . . . . 110
5.5 Mechanical design . . . . . . . . . . . . . . . . . . . . . . . . 116

Conclusions 116

2
Introduction

Diagnostics referred to cultural heritage goods is a well established research

field, demanding high performance, non-destructive and portable instru-
ments. One of the main focuses is the characterization of the constituent
materials (often including medium- and high-Z elements such Ag, Sn, Sb, Ba,
and Cd), which may provide information on the manufacturing techniques,
dating, provenance, authenticity, and conservation conditions. When deal-
ing with ancient artifacts, the need of analyzing fine details or small abraded
areas already present on the surface, without producing further abrasions,
is frequent and demands for a high spatial resolution analysis (< 1 mm).
In addition, multilayered matrices are not uncommon among the cultural
objects (paintings, jewelry, deteriorated artifacts), and their investigation
usually requires a destructive stratigraphic sampling.
X-ray fluorescence (XRF) spectrometry satisfies most of the art histori-
ans and restorers requirements, since it is fast, portable, user-friendly, non-
destructive, and provides qualitative and quantitative information about the
elements content. For these reasons, it has been one of the earliest techniques
applied in this field, and it still remains among the most successful ones to
characterize the elements in inorganic materials, not only of cultural interest,
but in many di↵erent fields (medicine, industry, geology, etc.). The quan-
titative analysis of the data can be performed either by methods based on
empirical calibration curves or by mathematical models, as the Fundamen-
tal Parameter (FP) method, by means of several software also open-source.
Some of these codes, such as PyMCA, are able to deal also with multilay-
ered matrices. Portable spectrometers working with high energy excitation
beams (X-ray tube voltages  60 kV) allow the detection of the fluorescence
K-lines of medium-Z elements, with better counting statistics and avoiding
their overlapping respect to the L-lines case. Micro-XRF spectrometers pro-
vide also a high spatial resolution (ten-hundreds of microns) analysis. Their
portable versions are obtained by employing polycapillary lenses (polyCO),
which unlike other kind of X-ray optics are characterized by size and working
distance of the order of few cm. These focusing lenses are made of thousands
of hollow glass channels arranged in a barrel shape, in which X-ray photons
propagate by multiple reflections. They collect a large solid angle of radia-
tion with a gain of 3-5 order of magnitude respect to a pinhole, therefore can

3
be efficiently coupled with conventional X-ray tubes. On the other hand,
polyCO act as a low pass filter, as the acceptance angle inversely depends on
the photon energy. Actually, fourth generation lenses are mainly optimized
for the medium energy range (8-17 keV), with a decreasing transmission
efficiency up to 50 keV (as the extreme upper limit).
The principal aim of this PhD project is the study and assembling of
a novel portable micro-XRF spectrometer, suitable for the investigation of
inorganic materials, mainly of cultural interest. The high spatial resolution
will be achieved by the use of a polycapillary lens, selected according to
its transmission efficiency in the medium-high energy range (15-30 keV).
The other instrumental components (X-ray tube, primary beam filter, and
detector) will be selected in order to maximize the K-lines fluorescence ex-
citation and detection of the elements of interest above-mentioned, and to
compensate the partial intensity loss due to the use of the polyCO at those
energies. Within this project activities as both instrument developer and
final user are carried out. By this way the skills and know-how about not
only the instrument design, but also its analytical performance and data
interpretation will be acquired.
In the first two chapters a deep description of the analytical technique
and the polyCO physical working principle will be illustrated.
In chapter 3 the latest version of PyMCA, which allows taking into ac-
count SE and scattering e↵ects, will be tested for the quantitative analysis of
metals and glass alloys. This part is carried out as an informal collaboration
with the software developers (Solé from ESRF, and Schoonjans from Dia-
mond Light Source) in order to provide feedback as final user, being this last
version on development. Then, a coating thickness determination method
is applied to another type of two-layers matrix, the PVD coated steel sub-
strates. By this way the application of the basic principle of the method
to di↵erent matrices and disciplinary fields will be verified. The evaluation
and optimization of the quantitative analysis method will be important for
the treatment of the data collected in the next chapters.
In chapter 4 a case study is presented, regarding the in situ investigation
campaign on the fragments of a XV Century processional cross, consisting
of gilded silver sheets and enameled silver plates. In this study, in collabora-
tion with ITABC-CNR, LNF-INFN (Servizio di Radioprotezione: Esposito
and Gorghinian) and Ente dell’Artigianato Abruzzese (Marsibilio and Vita-
colonna), both a portable XRF and a micro-XRF (with a sample chamber)
spectrometers are employed. By this way the actual complementarity of
these di↵erent instrumentations, which makes unavoidable their combined
use for a comprehensive analytical approach, will be highlighted. Obtaining
in one spectrometer a compromise between the advantages of both (exci-
tation of high-energy fluorescence lines and applicability to large objects of
the portable XRF system, and excellent spatial resolution of the micro-XRF
one) will be the core of the next chapter.

4
 In chapter 5 the study related to the new XRF spectrometer is deeply
illustrated, and carried out in collaboration with LNF-INFN (XLab Fras-
cati). First, a preliminary study of feasibility is presented, in order to obtain
the skills to work with polycapillary lenses and their operative conditions.
In addition, the results will be the basis for the choice of the instruments
components parameters. Later, each one of the selected components will
be experimentally characterized. Finally, a validation study of all the com-
ponents assembled together, in a preliminary experimental layout, will be
performed. In particular, the limits of detection of the resulting system
will be investigated for di↵erent type of matrices, and a first attempt of
quantitative analysis of the data will be carried out.

5
1

X-ray Fluorescence
Spectrometry

1.1 Physics of X-rays emission

X-ray radiation is very energetic portion of the electromagnetic spectrum as
its energy ranges from few eV to hundreds of KeV.
Although observed during several experiments, X-rays have been offi-
cially discovered by Roentgen in 1895 and named “X” because of their mys-
terious nature. He produced the first radiographic image of the history, the
so-called Hand mit Ringen, and in 1901 was awarded with the first Nobel
Prize for Physics. This discovery paved the road to a series of studies and
analytical techniques based on X-rays, with a big impact in both the re-
search field and the common life. At present, X-rays are greatly employed
in various application fields, from medical diagnostic to industrial quality
monitoring. They allows many kind of non-destructive investigations to be
performed, for what regards both imaging (radiography and tomography)
and compositional analysis (absorption, fluorescence, di↵raction, etc.) [1].
X-rays are basically produced by the collision of an electronic beam
onto a metal target. Successively, a X-ray beam is emitted, the spectrum
of which is the result of the combination of two main e↵ects (Fig. 1.1).
One component originates from the violent deceleration of the electrons,
which release part of their kinetic energy as X-ray photons, and results in
a continuum spectrum called bremssthralung. The other one is produced
by the excitation and the successive relaxation of the target atoms. During
the transaction from an external shell to an inner one, the atomic electrons
release energy as X-ray photons. Due to the fact that the atomic orbital
energies are discretized and characteristics of the element, discrete emission
lines are obtained.

6
Figure 1.1 Example of a typical X-ray spectrum: both the bremssthralung and
the characteristics anode fluorescence lines (W L-lines in this case) are visible.

1.2 X-ray fluorescence analysis

X-ray fluorescence spectrometry has many positive features making it a suit-
able technique for a wide range of applications. It provides a cheap, fast, sen-
sitive, multi-elemental, non-destructive analysis. No sample pre-treatment
is required, and the instrumentation is often portable, for in situ campaigns.
On the other hand, XRF presents some problems for the detection of low
energy elements (Z < 3).
When interacting with matter, an X-ray beam is attenuated by various
e↵ects, depending on the energy of the incident photons and the material
composition. One of the results of this interaction is the X-ray fluorescence
(XRF) phenomenon, consisting in the emission of characteristics X-rays and
caused by the photoelectric e↵ect (Fig. 1.2a). After an inelastic collision the
incident photon energy is transferred to the atomic electron of an internal
shell (K, L, M), and in the X-rays case this energy is enough to extract it
as a photoelectron. Then, an electron from an external atomic shell will
occupy the hole left by the photoelectron releasing a photon with an energy
equivalent to the di↵erence between the two electronic levels.
By this way we have an emission of X-rays with an energy characteristic
of the element, as it depends on the scheme of the atomic orbitals (Fig.
1.2b). In the XRF spectrum this signal is represented by the characteristics
“fluorescence peaks” (Fig. 1.3).
If the electron is extracted from the K shell four lines are emitted (K↵1 ,
K↵2 , K 1 and K 2 ), while if it comes from the L shell the fluorescence lines
are nine (L↵1 , L↵2 , L 1 , L 2 , L 3 , L 1 , L 3 , L1 and L⌘ ). However, for
what regards elements with an atomic number under 40, the combination of
the K↵1 -K↵2 and K 1 -K 2 and the L↵1 -L↵2 , L 1 -L 2 -L 3 results in singular
peaks (while for example silver K 1 and K 2 are separated). Therefore the
K-lines are usually two (K↵ and K ) and the L-lines six (L↵ , L , L 1 , L 3 ,
L1 e L⌘ ), and only the first of these is sufficiently intense. The presence of

7
 Figure 1.2 a) Photoelectric e↵ect, b) scheme of the atomic orbitals.

the less intense lines and their ratio, known in literature, allows the element
to be identified. The energy of the fluorescence lines is proportional to the
atomic number Z and, as a less energetic radiation undergoes to a stronger
scattering, for light elements the background noise increases.
The energy of the fluorescence lines provides qualitative informations,
while their intensities (the peak areas) are related to the amount of the
elements in the matrix, as it will be discussed in the section dedicated to
the quantitative analysis (section 1.4).

Figure 1.3 Example of a XRF spectrum of a copper alloy.

Actually, only some of the photoelectrons induces fluorescence, while

others transfer their energy to external atomic electrons, emitted as Auger
electrons. The fraction of the electronic vacancies of the K shell of an el-
ement i generating fluorescence is indicated by the fluorescence yield !Ki
(Fig. 1.4a). The fluorescence cross section, which is the probability that
it takes place, is directly proportional to the photoelectric e↵ect cross sec-

8
tion, the fluorescence yield and the atomic number. The photoelectric cross
section influences the trend of the mass attenuation coefficient ⌧ (E) versus
the energy of the incident photons, resulting in a plot characteristic of the
element: it shows peaks at the extraction energies (a bit higher than the
fluorescence energies) and then rapidly decreases (Fig. 1.4b). The total
mass attenuation coefficient µ(E) characteristic of a material results from
the major component ⌧ (E), plus the coherent and Compton scattering co-
efficients.

Figure 1.4 a) Auger and fluorescence yield: the two e↵ect are in competition. For
high Z elements a fluorescence phenomenon is more probable than Auger, while it
is the opposite for low Z elements. b) Absorption edges for gold shells (K, L, M).

1.2.1 Analysis of Cultural Heritage materials

XRF spectrometry is widely applied in many disciplinary fields (environ-
mental science [34], industry, geology, etc.), as it essentially provides a fast
elemental analysis, with both qualitative and quantitative informations, for
a wide range of inorganic materials. Its non-destructivity is an important
requirements for many applications, as it allows both to repeat the mea-
surements and to preserve the integrity of the sample. XRF spectrometers
can be of di↵erent sizes and geometry, according to the specific application
they are dedicated to. Some are table-top instruments equipped with sam-
ple chambers, and usually provide best energy and spatial resolution and
allow in vacuum analysis to detect light element signals, but the samples
have to be brought in the laboratory and for big objects sampling would
be required. The portable versions are small sized and can be used also on
great and geometrically elaborated objects, but usually have a less excitation
power.
Because of all these characteristics, since the 1970’s XRF spectrometry
is among the most commonly used techniques in the diagnostics for cultural
heritage, especially because it is suited for in situ and non-destructive analy-

9
sis. Almost all kind of inorganic materials can be investigated in this way, for
example pigments (in paintings, mural paintings and ancient manuscripts),
metals, glasses, and pottery.
The elemental characterization of the raw materials can provide many
useful informations to restorers and art-historians, helping them to under-
stand the manufacturing technique. In archaeometric studies it is important
to determine the amounts of the trace elements, especially for mineralogical
samples, because they can indicate the provenance mine and this informa-
tion can be used to trace back the ancient trade-routes. Characterizing the
composition can also help to confirm the possible dating and author attribu-
tion of an artifact, as e.g. some elements are known to be discovered, used
and/or synthetized only since a certain period. It is also possible to recog-
nize eventual restoration parts, and determining the degradation products
is useful for the conservation approach.
The composition of the artifacts often includes medium-Z elements (Ag,
Sn, Sb, Ba, Cd etc.), for which the excitation and detection of the fluo-
rescent K-lines would be more useful with respect to the L-lines, in order
to have better counting statistics and to avoid the overlapping of the lines
themselves (Fig. 1.5). For this purpose, the excitation beam must have a
component at sufficiently high energy, and the detection efficiency has to
be reasonably high in the energy range of the investigated K-lines. Such
a spectrometer, due to the X-ray source parameters, is subject to operat-
ing (safety laws) and portability restrictions. Anyhow, there are examples
of homemade spectrometers working at 60 kV (HE system, i.e. high en-
ergy system) [35] with high analytical performances, which require a proper
shielding and operating authorization by a qualified forensic. These reasons
encourage the commercial use of low-power tubes with voltages up to 40 kV
that result less efficient in the excitation of, e.g., the K-lines of Sn or Sb.

Figure 1.5 Example of a XRF spectrum, where the K-lines of Ag, Sn and Sb are
perfectly distinguishable, while the L-lines are difficult to resolve.

XRF can be used also for imaging purposes, as by a spatial scanning of

the sample or the spectrometer, a XRF spectrum for each point is registered
and elemental distribution maps can be obtained (Fig. 1.6) by selecting their

10
lines energy region.

Figure 1.6 Scheme of an XRF imaging layout, and a result for the fragment of a
Middle Ages earthenware jar from XVI Tuscan furnace [33].

1.3 Instrumentation
A XRF spectrometer is basically composed of an X-rays source to induce
fluorescence in the analyzed object, a detector, and a system for data ac-
quisition and treatment. A general experimental layout is shown in Fig.
1.7.

Figure 1.7 General scheme of an XRF experimental geometry.

1.3.1 Sources
The most conventional and ancient kind of radiation source is represented
by X-ray tubes. The first prototype was the Crookes tube dating back to
the second half of the 19th century, which was substituted by the cathodic
tube, also known as Coolidge tube.
An X-ray tube mainly consists of two electrodes put inside a vacuum
glass chamber (Fig. 1.8). The cathode is connected to a tungsten filament
heated by an electric current in order to release electrons by thermionic

11
e↵ect. Due to the voltage applied to the two electrodes, these electrons go
to impinge onto a metal target placed on the anode at the other tube side.
As X-rays are emitted in all directions, the glass chamber has to be shielded
so that the beam exits only from a window (usually a beryllium window).
The energies of the bremssthralung spectrum are proportional to the voltage
and independent from the target material (Fig. 1.9a), while the intensities
depends on the current (Fig. 1.9b) and follow the inverse square law for the
distances.

Figure 1.8 Layout of a X-ray tube in reflection mode: C) cathode with tungsten
filament, A) anode and T) target, W) beryllium window with B) outcoming beam.

Figure 1.9 Trend of the continuum in function of the voltage (expressed in kV)
(a) and the current (expressed in mA) (b) of the tube.

There are many kind of commercially available tubes, of di↵erent sizes

and parameters (voltage and current). Some types are very powerful and
heavy, and can be efficiently employed in laboratory set-ups. However there
is a good choice of small and light ones, suitable for in situ analysis. In gen-
eral, tubes for portable XRF devices has a voltage ranging between 30 and
60 kV and a current between 0.5 and 1.5 mA. Moreover, as they emit radia-
tion only when turned on (instead of other kind of sources), radioprotection
restrictions are reduced (section 1.5). In modern tubes the emitted elec-

12
trons are collimated in a small focal spot on the target, in order to obtain
a micro-focus source. The most common anodes are: copper, chromium,
molybdenum, silver, tungsten.
The majority of these tubes works in reflection mode, as illustrated in
Fig. 1.8, but there is also the transmission mode (described in section 5.3.1).
The production of X-rays is a very inefficient process: less than 1% of the
electric energy given to the tube is converted in X-ray radiation, while the
remaining part is dissipated as heat. This fact makes necessary a cooling
system. Thanks to the higher sensitivity of the newest detectors, in the
modern instruments the voltage can be kept lower allowing to overcome this
problem.
Another kind of compact X-ray source is represented by radioactive
sources (such as americium 241), which unlike conventional tubes produce
monochromatic beams. The radioisotope is chosen in order to avoid over-
lapping between its emission lines and the fluorescence signal we want to
detect (Tab. 1.1), and with a half-life not too short. This kind of source
can be used also to induce X-ray emission from secondary targets: by this
way, with the same source it is possible tuning the device on the desired
primary beam energy. Usually the radioisotope is incapsulated, to avoid
contamination, and shielded in order to limit the radiation emission only in
one direction (Fig. 1.10). However, their radioactivity is always “active”,
and this strongly restricts their use in public places. In addition, their low
flux beam requires quite long measurement times.
isotope energy (keV)
147
Pm/Al 10-40
238
Pu 12-17
109
Cd 22
241
Am 60
57
Co 122

Table 1.1 Emitted energies for di↵erent types of radioactive sources.

Figure 1.10 Scheme of an Amersham source: the -rays from the americium (59.6
KeV), a circular sealed source, impinge on one of the six targets (Cu, Rb, Mb, Ag,
Ba e Tb), which emits characteristic X-rays fluorescence.

13
 A third kind of X-ray source is represented by synchrotron radiation
light facilities, which are usually equipped with many X-ray beamlines (Fig.
1.11). This huge structures allows very brilliant and monochromatic beams
to be obtained, which can be handled with complex and advanced optics
to produced high focused or quasi-parallel beams. Unfortunately, they are
incompatible with the request for in situ analysis, and even when the object
movimentation is possible the application procedure for beam time is quite
long and complicated.

Figure 1.11 Artistic rendering of Diamong Ligth Source, one of the many syn-
chrotron radiation structures in the world. The electrons in the accelerator ring are
forced to curve by magnets placed along their trajectory, and in this process they
emit synchrotron light that goes into a beamline, equipped with a monochromator.

In order to cut o↵ the low energy fraction of the primary beam, which
would undergo to scattering increasing the noise, di↵erent kind of filters can
be used. Usually they are metal sheets (Al, Fe or Cu) with a thickness
of tens of microns. They are chosen according to their absorption edges,
allowing also the selective filtering of the characteristic anode lines. By this
way, the saturation of the detector is also prevented. Usually the X-ray
beam is also collimated by means of a pinhole (e.g. Pb) in order to obtain
a spot size of around 1 mm, but if a higher spatial resolution is required
more advanced X-ray optics (deeply discussed in chapter 2) are necessary.
In addition, a pointing system generally consisting of two lasers helps to
control the analyzed area.

1.3.2 Detectors
The fluorescence radiation is collected by the detector and converted into
an electric signal by the acquisition system. The beam flux is registered in
terms of counts per time unit, therefore the intensity is expressed as number
of photons versus the energy (XRF spectrum). This procedure requires fast

14
detector response and signal elaboration with respect to the velocity of the
quantum absorption, related to the beam flux.
Detectors can be divided in three main types of transducers: gas de-
tectors, scintillators, and semiconductor detectors. Solid state detectors
consisting of a semiconductor crystal (Ge or Si) are the most common type
presently used for X-rays. Usually the detector is equipped with a beryllium
window absorbing the low energy fraction of the spectrum. For particular
applications requiring a high sensitivity for light elements, devices with poly-
meric windows or with the crystal exposed can be used. The crystal consists
of a p layer facing the X-rays, a middle part and a n layer that transfers the
signal to a preamplifier. The photon impinging on the crystal originates a
high energetic photoelectron and a cascade e↵ect. If a voltage is applied,
this photon absorption results in an electric impulse with an amplitude pro-
portional to the photon energy (Fig. 1.12). Then, it is converted into a
digital signal by the multichannel analyzer, that registers the counts for ev-
ery channel (each one associated to a di↵erent amplitude and therefore to a
di↵erent energy value) and provides the fluorescence spectrum.

Figure 1.12 Scheme of the signal conversion. The shaping time is important, for
example, to avoid the generation of sum peaks and having good time resolved data.

Nowadays it is common working in EDS mode (energy dispersive sys-

tem), in which all the energy values are registered at the same time. The
WDS mode (wavelength dispersive system) involves the use of a monochro-
mator to acquire one wavelength at time, resulting in very long acquisition
times, but providing a better energy resolution.
A fluorescence spectrum does not consist only of the characteristic lines
of the analyzed sample, but also of other components (Fig. 1.13).
The elastic and anelastic scattered peaks of the tube anode characteristic
lines can appear in the XRF spectrum, if the voltage applied to the source
is high enough to excite them and the primary beam is not properly filtered.
The X-ray photon impinging on the detector crystal (e.g. Si) excites a
silicon atom and the successive emission of a characteristic photon (ESi =
1.74 keV). If this phenomenon takes place on one edge of the crystal, this
photon could escape from the detector, and only the photoelectron energy

15
Figure 1.13 Example of an iron XRF spectrum, presenting also the escape peak,
the sum peaks and the source scattering.

(Ee ) given by the following formula is registered:

Ee = E0 ESi (1.1)
where E0 is the energy of the ‘primary incident’ photon. This e↵ect
results in the so-called escape peaks, which have a much lower intensity
than their generating fluorescence one.
If two photons (EX ) arrive at the same time on the crystal, they can be
seen as a single photon resulting in a sum peak with energy Es = 2EX .
An important parameter to be considered is the detection efficiency ⌘
for the di↵erent incident energies Ei (Fig. 1.14). It can be expressed as
the percentage of the photons e↵ectively measured for every energy value.
It can be considered as the counterpart of the detector material transmis-
sion efficiency. It depends on the mass attenuation coefficient µEi , which
decreases with the increase of the energy of the incident photons, and the
crystal thickness x.

µ(Ei ) x
⌘=1 exp (1.2)
It should be corrected for the geometric efficiency ⌘G of the system:

⌦
⌘G = (1.3)
4⇡
where ⌦ is the radiation solid angle captured by the detector and depends
on the active area of the crystal and the distance from the sample.

16
Figure 1.14 Example of a detector efficiency trend in function of the incoming
energy, experimentally measured.

A good energy resolution allows to distinguish between close peaks (Fig.

1.15). The detector resolution is usually indicated by the full width at half
maximum (FWHM) of the peak.

Figure 1.15 Comparison between two fluorescence peaks registered with high and
low energy resolution. High energy resolution results in thin and high peaks.

Another parameter useful to evaluate the performances of an XRF sys-

tem is represented by the Limits Of Detection (L.O.D.) for each element
and can be calculated as [2]:

2.33Cstd
CM DL = p (1.4)
(P/B)(P/tlive )tlive
where CM DL is the detection limit (with a reliability of 95%), Cstd the
concentration of the analyzed element, P the peak net area, B the back-
ground and tlive the counting time.
Once the acquisition campaign is finished, the data are processed by
means of proper softwares. Firstly the XRF spectra are calibrated and

17
converted from channels to energy values, so the qualitative analyses can
be performed. Some dedicated code also allows quantitative informations
to be achieved. Each fluorescence peak if fitted by a gaussian curve and
the area (the number of photons for that fluorescence line) is related by
proper calculations (section 1.4) to the element amount in the matrix. An
alternative and more empirical way to obtain quantitative informations is by
producing an experimental calibration curve based on a series of standards
with a matrix similar to the analyzed sample.

1.4 Methods of quantitative analysis

The basic principle for a quantitative interpretation of XRF data is that the
fluorescence lines intensity (more correctly the peak area) is proportional
to the element concentration. But this intensity is influenced also by many
other parameters that have to be taken into account in order to achieve
an accurate interpretation (in the so-called Fundamental Parameters ‘FP’
method). Among these parameters we have: the overall matrix mass atten-
uation coefficient (given by its composition), the photoelectric cross-section,
the thickness of the analytical volume, and the secondary fluorescence ef-
fects.
Due to the complexity of the calculations required to manage all these pa-
rameters, many times an experimental calibration curve is preferred. How-
ever, this latter approach requires for every di↵erent experimental set-up
and analyzed material a new series of measurements on a set of standards
with similar composition, which is not always so easy to accomplish. On
the other hand, the modern and advanced softwares allow to manage the
numerous parameters to perform the FP method. It consists of mathemati-
cal calculations based on the theoretical expression relating the fluorescence
intensity to all these features, derived by De Boer [3] for both homogeneous
and multilayered materials. By this way, the composition and thickness of
all the layers comprised in the analyzed volume can be obtained [4].

1.4.1 The Fundamental Parameters (FP) method

Every radiation with an incident intensity I0 , when passing through an ob-
ject of finite thickness x, interacts with the matter and consequently under-
goes to an attenuation defined by Lambert-Beer law:

µ(E)⇢x
I(E) = I0 (E)e (1.5)
where ⇢ is the sample density and µ(E) its overall mass attenuation
coefficient depending on the incident energy. If the matrix is heterogeneous,
the resulting µ(E) is given by the sum of the µi (E) of each element i weighted
for its mass fraction Wi .

18
 In order to determine the primary fluorescence intensity produced, both
the incident beam intensity exciting it and the successive interactions be-
tween the sample and the detector have to be taken into account (Fig. 1.16).

Figure 1.16 Geometry of an XRF system.

The intensity of the primary beam impinging on the sample surface with
an angle 1 and in an energy range E0 + dE0 depends on the flux emitted
by the source in a solid angle ⌦1 . Before arriving to a certain deep x where
the fluorescence radiation is excited, this primary beam undergoes to the so-
called primary attenuation phenomenon along its path xcsc( 1 ) inside the
sample. Therefore, the e↵ective primary beam intensity which will induce
fluorescence in the volume dx is:

µ(E0 )⇢xcsc( 1)
I1 = I0 (E)dE0 d⌦1 e (1.6)
Then, the intensity of a single fluorescence line f produced in the volume
dxcsc( 1 ) and emitted with a solid angle of 4⇡ by the element i is:

I2 = I1 dxcsc( 1 )Qif (E0 ) (1.7)

where Qif (E0 ) includes all the fundamental parameters associated to
that element specific X-radiation, such as its weighting factor, the mass
attenuation coefficient, the relative fluorescence yield and the fraction f of
that fluorescence line (e.g. K↵ ) with respect to all the element shell lines.
This radiation itself, before outgoing from the sample along the path
xcsc( 2 ), undergoes to the so-called secondary attenuation phenomenon,
and the intensity registered by the detector depends also on its efficiency:

d⌦2 µ(Ei )⇢xcsc( 2 )

I(dxdE0 ) = I2 e ⌘(Ei ) (1.8)
4⇡
In order to calculate the intensity excited by a polychromatic primary
radiation and emitted from the overall sample thickness included in the an-
alyzed volume, the equation has to be integrated for both the thickness

19
and the energy values. The energy range is comprised between the absorp-
tion edge of the fluorescence line under consideration and the primary beam
maximum energy:

Z Emax
⌘(Ei ) 1 e⇢T [µ(E0 )csc( 1 )+µ(Ei )csc( 2 )]
Ii (Ei ) = Qif (E0 )I0 (E0 )dE0
4⇡sin( 1 )E0 = K µ(E0 )csc( 1 ) + µ(Ei )csc( 2 )
(1.9)
If a sample has an attenuation µ(Ei )x >> 1 for an energy line Ei , it
is considered to have an “infinite” thickness for that energy. This means
that the sample is emitting its maximum intensity for that line. The critical
thickness T99% emits the 99% of the intensity emitted by an infinite thick-
ness, and it is sufficient to consider a sample having infinite thickness. In
this case, the exponential term of the last equation disappears.
The fluorescence radiation absorbed by the matrix does not just disap-
pear, but among the other e↵ects, it can excite other elements present in
the matrix. This phenomenon is knows as secondary fluorescence and usu-
ally happens between two elements of similar Z, because the higher energy
element (h) has an energy very close to the absorption edge of the lower one
(l) (Fig. 1.17). This fact leads to an overestimation of the concentration
of l and an underestimation of h. Some theoretical estimations for the re-
lation between secondary fluorescence e↵ect and sample thickness, at least
for monochromatic sources, are available in literature [5, 6].

Figure 1.17 Left: scheme of the fluorescence e↵ect, where the fluorescence from
Ni excites both Fe and Cr. Right: XRF spectra of a steel alloy, in which the
proximity between the fluorescence peaks and the absorption edges of the elements
is highlighted.

Looking at these equations, is is clear that the matrix e↵ects on the

secondary attenuation are very important, therefore if it is not possible to
determine its composition (as for the dark matrix issue) the quantitative
analysis becomes much more complicated.
As already explained before, the ratios between the fluorescence lines of
an element are fixed and known in literature. But such values can change
because of five di↵erent e↵ects. The first one is the above-mentioned sec-
ondary fluorescence e↵ect, due both to photoelectrons and Auger electrons

20
excitation. The second can be classified as a particular case of secondary
fluorescence which can be called self-excitation (or self-attenuation): for the
same elements, the lines of the group with higher energy excite the others
(e.g. the K-lines excite the L-lines) or even those from the same shell (e.g.
the L excites L↵ ). The third is a cascade e↵ect originated by an electronic
jump, for example from L to K resulting in a vacancy in the L shell that
leads to other electronic transactions from the outer shells, increasing the
intensityt of the lower energy lines. The forth one is due to the scattering
of both the primary and fluorescence radiation, and its contribute is impor-
tant in particular for light matrices (such as glass). Finally, in multilayered
objects this ratio changes in relation with the di↵erential absorption in the
upper layers [7, 8, 9] (section 1.4.2).

1.4.2 PyMCA software

PyMCA (Python MultiChannel Analyzer) code [10] is one of the most widely
used software based on the FP method. It has been developed starting from
a code working with the Levenberg-Marquardt [11, 12] algorithm at ESRF
(European Synchrotron Radiation Facility). It has a GUI to insert all the
experimental parameters required for the data analysis and the attenuation
corrections. It can handle many variables, describing the primary beam,
the geometry of the set up, the various absorbers between the sample and
the detector (such as air, Be window etc.), the detector parameters, and a
first approximation of the matrix composition to be analyzed. In the matrix
description also a multilayer object can be defined.
The background of the XRF spectrum can be modeled in two di↵erent
ways. PyMCA can operate iteratively before fitting the data by comparing
the counts of each channel with the next one’s and taking the average value.
Otherwise, the background can be described as a polynomial element, x =
(E Emean ) or x = exp(E Emean ), and included in the least squares fit of
the peaks, where Emean is given by the fit of each peak. In general PyMCA
fits the peaks as gaussian curves, however it is possible to choose also other
models (short tail, long tail, step tail and hypermet).
The sum peaks are individuated by checking the contribute of every
channel i to the counts of the channel corresponding to its double value.
The code makes a first approximation of the peak shape according to its
maximum position x0 (in terms of energies) and width s (s = F W HM/2.3548).
Then, it proceeds via iteration with the linear method of the least squares.
The function used to fit the fluorescence gaussian peak is
E(i))2
GAIN [ (Ej
]
G(i, Ej ) = p e 2s2 (1.10)
s 2⇡
where GAIN converts the channels into energy values. For a further
simplification, the user can choose to consider the overall area A of the

21
fluorescence lines group of an element instead of fitting each line separately,
by taking into account the relative intensity fj of each line. The theoretical
values of fj are corrected for the various attenuation e↵ects (by menas of the
overall element TA (Ej )), the fluorescence yield and the detector efficiency,
as follows:

!j Pj (E0 )fj TA (Ej )⌘(Ej )

fj0 = (1 e⇢x(µT (E0 )csc( 1 )+µT (Ej )csc( 2 )
) (1.11)
µT (E0 ) + µT (Ej ) sin(
sin(
1)
2)

where Pj is directly proportional to the photoelectric cross-section for the

energy of the lines group j, and µT is the total mass attenuation coefficient.
If dealing with a polychromatic source, the equation must be adapted for a
set of discretized and weighted energies. PyMCA can simulate the primary
beam by defining the type of source (anode, voltage, current etc.), otherwise
the user can manually insert a set of energies directly measured.
PyMCA is useful also for what regards XRF spectra simulation. Starting
from the parameters inserted in the configuration file, it can build up a
theoretical matrix spectrum, which can be compared to the experimental
one in order to estimate the reliability of our assumptions.
The matrix composition is iteratively corrected until the sum of the
squared di↵erences between the fitted and experimental areas is less than
0.1%. The procedure starts by inserting a simple matrix in the configuration
window, based on a first qualitative analysis. If PyMCA is not able to
iteratively adjust the composition, the matrix must be corrected manually.
By the Advanced Fitting interface of PyMCA, the user open the Config-
uration window where he can define, in many tabs, the various parameters.
In the FIT tab it is possible to set the fitting function (Mca Hypermet or Mca
Pseudo-Void), the background algorithm, the region to fit, and the extra-
fluorescence peaks (escape, pile-up, scattering etc.) to be considered, while
the peak shapes options are defined in the PEAK SHAPE tab. The DETEC-
TOR tab includes the spectrometer zero, gain, noise, Fano factor, pile-up
factor, and the detector crystal type. In the BEAM tab the source param-
eters are inserted, by producing or inserting the primary beam weighted
energies. In the PEAKS tab it is possible to select, for each element, the
fluorescence lines to fit. In the ATTENUATORS tab components such as
the beamfilter, the detector window, the atmosphere, and also the sample
matrix are described by composition, density and thickness (Fig. 1.18). In
the MATRIX tab the incoming and outcoming angles are defined.
As already mentioned, PyMCA can handle also a multilayered matrix.
It is possible to select up to 10 layers in the MATRIX tab, and for each one to
define a di↵erent composition, density and thickness (Fig. 1.19). However
this procedure implies some unavoidable simplifications, such as considering
the matrix made of well separated layers.

22
 Figure 1.18 PyMCA ATTENUATORS window.

Figure 1.19 PyMCA MATRIX window.

In addition, the quantitative analysis does not work for those elements

23
present in more than one layer, because the code cannot distinguish the
same signal coming from di↵erent layers. As a results, its concentration in
each layer would be estimated as if the fluorescence signal comes entirely
from that layer.
The CONCENTRATIONS tab is essentially deputed to define the incident
flux and the quantification method to use. The incident beam flux is one the
fundamental parameters as the fluorescence line intensities are linearly pro-
portional to its value. This parameter is usually only approximately known,
and this fact can lead to an error propagation into the results. However,
there are some empirical ways to estimate it. If the Rayleigh scattering peak
is present in the experimental spectrum and PyMCA fits it, the simulated
matrix spectrum can be used to adjust the flux value until the simulated
Rayleigh peak intensity equals the measured one. However this method is
limited to the cases in which high excitation energies (and relatively effi-
cient detectors) are used. An alternative way consists in registering, during
a measurement run, a spectrum of a standard reference material. Then it is
possible to correct the flux both by comparing the simulated matrix spec-
trum with the experimental one or the obtained elements mass fractions
with the nominal values.

Coating thickness estimation

It is widely known that a non-destructive analysis is usually the ideal and
most appreciate approach to investigate many kind of materials, such as
in the field of cultural heritage. This point of view is important for the
preservation of the integrity of such unique objects and also for a potentially
infinite repeatability of the measurements. However this kind of analysis are
usually not sufficient to provide a comprehensive set of information on the
artifact, and bulk analysis as well as cross-sections sampling can be required.
A typical case when sampling is required is the study of the stratigraphic
distribution of the constitutive elements in a multilayered material, such as
in paintings and decorated metals. Many studies have been carried out on
the possibility of using non-invasive techniques to obtain at least a partial
stratigraphic information. Several methods have been proposed for this
purpose, relying on the selection of the investigated layer (e.g., confocal X-
ray fluorescence and laser induced breakdown spectroscopy LIBS [13, 14, 15,
16, 17]) or the unfold of the overall signal with respect to the contribution of
the single layers (e.g., particle induced X-ray emission PIXE and Rutherford
backscattering spectroscopy RBS [18, 19, 20, 21]).
Also XRF based on the FP approximation has been successfully applied
in this kind of analysis for both paintings [7, 22] and gilded metals [23], with
the advantage of portability.
At present, all the methods proposed to measure the coating thickness
tc via XRF rely on attenuation e↵ects and their energy dependence. The

24
Figure 1.20 Example of the attenuation of the substrate Ag K-lines from the gold
coating increasing thickness.

most sensitive approach is to measure the attenuation of a single line from

an element in the substrate (Fig. 1.20). This approach requires that at least
a portion of the substrate is exposed in order to measure the unattenuated
intensity. This condition is not always available, and an eventual abrasion
of the surface could not always be allowed by the restorer.
A preferable approach consists in measuring the ratio between two lines
of the same element [24, 25, 26, 27]. Cesareo et al. [8, 28] showed that the
ratio of the K-lines intensities from an element in the substrate depends on
tc :

IK↵ IK↵ ((µc (EK↵ ) µc (EK ))⇢c tc )

=( )t exp (1.12)
IK IK inf inite
A third method, described in [9], relies on the FP method and the itera-
tive application of PyMCA fit. Given a two-layered structure and assigned
a tc value, PyMCA calculates the composition of both the substrate and the
coating. This also involves to calculate the ratio IK↵ /IK corresponding to
the assigned tc . In real samples tc is unknown, so that one has to input a
first abritrary value and check its adequacy through the chi-square between
the simulated and the experimental spectrum in the K-lines of the substrate
element. The actual value t = tc is the one that minimizes 2 (t) (Fig.
1.21). However, when applied through PyMCA, this procedure is quite time
consuming.
A more rapid approach consists in fitting the K↵i and K i lines of
a substrate element i independently and deriving the corresponding mass
fractions CK↵i (t) and CK i (t). In general these values will di↵er from
each other, due to the fact that the experimental relative intensities of the
K↵i and K i lines are not what PyMCA expects for the assigned value
of t: therefore it calculates di↵erent mass fractions to fit the experimental
spectrum. For t = tc the two mass fractions equal to each other because
the experimental relative intensities equal the expected ones. Basically, the

25
 2
Figure 1.21 Trend of the for a selected fluorescence line, where x is the coating
estimated thickness.

Figure 1.22 Trend of an element mass fraction calculated separately on its two
K-lines, where x is the coating estimated thickness.

method to derive tc consists in verifying the condition (Fig. 1.22)

CK↵i (t) = CK i (t) (1.13)

This method was tested for silver substrates, with gilding and glass (for
enamels) coatings [9]. The Ag K-lines were chosen as reference, thanks to
an experimental portable system able to efficiently excite their fluorescence
(60 kV, 1.5 mA). In the gilding case, for a coating thickness ranging from
1.97 to 7.3 µm a relative error of ⇠ 5% was found.
For the glass coatings, a significant systematic deviation of the measured
thickness from the nominal one was found (Fig. 1.23). The negative inter-
cept also involves negative thicknesses, which is apparently meaningless from
a physical point of view. Such a behaviour is not completely clear: it can be
possibly related to Compton scattering in the coating, that is not negligible
at the relatively high energy of the exciting radiation. The e↵ect is a more
superficial excitation in the substrate and a K↵/K ratio higher than that
for its infinite thickness [29]. This causes an underestimation of the coating
thickness that increases with the thickness of the scattering medium, i.e. the
coating itself. Such an e↵ect is apparent for glass coatings, characterized by
low Z and high incoherent scattering cross-section, whereas it is negligible
on gold coatings, with high Z and low incoherent scattering cross-section.
On the other side, also a bad approximation of the glass matrix, due e.g. to

26
Figure 1.23 Left: experimental results for the gilding thickness. Right: glass
thickness experimentally determined by the proposed method versus the nominal
values, and a scheme of the possible Compton scattering influence on the coating
thickness determination.

unconsidered secondary fluorescence e↵ects, would limit the quantification

accuracy. An underestimation of the glass thickness would increase the er-
rors in the quantitative analysis, a↵ected also by the difficulty in detecting
light elements. The latest PyMCA version has been implemented in order to
consider secondary fluorescence phenomena and has a Monte Carlo simula-
tion plug-in from XMI-MSIM code, in order to take into account scattering
e↵ects too.

Monte Carlo simulation, XMI-MSIM

Monte Carlo code refers to a series of computational algorithms working
with reiterated random samplings in order to obtain numerical results. It
can be used to simulate the fraction of every event involved in some kind
of phenomenon, or for example the trajectory of photons and/or particles
inside the matter.
Monte Carlo simulation can be applied to model a wide range of phenom-
ena, therefore it is very useful in the interpretation of di↵erent analytical
results. Among its applications, it has been employed in the modeling of
the various e↵ects involved in the XRF spectrometry. The various code
actually available are able to consider almost all the physical phenomena
occurring along the trajectories of the X-ray photons (photoelectric e↵ect,
secondary excitation, matrix e↵ects, Auger electron, M-lines, cascade ef-
fect, etc.). They can simulate the various aspects of the measurement, such
as the spectral response of the detector and the photon-matter interactions,
and take into account divergent polychromatic primary beams, enhancement
e↵ects due to scattering interactions, non-homogeneous or multilayered ma-
trices.
XMI-MSIM is one of the many open-source Monte Carlo packages now

27
 Figure 1.24 XMI-MSIM and PyMCA flow-chart [32].

available [30]. It simulates the story of every individual photon starting

from where it impinges the sample (taking into account the incident beam
parameters) until where it is totally absorbed or emerges from the matter
and is eventually detected. The trajectory of each photon is modeled as a
series of straight steps, each one ending with an interaction (photoelectric
e↵ect, coherent and incoherent scattering) with the matter. After every
event the code changes the energy and direction of the photon accordingly to
the type of interaction. The atom interacting with the photon, the distance
between two successive events and their type are randomly selected by the
code, by mean of a Mersenne twister random number generator [31].
A plug-in of XMI-MSIM has been included in the PyMCA package [32],
in order to provide an additional tool to the basic FP method for the quan-
titative analysis. The Monte Carlo code provides corrections coefficient for
a better fit of the experimental data, unlike in its usual employment when
it predicts theoretical XRF spectra. The reliability of this quantification
procedure has been validated by the software developers (Schoonjans et al.)
by collecting experimental spectra for various reference materials.
With this plug-ing, PyMCA firstly performs its usual fitting procedure,
then the generated file is integrated with further informations required by
the Monte Carlo routine and inserted by the user in the proper additional
tag of PyMCA configuration window. These additional parameters include
the degree of linear polarization, beam size and profile, source to sample
distance. This file is processed by the plug-in.

28
 First of all, the code selects the elements quantifiable according to some
criteria. The intensity of the alpha lines of an element (K or L) must be
positive and, still, the element can not be present in more than one layer
of a multilayered sample. Then, XMI-MSIM simulates a first spectrum and
the net-line intensities of the di↵erent elemental lines, which are used to
adjust the elemental weight fractions estimated by PyMCA. This procedure
proceeds iteratively by using this estimation as new inputs for the next
Monte Carlo simulation until a convergence is reached (e.g. the intensity
deviations is less 0.1%). By performing an early PyMCA estimation it is
possible to reduce the number of iteration and to start with a more realistic
initial model of the matrix instead of arbitrary values. Clearly the goodness
of the quantification strongly depends on the quality of the fit, helped by
the first PyMCA fit providing more reliable starting parameters.

1.5 Principles of radiation protection

Working with X-rays requires particular attentions and is clearly regulated
by the law and the radio-safety discipline. X-rays are among the so-called
ionizing radiations, which are characterized by an energy sufficient to induce
alteration and damages to biological cells. All this aspect are regulated by
the national D. Lgs. 230/95, dedicated to the safeguard of workers and
public.
Cellular changes take place only if the radiation releases some energy in
the material, in this case in biological tissues. The damage entity is related
to how much energy has been absorbed by a mass unity, indicated as the
absorbed dose D and measured in gray (1 Gy = 1 J/kg). In addition to D,
the radiation risk is proportionally related also to the radiation type and
the radio-sensitivity of the tissues and organs involved, which influence the
equivalent dose absorbed by a tissue (HT ). The most important parameter
to bePconsidered for the damaging stochastic e↵ects is the e↵ective dose
E = T wT HT received in a time unit (µSv/s), weighted for every tissue.
The ICRP (International Commission on Radiological Protection) has
based the radiological protection system on three fundamental principles:
motivation of the practice, protection optimization, and limitation of the
individual dose. Particular attention is dedicated to the ALARA (As Low As
Reasonably Achievable) principle: limits for the exposition and the e↵ective
dose are established both for unexposed workers/public (1 mSv/year) and
exposed workers (20 mSv/year).
The working condition must be controlled by a qualified expert. In
the case of XRF devices, the laboratory set up should operates in properly
shielded boxes. The shielding material and thickness are chosen according
to their transmission for the radiation energy considered. For what regards
the portable instruments for in situ analysis,they are open device and there-

29
fore, although the X-ray source is shielded, the scattered and fluorescence
radiation have to be taken into account. In this case, a controlled area
(usually in the order of 1-3 m of diameter) that can not be accessed during
the acquisition has to be delimited. This aspect must be considered in the
planning of every in situ campaign in a public place (e.g. museums).

30
2

Micro X-ray Fluorescence

Spectrometry

Conventional XRF systems provide a primary beam spot size quite extended
(⇠ 1 mm2 ), which is very useful in the analysis of bulk and homogeneous
materials. However, it can happen to have to deal with heterogeneous ob-
jects too. This is particularly common in the cultural heritage field, where
archaeological objects with deteriorated surfaces (and with only very small
original parts exposed) or finely detailed artifacts (paintings, enamels, illu-
minated manuscripts, etc.) are abundant (Fig. 4). In such cases, close areas
(< 500 µm) of di↵erent composition result comprised in the same analytical
volume, leading to some complication in the quantitative interpretation of
the data. This situation has lead to an increasing demand for high spa-
tial resolution systems, meaning µXRF spectrometers working in punctual
and/or scanning mode, without losing the features of non-destructivity and
portability.

Figure 2.1 Pictures of some cultural objects requiring a high spatial resolution
analysis: an enamelled silver -plate, an heterogeneously degraded coin, and a minia-
ture book.

31
2.1 X-ray optics
To understand the issues related to X-ray transmission and focusing, it is
mandatory to introduce some principles of X-ray optics. When a whatever
radiation travels from a medium to another with di↵erent refraction index
n is split in two components (Fig. 2.2). One is specularly reflected by the
interface while the other propagates in the second material with an angle
according to n2, as the Snell’s law states:

n1sin✓1 = n2sin✓2 (2.1)

If the first medium is optically denser than the second (n2 < n1), then
the angle ✓2 between the beam and the surface normal will be greater than
the incident angle ✓1. As shown in Fig. 2.2, if the incident angle if small
enough, total reflection takes place in the first medium. This happens if the
incident angle is equal or lower than the critical angle ✓c :

✓c ⇡ (~!p )/E (2.2)

where E is the energy of the incident X photon, and !p the vibra-
tional frequency of the plasmons of the reflecting material (usually 30 eV
for glasses). A plasmon is an energetic quantum of the oscillations of the
electron plasma of a system.

Figure 2.2 Scheme of the reflection process.

For the visible light, the refraction index of the air is lower than the
glass one, therefore the radiation is reflected and propagates inside the glass
(optical fibers working principle). The situation is the opposite for X-rays:
the air is optically denser than the majority of the materials, according
to the following principle. The refraction index of a material is given by
p
n = ", where " indicates its dielectric constant:

32
 "=1 +i (2.3)
for X-rays we have , << 1 and " ⇡ 1, consequently also n is near the
unity value for every material except vacuum. This is why every material
has a low permittivity value (< 1) for X-rays, which are almost entirely
not absorbed. Only air has a high refraction index for X-rays, therefore an
external (being out of any material) total reflection (TER) takes place. The
TER ✓c is inversely proportional to the incident photon energy E, e.g the ✓c
for a borosilicate glass is

✓c (mrad) = 30KeV /E (2.4)

and only a little higher for leaded glass, however always very low (< 1 ).
This feature is usually achieved by employing a grazing incidence angle,
leading to very small angular apertures. This required parameter leads to
one of the main X-ray optics manufacturing issues, respect to those for
visible light and infrared, because is technologically complicated to obtain
systems ensuring such small incidence angles.
The first pioneering studies on the use of reflecting smooth surfaces for
X-rays beams manipulation and propagation were conducted by Laue [36]
and Compton [37]. Nowadays there are di↵erent types of configurations pro-
viding grazing incidence geometries. X-ray optical devices can be classified
in three main groups, based on the di↵erent working principle: reflective,
di↵ractive, and refractive optics.
The reflective optics, based on the TER phenomenon, have been the first
one to be employed. In 1948 Kirkpatrick and Baez [38] proposed a couple of
orthogonal curved mirrors (Fig. 2.3.a, presently widely used in synchrotron
facilities), while in 1952 Wolter [39] presented a combination of two tubular
rotationally symmetric mirrors (Fig. 2.3.b, employed in X-ray telescopes).
A perfect coincidence of the optical axis is mandatory in both cases, and a
nanometer focusing can be obtained in both dimensions. Another solution is
represented by planar waveguides [40], providing one-dimensional focusing
(Fig. 2.3.c). Two metal layers enclose a low absorbing material in which the
radiation propagates by TER and the layer thickness determines the beam
vertical size (down to 100 nm).
Fresnel zone plates (FZPs) are circular di↵raction plates working by
constructive interference. They are efficient especially for monochromatic
soft X-rays (spots down to 20 nm) [42].
In the compound refractive lenses (CRL) [41] a series of cylindrical holes
focuses the beam (Fig. 2.4). The matter portions comprised between the
empty spaces work like biconcave refractive lenses in sequence. They are
efficient for energies between 5 and 80 keV and can provide few microns
spots.

33
Figure 2.3 Working schemes of KB mirrors (a), Wolter mirrors (b), and waveguides
(c).

Figure 2.4 Working principles of Fresnel zone plates (left) and compound refractive
lenses (right) [43].

All these X-rays optics are characterized by very small apertures corre-
sponding to a strong reduction of the intensity radiation transmitted, there-
fore they can be efficiently employed only with very high brilliant sources,
as those available only at synchrotron facilities. Moreover, the majority of
them is characterized by big sizes and long working distances. All these
aspects limit their application for in situ analysis.

2.2 Polycapillary lenses

At the beginning of 80’s, Kumakhov proposed a new kind of compact re-
flective optics compatible also with conventional X-ray tubes, the so-called
capillary lenses [44, 45]. By employing properly curved surfaces it has been
possible to develop multiple reflections optics for a wide energy range able
to deflect the beam of a resulting angle much greater than the critical angle.
The simple principle of a TER from a planar surface has been applied to a
hollow straight channel along which a photon can travel by multiple reflec-
tions. The next crucial step was passing to a curved channel (Fig. 2.5.a),
under to the following condition:

34
Figure 2.5 a) Scheme of the TER phenomenon inside a single curved channel. b)
Capillaries with a barrel shape for focusing purposes.

R > d/✓c2 (2.5)

where R is the curvature radius of the channel and d the channel internal
diameter. The curvature radius R depends on the TER condition:

R  (d✓c2 )/2 (2.6)

where d is usually between 5-25 microns (4th generation lenses), very
much lower than the curvature radius (⇠ 500 mm), in order to maximize
the number of photons with an incident angle lower than the critical angle.
Optics based on a single reflection can deflect the beam for a maximum
angle of 2✓c , therefore they can focus only a very small angle of the primary
radiation. On the contrary, the multi-reflection capillaries, which are bun-
dles of many curved channels with smooth internal walls arranged in a barrel
shape (Fig. 2.5.b), allow collecting a great solid angle and focusing it into
a small spot size, for a wide energy range (useful for polychromatic beams).
The channels are arranged in layers, each one with a di↵erent curvature:
the central channels are almost straight while the curvature radius increases
towards the exterior, where the higher deflections takes place. Each layer
channels have a di↵erent inclination, in order to provide similar incident an-
gle conditions to all the incoming photons. Bundles of these glass capillaries
forms the so-called polycapillary optics/lenses (polyCO).
Polycapillary optics can be employed not only for focusing purposes,
but also to collimate a quasi-parallel beam from a divergent source, e.g. for
di↵raction or tomographic applications. The collimating lenses, called half-
lenses or semi-lenses, have a half-barrel shape and can operate also in the
opposite way (focusing a parallel beam).
The principal parameters of a focusing polyCO (full-lens): input focal
distance (IFD), output focal distance (OFD), focused spot size, working
energies, transmission and gain.
The IFD must be chosen by taking into account the source spot size and
the accessible distance, in order to provide the right incidence angle condi-
tions. The efficiency of a source-optics system is maximum if the input spot

35
Figure 2.6 Example of the focused spot size vs the energy, keeping constant the
other parameters (such as IFD and OFD).

size Si (a theoretical region indicating the X-ray area e↵ectively captured

by the optics) equals the source size and the lens is placed at the right IFD,
while for bigger sources part of the radiation gets lost as it is not included
in the captured solid angle. Si and IFD are related as follows [46]:

Si ⇡ 2IF D✓c + din (2.7)

where din is the channel internal diameter at the optics entrance. Com-
bining it with the critical angle equation, we have

Si (µm) ⇡ 60IF D(mm)/E(keV ) (2.8)

According to this relation, for higher energies the distance between
source and optics decreases.
The OFD depends on the focused spot size S, with relations similar to
Eqs. 2.7-2.8 (with dout at the optics exit), therefore it decreases for higher
energies.
From this equations it can be observed that working with high energies
implies some geometrical restrictions. Not all the X-sources allow working
with low IFD values, because the distance between the anode and the exit
window is too large (e.g. in the reflection mode tubes). Also low OFD values
implies operative problems, e.g. when performing a scanning of an not-flat
surface (tridimensional objects).
It is also evident that the spot size varies depends on the critical angle
and the photon energy, as shown in Fig. 2.6.
The spot size can also be experimentally determined, in two di↵erent
ways. The first is the so-called “knife method”: a very sharp edge (the
knife) is moved across the beam section starting by completely occluding
the beam (zero counts) until all the radiation passes (maximum count).

36
The spot size is given by the (FWHM) of the derivative of this scanned
profile (Fig. 2.7).

Figure 2.7 Illustration of the knife method results.

The second method, useful to determine both the OFD and the spot size,
consists in taking some CCD images at various distances from the lens (Fig.
2.8). The focus position corresponds to where the beam spot is smallest and
most intense.

Figure 2.8 Scheme of the OFD determination procedure.

Another important parameter is the transmission efficiency, which de-

pends also on the radiation energy. Every polycapillary lens, according to its
geometrical characteristics, is optimized for a di↵erent energy range. To ex-
perimental determine the transmission, two energy-resolved measures must
be taken, at the lens entrance and exit. Then, the ratio between the two
intensities, vs the energy, gives the transmission curve (Fig. 2.9).

37
Figure 2.9 Scheme of the Transmission determination procedure, and a generic
result showing the transmission curve.

The gain G in the radiation density can be theoretically estimated as

follows:

⌦2l
G= kT , (2.9)
⌦2p
where ⌦l is the solid angle collected by the lens, ⌦p is the solid angle
viewed in the spot s obtained with the pinhole at the same distance (L)
from the source, and kT is the polyCO transmission efficiency (Fig. 2.10).

Figure 2.10 Scheme of the Gain determination procedure.

The X-rays propagation through the polycapillary optics is the result

of the interactions between the radiation and the walls. Only part of the
beam propagates by reflection, while the rest travels by refraction through
the walls, contributing to the scattered radiation and to the halo e↵ect
surrounding the spot. The halo e↵ect consists of two components: the
“penetration halo” (for X-rays energies > 40 keV and too low ✓c , which

38
penetrate the matter and propagate through the wall), and the “escape
halo” (soft X-rays absorbed near the lens exit). Part of the halo e↵ect can
be reduced by operating at lower energies.
The alignment procedure between the polyCO and the X-ray source is
a very crucial step, not only to get the best radiation transmission, but for
the lens working itself. If the polyCO is wrongly aligned, the absence of
the grazing angle condition completely avoid the beam transmission. First
of all, the lens axis must be placed along the geometric line between the
source and the detector (usually a scintillator). Then, the lens entrance is
fixed by an holder and undergoes to a double angular scanning, while the
intensity of the transmitted radiation is registered by the detector. The
optimal placement is given by the higher intensity position (Fig. 2.11). The
entire procedure can be remotely operated.

Figure 2.11 Schematization of the alignment procedure and the resulting outputs.

Figure 2.12 Schematization of the IFD determination procedure.

39
 The polycapillary optics manufacturing process consists in heating and
stretching glass tubes in order to obtain small diameter channels (usually
around 1 mm). Then, they are put in bundles, heated and stretched again,
until the desired internal diameter and arrangement section are achieved.
Finally, the extremities are cut. The last technological advances allow pro-
ducing optics with a variable curvature, which increases the density flux
and reduces the spot size with respect to a constant one. The result is an
asymmetric lens.
In the last years, one of the major technical problems in manufacturing
grazing angle optical systems is the treatment of the surfaces, because of
the influence of the superficial roughness on the reflected beam. The general
rule states that for incident angles ✓ ⇠ ✓c (✓ << 1) the superficial roughness
must be lower than 10-50 Å, which is technologically challenging to achieve.
To solve this, the process relies on the internal channel walls strains of the
material to obtain vey smooth surfaces.

Figure 2.13 Images of the 1st (a), 4th (b) and 5th (c) lens generations.

Polycapillary optics are formed by 10.000 up to millions of hollow glass

channels, joint in bundles, with a diameter of 5-10 µm and a a resulting
section of 500 µm. The 1st generation of polycapillary lenses were bundles
of monocapillaries (Fig. 2.13 and Tab. 2.1). In the 2nd generation, they
evolved to their monolithic version, with the capillaries packed and fused
together. This solution allows have a d varying along the optics length,
optimizing the transmission efficiency by the TER conditions preservation.
Successively, instead of single capillaries this optics passes to a multifiber
system, in which every capillary fiber contains many channels. These repre-
sents the 3rd generation, and their monolithic version the 4th . They allowed
increasing the transmitted energy range. The last generation (5th ) is repre-
sented by monolithic polycapillaries micro-lenses, of smaller size and efficient
at higher energies.

40
 generation length channel diameter energy (keV)
1st 1 m 1 mm < 10
2nd 10-30 cm 0.1-1 mm < 10
3rd 10 cm 10-50 µm < 20
4th 4-10 cm 1-10 µm < 50
5th 1-3 cm 0.3-1 µm < 100

Table 2.1 Principal characteristics of the various polyCO generations.

2.3 µXRF for cultural heritage: state of the art

Actually, the best µXRF performances can be achieved at Synchrotron Ra-
diation structures, where optics like KB mirrors coupled with high intensity
beams provide very high spatial resolution (down to the nanoscale). Al-
most every SR facility in the world is equipped with at least one beamline
dedicated to XRF microscopy (Fig. 2.14), where some times also polyCO
are employed. SR microprobe provides a significantly higher sensitivity and
lower LOD (< tens of ppm) with respect to other micro-XRF devices. How-
ever, in the cultural heritage field, SR has the main disadvantage on being
incompatible with the request for in situ analysis, and however, also when it
is possible to bring the sample or the object to the beamline, the application
for SR beamtime is a quite expensive and long-time consuming procedure
with respect to that for a classical diagnostic laboratory. Therefore, µXRF
instruments realized with conventional X-ray tubes, both in the portable
and laboratory versions, are strongly preferred for this application field.
Another important aspect to consider when planning a µXRF campaign
in this field is the measuring time. When working in archaeological sites
and museums it is important to be able to carry out many measurements in
a few days, even in a few hours. As simple collimators as pinholes strongly
reduces the flux beams, their use leads to longer acquisition times. On
the contrary, polycapillary optics focuses much higher intensities, allowing
shorter measurement times.
In the last years there have been some attempts to realize customized
µXRF spectrometers combined with polyCO.
Cheng et al. [48] developed a laboratory µXRF device for archaeological
applications. They used a rotating Mo anode tube from Rigaku, producing
a more intense beam, coupled with a polycapillary optics (manufactured by
their research groups led by Prof. X. L. Ding, BNU). The polyCO param-
eters are: spot size ⇠ 65 µm, IFD 61.6 mm, OFD 18.7 mm, length 68 mm,
and for the Mo K↵-line (17 keV) a transmission efficiency of 3.8% and a gain
of 1560. A Si-PIN detector is used, and the entire system is equipped with
a xyz sample stage for scanning analysis. The polyCO distorts the primary
spectrum towards lower energies (5-10 keV) and it is cut o↵ over the 17 keV
(Fig. 2.14), therefore it is not suitable for the detection of medium/high Z
elements.

41
Figure 2.14 Left: example of a µXRF beamline (I08 at Diamond Light Source
[47]). Right: The excitation spectra of Cheng et al. system, focused by the polyCO
and registered after being scattered by a glass matrix (1 min counting time, tube
set at 35 kV and 10 mA).

Figure 2.15 Buzanich et al. spectrometer.

Buzanich et al. [49] designed and developed a portable µXRF spectrom-

eter equipped with a vacuum chamber for low-Z elements detection (Fig.
2.15). They employed a micro-focus Pd anode (L-lines) tube (50 kV, 1
mA). It has the possibility to switch the optical configuration, using alter-
natively a polycapillary optics from XOS (spot size 160 µm) or a pinhole
with a 0.7 mm diameter for a resulting spot size of 1 mm. It is particularly
efficient in detecting light elements (Na, Mg, Si, etc.) but for energies start-
ing from the Pb-L lines the polyCO performance is worse than the pinhole
(Fig. 2.16), losing the advantage of working with a 50 kV source.
Also some commercial µXRF spectrometer polyCO based are available.
For example, Bruker, one of the leader companies in spectrometry instru-
mentations, o↵ers di↵erent products: a laboratory µXRF scanner for small
samples (M4 TORNADO), a portable µXRF spectrometer for punctual anal-
ysis (ARTAX), and its latest upgraded version for 2D scanning (M6 JET-
STREAM). M4TORNADO has a sample chamber with 60 x 35 x 26 cm of
size, a tube working at 50 kV and a spot size < 25 µm. It is very highly
performing for the elemental mapping on the microscale, but it is limited

42
Figure 2.16 XRF spectra, for a metal alloy, obtained in vacuum with both the
pinhole and the polyCO, by the Buzanich et al. spectrometer.

Figure 2.17 ARTAX micro-XRF spectrometer.

to the analysis of very small samples and cross sections. ARTAX [50] char-
acteristics make it the a suitable example (Fig. 2.17) of what we want to
realize in this project, possibly with some improved performances (e.g. in
the energy range). It is portable, compatible with the analysis of big and
not-flat objects, equipped with exchangeable tubes (di↵erent anodes) with
50 kV and 600 µA, and a polyCO focusing a beam down to 70 µm. It works
in a nominal energy range, for K-lines, between Ti (4.5 keV) and Sb (26
keV), and the detection limits are of the order of tens-hundreds of ppm. It
is also equipped with an helium flux to provide detection of light elements
(nominally down to Al and even Na).

43
3

Configuration and test of the

latest PyMCA version

In this section, an evaluating study of the latest PyMCA version (5.1.n)

is carried out. Both the XMI-MSIM plug-in (for Monte Carlo simulation
about the scattering e↵ects) and the new PyMCA flag for secondary excita-
tion consideration are tested, in order to provide some useful performance
feedbacks to the code developers as part of a collaborating user community.
The XMI-MSIM plug-in has been tested only for homogeneous matrices
(metals and glasses), as it is not implemented yet for multilayered samples.
Considering the time required for every simulation, further tests regarded
the stand-alone PyMCA secondary fluorescence option, working also with
multilayer matrices, although without the Compton scattering considera-
tion. If the latter option gives results analytically reliable, it would be the
best option not only for the data treatment of cultural objects, but also for
other application, e.g. fast quality control of industrial coatings.

3.1 Experimental set up

XRF spectra were collected for metal (silver alloy and bronze alloys, Tabs.
3.3-3.2) and glass matrices (Tab. 3.5). Stainless steel samples (Tab. 3.3)
were analyzed, in order to consider the method for industrial application,
and because they represent a proper case study for secondary fluorescence
influence. Also some multilayered samples, PVD coatings on stainless steel
(Tab. 3.4, Figs. 3.1-3.2), were investigated in order to evaluate the method
both for a substrate subject to secondary fluorescence e↵ects and for coat-
ing thickness determination. Molybdenum coatings are usually applied to
improve the corrosion resistance of the material, while a layer of TiN is used
to harden and protect cutting and sliding surfaces, for decoration (having
a gold appearance) and as a non-toxic interface for medical implants. It
is sometimes applied to a softer Ti layer to avoid crack propagation and

44
increase the coating toughness ([51]). The XRF measurements were carried
out at ITABC - CNR. The X-ray source is a W anode tube, working at 60
kV and 1.5 mA, with a spot size of 1.7 mm. Two similar SDD detector with
an energy resolution of 173 eV at 5.9 keV were used, for an acquisition time
of 120 sand an active area of 10 mm2 on the silver alloys, while for the bronze
the one with 30 mm2 was used. For the analysis of silver alloys, stainless
steel and the multilayered samples, the detector with an active area of 10
mm2 was used, a nd for the rest one with a 30 mm2 active area. This di↵er-
ence is due only to detector availability reasons. For every standard, a set of
5 XRF spectra was collected, for statistic significance, except for the three
homogeneous steel samples (being considered like one standard, as they have
comparable compositions) for which only two spectra were collected.
Id Cu wt% Au wt% Ag wt%
ICR1 2 0 98
ICR2 6 0 94
ICR4 2 2 96
ICR5 2 6 92
ICR6 6 2 92
ICR7 6 6 88
ICR8 10 2 88
ICR9 10 6 84
INFN1 2 0 98
INFN2 4 0 96
INFN3 10 0 90
INFN4 15 0 85
INFN5 12 2 86
INFN6 9 4 87
INFN7 5 6 89
INFN8 3 10 87
INFN9 1 1 98
INFN10 0 8 92

Table 3.1 Nominal composition of the standard silver alloys.

Id Si wt% P wt% Fe wt% Ni wt% Cu wt% Zn wt% Sn wt% Pb wt%

SS551 0.018 1.01 0.2 0.76 87.4 0.74 8.92 0.7
SS552 0.019 0.77 0.1 0.56 87.7 0.35 9.78 0.63
SS553 0.022 0.68 0.056 0.44 87 0.49 10.8 0.47
SS555 0.005 0.18 0.01 0.11 87.1 0.09 12.1 0.24
SS556 0.005 0.1 0.004 0.014 86.4 0.09 13.2 0.16

Table 3.2 Nominal composition of the standard bronze alloys.

Id C wt% Mn wt% Si wt% Cr wt% Ni wt% Mo wt% V wt% Fe wt%

Std002 0.04 1.78 0.67 18.5 8.6 0.53 0.08 69.8
Std37 0.04 1.43 0.48 18.2 8.6 0.21 0.06 70.98
Std303 0.04 1.85 0.59 19.1 9.00 0.54 0.07 68.81

Table 3.3 Nominal composition of the stainless steel alloys.

45
 StdMo StdTiTiN
Cr wt% 17.54 17.74
Fe wt% 69.5 68.88
Ni wt% 7.62 7.63
coating thickness (µm) 2.332 2.442

Table 3.4 Composition and coating thickness of the standard steel coated by Mo
(stdMo) and TiTiN (stdTiTiN), determined by the SEM and EDS analysis.

wt% lead glass BRC3 fluxana

K 8.301 5.728 4.15
Ca 0.739 0.021 3.57
Ti - 0.06 3.06
V - 0.146 0.28
Cr - - 0.34
Mn - 0.364 0.39
Fe 0.0039 3.777 0.35
Co - - 0.37
Ni - 0.228 0.39
Cu - - 0.44
Zn 0.820 - 0.80
Ge - 0.243 -
As - 0.591 0.151
Se - - 0.213
Sr - - 0.85
Y - - 0.23
Zr - - 0.37
Nb - 0.42 0.35
Mo - 1.895 0.40
Cd - 0.14 0.438
Sn - - 0.394
Sb 0.243 - 0.167
Ba 0.829 0.896 1.164
La - - 0.427
Hf - - 0.424
Ta - - 0.41
W - 0.875 -
Pb 22.29 - 1.860
Bi - 0.476 -
Ce - - 0.408
Pr - 0.186 0.249
Nd - 0.395 0.257
Sm - - 0.237
Gd - - 0.239
Dy - - 0.262
Er - - 0.263
Yb - - 0.244

Table 3.5 Nominal composition of the glass standards.

Figure 3.1 a) SEM image and b) overlay of the elemental maps for the stdMo.

46
 Figure 3.2 a) SEM image and b) overlay of the elemental maps for the stdMo.

3.2 Experimental results

3.2.1 Homogeneous matrices
Silver alloys
In silver alloys the secondary fluorescence e↵ects were found to be quite
important: Ag K-lines excite Au L-lines, which successively excite Cu K-
lines, Fig. 3.3). In particular, the Monte Carlo plug-in calculates excitation
factors for the correction of Cu and Au mass fractions of the order of ⇠
2.7 (Tab. 3.6). Although the simple PyMCA provides good results on Cu
and Au, it strongly underestimates the Ag mass fraction, as the major con-
stituent element, which has to be derived by further relative calculations
substraction the other elements’s amounts. With the Monte Carlo simula-
tion, the relative error on both copper and gold is halved, and even for the
silver quantification the result is improved (Fig. 3.4, Tab. 3.11) with respect
to the old PyMCA version.

Figure 3.3 XRF spectrum of a silver alloy, where the fluorescence peaks and the
absorption lines for the principal constituent elements are indicated. The Zr signal
is due to the detector collimator. The intensity is in log scale.

47
 fluorescence line excitation factor
Ag Ka 1.018
Ag Kb 1.020
Ag L1 1.739
Ag L2 1.161
Ag L3 1.214
Au L1 2.393
Au L2 2.961
Au L3 2.798
Cu Ka 2.795
Cu Kb 2.861

Table 3.6 The excitation factor calculated by the Monte Carlo plug-in to correct
the PyMCA data for the silver alloys.

Figure 3.4 Comparison between the Cu and Au calculated mass fractions and
their nominal values, for silver alloys, by means of the simple PyMCA (black) and
the Monte Carlo plug-in (red).

element err% (PyMCA) err% (MC)

Cu 27 15
Ag 51 12
Au 27 12

Table 3.7 Average relative error on majority elements of the standard silver alloys,
obtained with (MC) and without Monte Carlo (PyMCA).

Bronze alloys
In the copper/bronze alloys the contribution by the Monte Carlo plug-in is
less evident (Tab. 3.8), although we still have some secondary fluorescence
e↵ects: Sn K-lines excite Pb L-lines and Zn K-lines, while Cu K-lines excite
Ni and Fe K-lines (Fig. 3.5).
In particular, with the Monte Carlo simulation there is a reduction in the
relative error on lead and copper, the major constituent (as for Ag in silver
alloys), but on the other side the quantification on tin gets systematically a
little worse (Fig. 3.6 and Tab. 3.11) although still acceptable, with respect
to the old PyMCA version. The quantification on zinc, iron and nickel
is improved too, but not sufficiently (relative errors still over one hundred
percent), maybe due to bad detection limits or their very low amounts in
the matrix.

48
Figure 3.5 XRF spectrum of a bronze alloy, where the fluorescence peaks and the
absorption lines for the principal constituent elements are indicated. The Mo signal
is due to the detector collimator. The intensity is in log scale.

fluorescence line excitation factor

Cu Ka 1.0808
Cu Kb 1.0853
Pb L1 1.0404
Pb L2 1.0486
Pb L3 1.0453
Sn Ka 1.0241
Sn Kb 1.0273

Table 3.8 The excitation factor calculated by the Monte Carlo plug-in to correct
the PyMCA data for the bronze alloys.

Figure 3.6 Comparison between the Sn and Pb calculated mass fractions and their
nominal values, for bronze alloys, by means of the simple PyMCA (black) and the
Monte Carlo plug-in (red).

element err% (PyMCA) err% (MC)

Cu 33 14
Sn 2.4 4.2
Pb 24 8

Table 3.9 Average relative error on majority elements of the standard copper
alloys, obtained with (MC) and without Monte Carlo (PyMCA).

49
Stainless steel alloys
In the stainless steel alloys case secondary fluorescence e↵ects involve, in
particular, Cr, Fe and Ni K-lines, because of their energy proximity (Fig.
3.7 and Tab. 3.10). This time the Monte Carlo plug-in and the latest
version of PyMCA secondary fluorescence option were tested. In both cases
the relative error is strongly reduced (< 10%) on chromium, nichel and even
iron (the major constituent), in addition the stand alone PyMCA provides
better results also for the trace elements (manganese and molybdenum).
Considering these results, and the advantage of a faster processing respect
to the Monte Carlo plug-in (which when operating with not super-efficient
computers can take more than 15 minutes), the PyMCA stand-alone latest
version should be preferable, in particular when dealing with large sets of
data.

Figure 3.7 XRF spectrum of a stainless steel alloy, where the fluorescence peaks
and the absorption lines for the principal constituent elements are indicated. The
Zr signal is due to the detector collimator. The intensity is in log scale.

fluorescence line excitation factor

Cr Ka 1.876
Cr Kb 1.895
Mn Ka 1.176
Mn Kb 1.173
Fe Ka 1.072
Fe Kb 1.073
Ni Ka 1.031
Ni Kb 1.031
Mo Ka 1.028
Mo Kb 1.030

Table 3.10 The excitation factor calculated by the Monte Carlo plug-in to correct
the PyMCA data for the stainless steel alloys.

50
 element err% (PyMCA) err% (MC) err% (SE)
Mn 30.2 18.8 9.4
Cr 2.7 0.4 2.6
Ni 48.4 8.1 9.9
Mo 50.7 63.8 11.7
Fe 43.1 6.2 1.9

Table 3.11 Average relative error on majority elements of the stainless steel al-
loys, obtained with (MC) and without Monte Carlo (PyMCA), and with the latest
version of PyMCA including the secondary excitation e↵ects (SE).

Glass matrices
In the glass matrices, things become a little bit more complicated due to the
large amount of trace elements influencing each others (Fig. 3.8 and Tab.
3.12). Moreover, in such a light and amorphous matrix, also the scattering
e↵ects influence can be stronger (necessity of the Monte Carlo simultation).
The Monte Carlo plug-in calculated excitation factors (Tab. 3.12) indicate
that the lighter elements are more influenced by this secondary e↵ects.

Figure 3.8 XRF spectrum of one of the glass standards (BRC3), where the fluo-
rescence peaks and the absorption lines for the principal constituent elements are
indicated. The Zr signal comes from the detector internal collimator. The intensity
is in log scale.

In the lead glass case (Tab. 3.13), the three versions of the software
provide comparable results for the element Zn-Pb, but only the SE PyMCA
version gives acceptable results (relative errors < 5%) for K and Ca, which
are among the most important elements in the glass classification. In the
BRC3 standard (Tab. 3.14) the SE version still gives the best result for K,
but the Monte Carlo plug-in is better for Mn, Ni, As, Cd, Ba, Pr, Nd. For
the other elements, the results with the di↵erent versions are similar. In
the fluxana standard (Tab. 3.15) the results are not so good for some the
elments, in particular those with a high Z (starting frmo Cd) and present in
trace amounts: this could be due to poor detection limits of the system, but
also to the fact that such a huge amount of elements from the periodic table
could induce some calculation difficulties in the algorithm, as in some cases

51
the old PyMCA version provides the better results. However, for the other
elemnts, such as Ti, Zn, Cr, and Fe, there is a sort of balance between the
performances of MC and SE versions, and this time it is the Monte Carlo
plug-in to provide the lowest errors on K and Ca.
fluorescence line excitation factor
K Ka 1.3712
K Kb 1.3758
Ca Ka 1.3677
Ca Kb 1.3729
Mn Ka 1.3135
Mn Kb 1.3216
Fe Ka 1.3105
Fe Kb 1.3193
Ni Ka 1.3091
Ni Kb 1.3195
As Ka 1.2719
As Kb 1.2829
Bi L1 1.2083
Bi L2 1.2728
Bi L3 1.2566
Nb Ka 1.1781
Nb Kb 1.1910
Mo Ka 1.1656
Mo Kb 1.1767
Ba Ka 1.0974
Ba Kb 1.1035

Table 3.12 The excitation factors calculated by the Monte Carlo plug-in to correct
the PyMCA data for some of the BRC3 glass standard constituents.

element err% (PyMCA) err% (MC) err% (SE)

K -33.0 -33.8 -3.7
Ca -39.6 -42.2 -2.3
Zn 7.7 6.3 8.2
Sb 6.8 8.8 10.3
Ba 5.9 6.9 9.1
Pb 0.8 2.2 3.3

Table 3.13 Average relative error on the elements of the standard lead glass, ob-
tained with (MC) and without Monte Carlo (PyMCA), and with the latest version
of PyMCA including the secondary excitation e↵ects (SE).

element err% (PyMCA) err% (MC) err% (SE)

K -8.8 -19.8 5.9
Mn 23.1 6.1 31.6
Fe 10.5 -10.2 10.6
NI 27.6 7.2 30.8
As 24.9 4.6 29.5
Nb -3.6 -11.2 -4.4
Mo 24.5 17.9 22.6
Cd 7.1 0.5 3.8
Ba 13.8 1.2 3.3
Pr 16.5 3.6 17.1

Table 3.14 Average relative error on the elements of the standard BRC3 glass, ob-
tained with (MC) and without Monte Carlo (PyMCA), and with the latest version
of PyMCA including the secondary excitation e↵ects (SE).

At this point is has been demonstrated that both the Monte Carlo and
the SE version can improve the quantitative analysis of metal and glass
matrices (with the exception of the fluxana sample, where the situation is
quite complicated). Each software option presents its own advantages, but

52
 element err% (PyMCA) err% (MC) err% (SE)
K 40.2 9.5 34.8
Ca 22.9 2.2 12.4
Ti 18.2 3.7 5.0
V 23.3 0.3 62.1
Cr 35.1 46.9 17.7
Fe 12.1 8.4 2.6
Co 10.2 10.2 10.7
Cu 10.5 25.6 19.6
Ta 13.3 25.6 20.0
Zn 31.1 9.3 18.9
Pb 16.5 25.4 23.9
Sr 21.3 29.1 26.3
Mo 7.1 4.3 1.4
Cd 46.3 53.0 51.0
Sn 33.4 42.0 39.5
Sb 38.0 46.2 43.8
Ba 50.8 55.1 53.3
La 60.6 63.8 62.6
Ce 58.0 61.2 60.1
Pr 61.7 64.5 63.6
Nd 63.9 66.3 66.2
Sm 65.0 66.7 66.7
Gd 69.0 70.2 84.2

Table 3.15 Average relative error on the elements of the standard fluxana glass,
obtained with (MC) and without Monte Carlo (PyMCA), and with the latest ver-
sion of PyMCA including the secondary excitation e↵ects (SE).

due to the much longer times processing required by the Monte Carlo plug-
in (especially if not working with powerful computers), from now on we will
use only the SE PyMCA version, faster and with comparable performances,
which is more conveniente in particular when dealing with large amounts of
data.

3.2.2 Multilayer samples

PVD coatings on stainless steel alloys
First of all, some tests were carried out in order to establish the best parame-
ter to determine the coating thickness for this kind of substrate, according to
the procedure illustrated in section 1.4.2 (Eq. 1.13). Sets of 5 XRF spectra
were collected for both the samples. In particular, the method (CK↵=CK )
has been tested for the di↵erent susbtrate elements (Fe, Cr, and Ni) in order
to find the most sensitive to the coating thickness. For both the coatings,
iron provided the best results (Tab. 3.16-3.17), probably due to the fact
that it is the main matrix consistuent (as happens for Ag in silver alloys).
However, only for the Mo coating we have acceptable results (a relative error
not higher than 10%), while for the TiTin layer the method is not enough
sensititve. Probably this fact is related also to the very low absorption that
the Fe (and the other elements) fluorescence radiation undergoes along a
quite low density matrix.
Then, also another approach was tested: the PyMCA Matrix simulation
tool, in order to verify the reliability of a virtual calibration curve for the
auto-attenuation e↵ect. Sets of 10 XRF spectra, for both the coatings (Mo
and Ti), have been simulated for a thickness range between 1 and 10 µm,

53
 reference element mean coating thickness dev. st. err %
Fe 2.085 0.474 10.6
Cr 2.788 0.165 19.6
Ni 3.44 0.67 47.5

Table 3.16 Results obtained for the Mo coating.

reference element mean coating thickness dev. st. err %

Fe 3.34 0.631 36.8
Cr 3.89 1.699 59.3
Ni 3.926 2.537 60.8

Table 3.17 Results obtained for the TiTiN coating.

using for the substrate matrix a composition that includes also Mo traces.
Then, the simulated spectra have been fitted as the experimental ones, this
time to obtain the intensity area of the fluorescence peaks of interest. The
ratios between fluorescence lines of the same element form the coating have
been plotted versus the coating thickness, as the auto-attenuation a↵ects
in di↵erent ways fluorescence lines of di↵erent energies (the more energetic
ones are less attenuated). Once obtained this calibration curves, our experi-
mental spectra have been fitted, in order to determine the coating thickness
according to the fluorescence peaks areas ratios.

Figure 3.9 Calibration curves, from the simulated data, between the Mo intensities
and thickness.

Figure 3.10 Calibration curve, from the simulated data, between the Ti intensities
(only K-↵ and K- in this case) and thickness.

54
 For the Mo coating, both the K↵/K and the K/L have been considered
(Fig. 3.9). In the Mo K↵/K it is possible to observe an interesting behavior
for low thickness values, maybe explained by the fact that in such situations
the Mo K from the substrate contributes to the upper layer signal. In
the Mo K/L graph, instead, we have the expected trend (giving a linear
fitting equation of y=10.672x + 12.653). From the experimental spectra
we obtained a mean value of 6.67 for the K↵/K ratio, which is out of our
simulated scale, while the K/L has a mean value of 26.9 corresponding to a
thickness of about 1.335 µm, instead of the 2.085 µm from the Fe K↵=K
method, with a relative error of 43%. This method is therefore unreliable
for our purposes, at least in this case.
For the TiTiN coating, a matrix of Ti has been used for the simulation
(as for the fitting procedure), and only the Ti K↵/K values have been
plotted (Fig. 3.10). From the experimental spectra we obtained a mean
value of 7.5 for the K↵/K ratio, corresponding to a thickness of about 3.5
µm, comparable with those obtained from the Fe K↵=K and Cr K↵=K
methods, and equally “unreliable” (a relative error of 43%.
At the end of this preliminary evaluation of the most suitable parameter
for the coating thickness determination for steel substrates, we can con-
clude that, at least for ‘medium-high’ density coating matrices (as Mo), the
experimental method based on Fe K↵=K is the most reliable one.
Then, once determined the parameter to use, a more accurate treatment
of the XRF spectra was carried out, in order to perform also a quantitative
analysis. First of all, the steel substrate composition has been experimen-
tally determined by a measure on the back side (with no coating) and com-
pared with the values given by the SEM-EDS analysis (Tab. 3.18): in this
simple bulk analysis we obtained very good results, as the relative errors
are lower than 5 %. Then, to simulate the case of an unknown sample,
the substrate composition so far determined were inserted in the PyMCA
configuration. Due to the fact that molybdenum is present both in the sub-
strate and the coating (a PyMCA quantification limit for the moment), we
are not going to evaluate its quantification.
element tw% err%
Cr 18.28 4.2
Fe 69.45 -0.1
Ni 7.503 -1.5

Table 3.18 Quantitative analysis of the coated steel matrix.

The final step was the estimation of the coating thickness and the quan-
titative analysis of the substrate matrix (Tab. 3.19-3.20). Both the simple
version of PyMCA (PyMCA) and its latest option for the secondary fluo-
rescence excitation (SE) have been used. The secondary excitation seems
to help the quantitative analysis, but we obtain worse results for what re-
gards the coating thickness determination. As already observed above, the

55
method results to be acceptably reliable for the Mo coating, while is less
sensitive for the Ti one. However, with the SE version it seems possible to
obtain a good quantification of the substrate composition also with a bad
coating (Ti) thickness determination.
err% (PyMCA) err% (SE)
Cr 14 27.3
Fe -18.9 3.6
Ni -33.1 3.3
Mo thickness [µm] -0.1 11

Table 3.19 Quantitative analysis and thickness estimation for the Mo coating.

err% (PyMCA) err% (SE)

Cr -9.6 2.3
Fe -32.1 -2.2
Ni -47.7 -2.5
Ti thickness [µm] 50.7 58.9

Table 3.20 Quantitative analysis and thickness estimation for the TiTiN coating.

56
4

Getting in touch with µXRF

analysis of Cultural Heritage
materials

This section compares the results of the investigations carried out in situ
on a processional cross made of gilded and enamelled silver sheets, with
both an XRF and a micro-XRF spectrometers. The results show that the
information provided by the two devices are in most cases complementary,
so that the combined use of both seems, at present, recommended. This
redundancy could be removed by the development of a single system with
the performance combination of both the system (as the prototype proposed
in Chapter 5), which will be possible when polycapillary optics with a wider
pass band will come into common use.

4.1 In situ investigation of the processional cross

by Nicola da Guardiagrele
Between the XIV and the XVIII centuries the goldsmithing in Abruzzo
(Central Italy, at that time part of the french Reign of Naples) reached
a industrial level of production combined with a very fine quality of the
manufacturing technique [52, 55].
One of the main product of this local tradition is represented by the
processional crosses, dedicated to the town patrons. They are around 1 m
height and usually made of a wood core on which some metal embossed
sheets are attached, following a classical iconographical scheme of represen-
tation. There are five sheets per side, a central one representing the principal
theme (the Crucifixion on the recto and the Maiestas Domini on the verso)
and surrounded by the others, usually showing the four evangelists on one
side and other topics (e.g. the Virgin) on the other.

57
 Sometimes the crosses are also decorated with a variable number of
enamelled silver plates, and di↵erent manufacturing quality. The enamels
were usually realized with the bassetaille technique, consisting of translucent
enamels and a substrate with bas-relief for shadowing e↵ects.
The most important goldsmith master of this local tradition was Nicola
di Andrea di Pasquale da Guardiagrele, which lived and operated during
the first half of the XV century [53]. Among his wide production there is
the cross of Santa Maria Maggiore of Guardiagrele (Fig. 4.1), date to 1431,
which has been investigated in this work. The cross was stolen from the
church in 1979, but during the years di↵erent parts of it (as it has been
dismounted in order to sell the singular components on the black market)
has been recovered.

Figure 4.1 Left: the cross, intact, in a picture of ⇠ 1930. Right: the cross
fragments nowadays, exposed in the museum.

The fragments of the processional cross are now exposed at the Museo
del Duomo di Santa Maria Maggiore in Guardiagrele. The remaining gilded
parts from the recto represent the Crucifixion, the Resurrection and the
Deposition of the Christ, and those from the verso the blessing Lord, Saint
John, and Saint Mark. The four enamelled plates represent the coronation
of the Virgin, the Magi adoration, the Virgin with the baby on the throne,
and the escape from Egypt. The gilding technique has a very high quality,
with some parts of the silver substrate exposed in order to distinguish the
flesh from the clothes and giving fascinating colouring e↵ects. Some of the
gilded plates have also a background of blue enamel and gold decorations.
The enamels are realized with the bassetaille technique, and has a diameter
of ⇠ 4 cm.
The fragments have been analyzed by both a XRF and a micro-XRF
spectrometers. The investigations were carried out in situ at the museum,
settled in the crypt of the church. Aim of the analytical campaign was the

58
acquisition of information about the composition and the manufacturing
technique of the artifact, to be considered in a future restoration phase. The
analysis concerned the elemental composition and stratigraphic sequence of
the metal parts and the enamel decorations.

4.2 Comparative use of a conventional XRF and a

µXRF spectrometer: experimental setup
The equipment used for the XRF analysis (‘MXRF’) is a portable spectrom-
eter designed at ITABC - CNR (Fig. 4.2.a). The X-ray source is a W anode
Oxford tube working at 60 kV and 1.5 mA, with a spot size of 1.7 mm. The
SDD detector from Bruker has a resolution of 173 eV at 5.9 keV, thickness
450 µm, Be window, Cu filter, 7 mm2 Zr collimator, and an active area of
10 mm2 . The acquisition time was 120 s. In such conditions and for metal
matrices the detection limits are 0.01 wt% for Au L-lines and 0.001 wt% for
Ag K-lines. The spectrometer has a total weight of 10 kg, plus the power
supply. About 85 ‘MXRF’ spectra have been recorded on the fragments,
both the gilded and the enamelled ones.
Micro-XRF analyses (‘mXRF’) were carried out with a Unisantis XMF-
104 (Fig. 4.2.b). It is provided with a closed measurement chamber (122x116
x78 mm) which limits the dimensions of the objects that can be analyzed.
For this reason, only the enamels of the cross were analyzed with this system.
The tube has a Mo anode, it works at 50 kV and 100 µA, and has a beam
spot size of 80 µm. The detector is of the Si-PIN type from Amptek, with
a resolution of 186 eV at 5.9 keV, thickness 500 µm, Be window, and an
active area of 7 mm2 . The acquisition time was 200 s. In this case, always
for metal matrices, the detection limits are 0.01 wt% for Au L-lines and
0.03 wt% for Ag K-lines [54]. The instrument weights 34 kg. About 65
‘micro-XRF’ spectra were collected, only for the enamelled ‘formelle’.

Figure 4.2 a) ITABC-CNR spectrometer, with one gilded fragment under analysis;
b) Unisantis XMF-104 location in the museum.

Fig. 4.3 compares the spectra of the exciting radiation of the instru-

59
ments. Due to the di↵erent intensities of the beams (because of both the
di↵erent current settings and the polyCO), the counts of each channel have
been normalized to the overall spectrum area, to highlight the shape of the
spectra. The substantial di↵erence observed is due not so much to the volt-
age settings (50 vs. 60kV), as to the presence of the polyCO in the mXRF,
which behaves as a low-pass filter. The lens, optimized for the Mo K↵ line
(⇠ 17 keV), strongly reduces the high energy fraction of the continuum,
while in the MXRF system this part of the spectrum is the major fraction,
also because of the copper filter.
To appreciate how the di↵erent beam shapes can a↵ect the detection
of the elements of the two experimental set up, the absorption edges of
important elements are also marked. As described above, the two systems
have similar detection limit for medium-energy element lines (Pb L-lines),
but the MXRF has better performances for high-energy ones (Ag K-lines).

Figure 4.3 Primary beams produced by the two XRF systems, with normalized
intensities. The Mo K- and W L-lines are visible. The absorption edges for some
significant elements K-lines are indicated.

In some cases, the spot size of the MXRF system can be too large to eval-
uate the distinction between close areas with di↵erent chemical composition
(related to the colors). As an example, we report the case the red frame and
the blue background in the Sant’Elpidio’s “formelle” (Fig. 4.4.a), studied
in a previous work [56]. The poor spatial resolution led to the detection of
cobalt also in the red enamel (Fig. 4.4.b, area < 1 mm), though its signal
was clearly due to the blue one as well-known from literature concerning the
chemical recipes for colored glasses. Here the need for a higher spatial res-
olution system to determine both qualitative and quantitative composition
of the enamels is clear.

60
Figure 4.4 a) Picture of an enameled “formella” from the Sant’Elpidio Cross (a
medieval cross of the Central Italy). Red and blue spots indicate the measurement
points. b) Spectra obtained with the MXRF spectrometer on a blue and a red
area. In the red spectrum also the fluorescence signal coming from the surrounding
gilded frame (Au and Hg) was detected.

Figure 4.5 a) Picture of an enamelled decorative component from the Guardia-

grele cross, with a spot indicating the measurement point. b) Comparison of the
spectra obtained with both the spectrometer for the same blue enamel. In the
spectrum detected by the MXRF system the Mo lines are due to the collimator
used, while in the one of the mXRF spectrometer they are present as the anode
tube characteristics lines.

However, in many cases the primary beam produced by the MXRF spec-
trometer can be essential, as it allows the excitation of the K-lines of medium
Z elements such as silver (from the substrate, useful in the coating thick-
ness estimation), tin and antimony (characteristics glass components). For
example, the spectra of a blue enamel, from a decorative element of the
Guardiagrele Cross, obtained with both the experimental systems are shown
in Fig. 4.5. It can be seen that the Sb K-(in trace) and the Sn K lines are
not detected by the mXRF system.
A good excitation of high energy fluorescence lines could be mandatory,
in some cases, for the potential authentication of an artifact. For example,
in the case of some medieval crosses [56], the detection in the blue enamels
of the indium K↵ line (Fig. 4.6) contributed to confirm the dating of the
“formelle”. This was possible because, as known in literature [58], indium is
a characteristic impurity of the cobalt mineral extracted from the Freiberg
mine, exploited in a short range of time between the XIII and XIV centuries.

61
Figure 4.6 a) Picture of one of the Rosciolo cross “formelle”. b) MXRF spectrum
of the Rosciolo blue enamel [56].

Finally, it should be noted that only the enamelled “formelle” size is

compatible with the mXRF chamber, not the gilded silver sheets, and how-
ever they can be analyzed only if dismounted (as in the Guardiagrele case,
or if the cross is under restoration).

4.3 Discussion and interpretation of the results

The metal alloys and the gilding technique

Figure 4.7 ‘MXRF’ measurement location: on the left the Deposition, on the right
the Resurrection.

In this section, only the ‘MXRF’ measurements are taken into account.
The silver alloy of the gilded parts resulted to contain an average Cu amount
of 3.5 % (expressed in weight fraction), whereas its content in the enamelled
plates was ⇠ 1 % (Fig. 4.11.a). The di↵erence in the alloys could be due to
the di↵erent manufacturing processes: the gilded sheets embossing required
a higher plasticity respect to the enamelled plates, given by a higher amount
of Cu. In addition, in the plates a lower amount of copper is required to
avoid the formation of oxides during the firing process that would prevent the

62
Figure 4.8 ‘MXRF’ measurement location: on the left the crucifixion of Christ,
on the right the blessing Lord.

Figure 4.9 ‘MXRF’ measurement location: on the left St. John, on the right St.
Mark.

Figure 4.10 ‘MXRF’ measurement location: the Virgin.

63
adhesion of the enamel layer. The detection of mercury confirmed the use of
the amalgam gilding technique, and the average gilding thickness was 3 µm
(Fig. 4.11.b). The di↵erent amounts of Au and Hg in the gilding layer are
reported (Fig. 4.12) for three type of situations: gilt parts, silver portions
and the “formelle” back. As expected, Au and Hg are quite abundant in
the gilded parts, and very low in the silver back. However, a particular
attention must be paid to the not-gilded portions of the front of the embossed
sheets. The flesh of the characters represented is ungilded, maybe to be
distinguished from the clothes, but a little amount of Au and Hg has been
detected as well in some cases, for example in the face of the Lord (Tab. 4.1).
In other cases the protruding parts (some heads, hands and feet) present no
gilding at all, and probably have been assembled after the gilding process.
In other points, near the gilded areas, mercury was detected but not gold.
It could be assumed that, in this case, the amalgam was removed from the
exceeding boundaries before firing it, but in the meantime the Hg of the
mixture combined with the Ag of the substrate. A fascinating explanation
could be that this amalgam remotion was consciously made by the artist, in
order to give a sort of translucent e↵ect to final result.

Figure 4.11 a) comparison between the Cu contents in the gilded and enamelled
plates. b) gilding thickness values.

Figure 4.12 Comparison between the Cu and Hg amounts in the di↵erent areas.
As expected, a correlation is observed for the gilded parts.

64
Id Subject type Cu wt% Ag wt% Pb wt% Au wt% Hg wt% gilding thickness µm
7 Magi adoration lacuna 0.49 37.29 0.21 1.57 0.02
8 Magi adoration gilded border 3.19 28.65 0.07 78.85 21.15 3.36
9 Magi adoration back 1.04 37.51 0.36 1.42 0.02
16 Virgin on the throne lacuna 0.43 37.52 0.18 2.73 0.23
23 Virgin coronation lacuna 0.31 34.24 0.13 3.28 0.36
24 Virgin coronation back 0.81 37.38 0.40 1.52 0.01
25 Virgin coronation gilded border 0.61 12.86 0.05 80.65 19.35 7.98
36 escape from Egypt back 0.86 36.00 0.41 1.45 0.02
37 Deposition not gilded 3.88 30.68 0.36 1.71 0.19
38 Deposition back 4.41 35.52 0.77 1.03 0.91
39 Deposition not gilded 3.69 29.31 0.31 1.32 0.19
40 Deposition not gilded 5.81 35.98 0.45 1.57 0.66
41 Deposition gilding 2.48 26.27 0.52 79.52 20.48 7.21
42 Deposition gilding 2.85 32.37 0.25 76.26 23.74 1.95
43 Deposition not gilded 4.23 33.70 0.53 1.07 4.04
44 Deposition back 4.38 34.12 0.70 0.99 1.34
45 Resurrection back 2.47 35.74 0.44 2.12 3.51
46 Resurrection back 2.14 30.34 0.31 14.96 85.04 0.57
47 Resurrection not gilded 3.83 32.81 0.46 1.50 3.24
48 Resurrection gilding 3.84 30.54 0.15 76.75 23.25 3.07
49 Resurrection gilding 3.07 30.46 0.00 77.08 22.92 3.47
50 Crucifixion not gilded 18.78 35.34 0.02 0.08 0.02
51 Crucifixion soldering 17.77 1.21 20.45 0.06 0.05
52 Crucifixion soldering 10.89 8.05 13.39 0.00 0.00
53 Crucifixion back 7.92 25.74 0.02 0.06 0.03
54 Blessing Lord back 4.45 31.90 0.76 3.39 2.40
55 Blessing Lord not gilded 4.59 31.54 0.43 3.85 96.15 0.77
56 Blessing Lord not gilded 3.09 30.50 0.43 6.74 93.26 0.72
57 Blessing Lord gilding 3.79 29.77 0.18 76.16 23.84 3.13
58 Blessing Lord gilding 1.25 31.56 0.22 79.59 20.41 4.67
59 Resurrection not gilded 4.15 29.23 0.37 16.35 83.65 0.80
60 Resurrection not gilded 4.25 28.00 0.24 37.67 62.33 2.65
62 St. John back 3.75 34.52 0.62 0.72 0.47
63 St. John not gilded 3.74 30.43 0.50 0.57 0.13
64 St. John not gilded 4.19 28.14 0.29 1.74 98.26 1.77
65 St. John gilding 3.63 31.19 0.07 74.36 25.64 3.13
67 St. John gilding 1.49 29.25 0.52 80.47 19.53 2.62
68 St. Mark back 3.39 33.62 0.58 0.93 0.22
69 St. Mark not gilded 4.16 32.07 0.40 0.91 4.69
70 St. Mark gilding 2.63 30.69 0.18 81.12 18.88 2.60
72 St. Mark gilding 0.68 29.70 0.30 80.94 19.06 1.47
73 St. Mark lacuna 0.35 38.03 0.20 4.92 0.72
74 Virgin back 2.64 35.26 0.58 0.83 0.19
75 Virgin back 59.46 9.90 0.02 0.45 0.02
76 Virgin not gilded 3.18 31.27 0.53 1.11 2.20
77 Virgin gilding 2.63 32.13 0.22 81.27 18.73 2.64

Table 4.1 ‘MXRF’ results on the enamelled plates (at the top) and the gilded
silver sheets (at the bottom). For the gilded parts, the Au and Hg amounts refer
to the gilding coating, while for the others to the substrate silver alloy.

The enamels

Figure 4.13 ‘MXRF’ measurement location: the Magi adoration on the left, the
escape from Egypt on the right.

65
Figure 4.14 ‘MXRF’ measurement location: the coronation of the Virgin on the
left, the Virgin on the throne with the baby on the right.

Figure 4.15 ‘mXRF’ measurement location: the Magi adoration on the left, the
escape from Egypt on the right.

Figure 4.16 ‘mXRF’ measurement location: the coronation of the Virgin on the
left, the Virgin on the throne with the baby on the right.

The average enamel thickness resulted to range from 50 to 100 µm, with
the maximum values for the blue parts (200 µm). The gray and pink enamels

66
resulted to be quite thin, maybe due to an underestimation error.
The quantitative results for the enamel layer composition, except for
the light elements (Si and Na, the principal constituent of a glass matrix)
impossible to detect with our experimental set ups, are reported in Figs.
4.17-4.24 and in Tabs. 4.2-4.3. The contents of the di↵erent elements used
as colourants and additives are coherent with the bibliographic data on the
composition of the XV century enamels. Due to the presence of potassium
and calcium, the matrix should be a potassic or mixed glass, composed by
K2 O as flux (together with low percentages of Pb in every colour) and CaO
as stabillizer. The amounts of Rb and Sr results correlated (Fig. 4.22),
being a typical impurity of the sands used as raw material: from the data
we can assume that all the enamels were obtained from the same raw glass
material.
The di↵erent colours are characterized as follows: blue by cobalt and
some amounts of Mn, Fe, and Cu; yellow by iron; green by copper, iron,
zinc (maybe due to the use of brass as Cu source), and antimony; violet by
manganese. The gray and pink contents are uncertain for what regards the
MXRF analysis, however from the mXRF analysis both resulted to contain
4 % of Mn, and the gray also 10 % of Fe and 5 % of Cu.
It has been possible to observe (Figs. 4.23-4.24) the correlations Fe-Cu
and Fe-Mn for the blue, Fe-Cu, Zn-Cu and Zn-Fe for the green.
In the blue enamels a Fe-Cu-Mn correlation was observed (Fig. 4.23).
Iron and manganese could be impurities of the cobalt mineral, while a little
amount of copper would have provided a di↵erent blue shade. The absence
of zinc (common in blue enamels of the XIV century) and nickel (usualy
present in those of the early XIV century) is coherent with the cross dating
at late XIV century [57].
In the green enamels a Fe-Cn-Zn correlation was observed (Figs. 4.23-
4.24). Only in the blue enamel of a decorative diamond was found an
important amount of Bi, which probably indicates it as an anachronistic
restoration part (Fig. 4.5).
The combined use of the ‘MXRF’ and ‘mXRF’ devices allowed to over-
come the single experimental limits: poor spatial resolution and light ele-
ments detection from one side, poor high energy excitation and incompati-
bility with large objects from the other. However, dealing with two di↵erent
sets of data is not simple, and the informations cannot always be compared.
That is way the use of a single system able to combine the strength point
of both the techniques would be recommendable, when possible.

67
Figure 4.17 ‘MXRF’ (big circles) and ‘mXRF’ (small circles) results for the dif-
ferent colour glass.

Figure 4.18 ‘MXRF’ (big circles) and ‘mXRF’ (small circles) results for the dif-
ferent colour glass.

Figure 4.19 ‘MXRF’ (big circles) and ‘mXRF’ (small circles) results for the dif-
ferent colour glass.

68
Figure 4.20 ‘MXRF’ (big circles) and ‘mXRF’ (small circles) results for the dif-
ferent colour glass.

Figure 4.21 ‘MXRF’ (big circles) and ‘mXRF’ (small circles) results for the dif-
ferent colour glass.

Figure 4.22 ‘MXRF’ (big circles) and ‘mXRF’ (small circles) results: correlation
between Rb and Sr for the di↵erent colour glass.

69
Figure 4.23 ‘MXRF’ (big circles) and ‘mXRF’ (small circles) results: correlation
Cu-Fe and Mn-Fe for the di↵erent colour glass.

Figure 4.24 ‘MXRF’ (big circles) and ‘mXRF’ (small circles) results: correlation
Zn-Fe and Zn-Cu for the di↵erent colour glass.

70
 Id Subject Colour K wt% Ca wt% Mn wt% Fe wt% Co wt% Cu* wt% Zn wt% Rb wt% Sr wt% Sn wt% Sb wt% Pb wt% Bi wt%
1 Magi adoration blue 7.556 2.805 0.322 1.192 0.674 0.850 0.001 0.053 0.058 0.308 0.007 0.432 0
2 Magi adoration green 6.536 2.361 0.066 4.663 0.000 4.683 0.574 0.004 0.012 0.282 0.024 0.371 0
3 Magi adoration violet 7.021 2.894 4.402 0.277 0.002 0.099 0.011 0.054 0.066 0.287 0.017 0.430 0
4 Magi adoration yellow 11.100 6.607 0.834 6.397 0.048 0.307 0.031 0.031 0.071 0.160 0.003 0.260 0
5 Magi adoration yellow 10.950 4.143 0.725 6.792 0.020 1.883 0.214 0.046 0.055 0.256 0.019 0.520 0
6 Magi adoration violet 5.545 3.083 1.684 0.306 0.002 0.173 0.029 0.087 0.086 0.372 0.009 0.412 0
10 Virgin on the Throne blue 4.484 5.086 1.752 2.497 1.110 1.951 0.009 0.107 0.145 1.169 0.018 2.563 0
11 Virgin on the Throne yellow 8.908 4.573 0.892 6.003 0.047 0.191 0.013 0.027 0.050 0.141 0.005 0.337 0
12 Virgin on the Throne green 6.590 2.733 0.504 3.325 0.289 3.647 0.391 0.031 0.032 0.525 0.030 0.896 0
13 Virgin on the Throne yellow 10.260 5.221 1.303 11.180 0.104 0.453 0.019 0.044 0.108 0.670 0.022 1.609 0
15 Virgin on the Throne blue 3.770 2.096 0.182 0.883 0.400 0.522 0.018 0.004 0.017 0.093 0.004 0.203 0
17 coronation of the Virgin blue 7.497 1.770 0.211 0.881 0.467 0.549 0.009 0.015 0.022 0.132 0.008 0.247 0
18 coronation of the Virgin blue 6.417 2.446 0.455 1.006 0.531 0.681 0.003 0.031 0.050 0.359 0.004 0.599 0
19 coronation of the Virgin blue 7.166 1.309 0.183 0.714 0.411 0.424 0.017 0.016 0.012 0.080 0.004 0.129 0
20 coronation of the Virgin green 11.220 3.513 0.125 4.781 0.013 5.045 0.542 0.035 0.038 0.358 0.037 0.416 0
21 coronation of the Virgin yellow 10.080 4.329 1.599 3.878 0.036 0.140 0.018 0.011 0.045 0.075 0.005 0.215 0
22 coronation of the Virgin violet 7.886 2.631 3.785 0.340 0.011 0.084 0.001 0.035 0.052 0.210 0.017 0.407 0
26 escape in Egypt blue 7.020 5.783 1.302 1.802 0.828 1.304 0.005 0.101 0.116 0.965 0.019 1.490 0
27 escape in Egypt green 8.528 2.246 0.089 5.012 0.010 5.221 0.648 0.001 0.010 0.265 0.033 0.352 0

71
28 escape in Egypt violet 6.661 2.745 4.469 0.224 0.003 0.096 0.009 0.073 0.073 0.286 0.021 0.249 0
29 escape in Egypt yellow 11.050 1.971 2.663 7.990 0.030 0.302 0.041 0.011 0.027 0.101 0.005 0.140 0
30 escape in Egypt yellow 10.230 4.631 1.172 5.635 0.043 0.340 0.023 0.026 0.067 0.106 0.006 0.215 0
31 escape in Egypt gray 10.710 5.099 3.251 4.985 0.176 2.273 0.152 0.076 0.172 0.460 0.007 0.806 0
32 escape in Egypt gray 10.800 5.445 4.082 7.062 0.433 3.620 0.224 0.109 0.214 0.884 0.024 1.838 0
33 escape in Egypt blue 6.063 2.821 0.286 0.645 0.412 0.437 0.005 0.039 0.046 0.226 0.009 0.238 0
34 escape in Egypt pink 4.816 3.988 3.007 0.760 0.072 0.606 0.055 0.182 0.202 1.009 0.024 1.156 0
36 Deposition blue 4.462 3.358 0.240 0.973 0.563 0.758 0.016 0.009 0.032 0.381 0.007 1.362 0
61 Blessing Lord blue 10.240 4.457 0.867 1.125 0.433 0.606 0.001 0.023 0.036 0.217 0.002 0.520 0
66 St. John blue 3.518 2.939 0.272 1.005 0.617 0.821 0.039 0.195 0.002 0.162 0.004 0.561 0
71 St. Mark blue 4.452 3.011 0.212 0.866 0.503 0.572 0.014 0.002 0.018 0.136 0.002 0.388 0
79 diamond* blue 10.950 5.157 0.231 0.902 1.154 7.483 0.009 0.020 0.032 5.354 0.040 6.830 6.125
84 column blue 5.125 4.386 0.710 0.936 0.359 0.665 0.010 0.044 0.030 0.327 0.004 0.815 0

Table 4.2 ‘MXRF’ results on the enamelled silver plates and sheets. The Cu values are not very reliable, due to its presence also in the
silver substrate.
 Subject Colour K wt% Ca wt% Mn wt% Fe wt% Co wt% Cu* wt% Zn wt% Rb wt% Sr wt% Pb wt%
coronation of the Virgin blue 3.59 1.47 1.2 2.97 1.63 2.84 - 0.1 0.11 1.25
coronation of the Virgin blue 1.79 0.59 0.34 1.67 1.07 1.9 - 0.08 0.08 0.44
coronation of the Virgin green 10.62 2.17 0.15 10.62 0.07 18.08 2.01 0.1 0.11 0.88
coronation of the Virgin green 10.61 2.11 0.17 11.69 0.09 19.96 2.3 0.13 0.11 1.19
coronation of the Virgin violet 2.95 1.03 7.47 0.41 - 0.1 - 0.06 0.05 0.21
coronation of the Virgin yellow 8.06 4.94 1.81 14.86 - 0.28 - 0.08 0.22 0.37
coronation of the Virgin yellow 9.07 4.93 1.94 14.86 - 0.38 - 0.08 0.21 0.42
Escape in Egypt blue 4.57 2.41 2.42 3.32 1.48 3.06 - 0.11 0.13 1.6
Escape in Egypt blue 3.18 1.82 1.77 2.47 1.07 2.15 - 0.08 0.09 1.23
Escape in Egypt blue 3.2 2.04 2.01 2.84 1.23 2.53 - 0.08 0.11 1.36
Escape in Egypt blue 1.55 0.18 0.27 1.36 0.91 1.57 - 0.07 0.06 0.38
Escape in Egypt blue 0 0.01 0.01 0.04 0.05 0.23 - 0.04 0.03 0.14
Escape in Egypt green 2.18 1.4 0.03 5.02 0.07 10.93 1.56 0.06 0.05 0.68
Escape in Egypt green 5.55 0.76 0.09 8.33 0.07 14.7 1.96 0.08 0.04 0.95
Escape in Egypt violet 3.48 0.98 8.01 0.31 - 0.19 - 0.06 0.05 0.28
Escape in Egypt violet 3.37 0.79 7.34 0.31 - 0.14 - 0.07 0.08 0.25
Escape in Egypt yellow 3.45 2.83 2.73 10.06 - 0.79 - 0.06 0.06 0.26
Escape in Egypt pink 1.74 1.06 2.66 0.31 - 0.46 - 0.07 0.07 0.33
Escape in Egypt pink 2.24 1.66 3.65 0.43 - 0.94 - 0.06 0.05 0.44
Escape in Egypt pink 3.78 2.18 4.53 0.61 - 0.47 - 0.1 0.08 0.43
Escape in Egypt gray 8.82 2.68 5.75 8.74 - 6.26 0.39 0.08 0.13 1.05

72
Escape in Egypt gray 7.85 2.64 5.63 8.96 - 6.38 0.47 0.07 0.18 0.97
Escape in Egypt gray 7.24 2.31 1.43 15.56 - 0.58 0.02 0.07 0.1 0.53
Escape in Egypt gray 4.81 1.72 3.43 5.8 - 4.41 0.27 0.06 0.11 0.82
Magi adoration blue 6.14 3.96 2.78 3.75 1.63 3.38 - 0.12 0.13 1.7
Magi adoration blue 5.96 2.93 2.56 3.67 1.51 3.08 - 0.1 0.11 1.65
Magi adoration blue 3.79 1.57 1.62 2.27 1 2.39 - 0.09 0.1 1.09
Magi adoration green 8.5 0.45 0.07 12.96 0.09 22.9 3.15 0.08 0.07 1.19
Magi adoration green 6.9 0.22 0.09 9.95 0.25 17.6 2.53 0.06 0.03 0.94
Magi adoration green 8.6 1.06 0.1 11.59 0.25 20.53 2.84 0.1 0.04 1.16
Magi adoration violet 2.63 1.21 7.91 0.41 - 0.22 - 0.05 0.06 0.4
Magi adoration violet 2.22 0.99 7.02 0.57 - 0.33 - 0.05 0.06 0.54
Magi adoration yellow 9.24 4.8 1.86 15.08 - 0.41 - 0.07 0.22 0.38
Magi adoration yellow 8.35 4.28 1.64 15.58 - 0.23 - 0.07 0.18 0.45
Magi adoration pink 3.6 2.33 5 0.76 - 1.18 - 0.08 0.05 0.87
Magi adoration pink 2.94 2.13 4.59 0.62 - 0.42 - 0.09 0.07 0.48
Virgin on the Throne blue 0.9 0.06 0.2 0.97 0.65 1.24 - 0.06 0.07 0.39

Table 4.3 ‘mXRF’ results on the enamelled silver plates. The Cu values are not very reliable, due to its presence also in the silver
substrate.
5

Development of a µXRF
spectrometer for Cultural
Heritage applications
(pHEMIX)

As already stated in the previous chapters, XRF is one of the leader tech-
niques in the cultural heritage field, but it has to fulfill some strict require-
ments. From one side, an XRF system must be able to excite and detect the
fluorescence K-lines of medium-Z elements (Ag, Sn, Sb, Ba, Cd, etc.), which
often characterize the artifacts. Such spectrometers employ high voltages
(typically 50-60 kV), therefore their use requires a proper shielding and oper-
ating authorization by a qualified forensic. On the other side, when dealing
with ancient artifacts, often a high spatial resolution is needed for the anal-
ysis of tiny details or small abraded areas (< mm) already present on the
surface, without producing further abrasions. For this purpose, some lab-
oratory micro-XRF spectrometers are equipped with polycapillary lenses.
However, such commercial instruments presently available have an upper
energy limit of detection around the Ba K-lines (32 keV) if they are labo-
ratory devices (chapter 4), or even just up to Sb K-lines (26 keV) if they
are portable. For these reasons, as highlighted in chapter 4, the information
provided by XRF and micro-XRF systems are in most cases complementary,
so that the use of both seems, at present, recommended. The main goal of
this project is the realization of a portable micro-XRF device combining the
capability of exciting high-energy fluorescence lines, typical of conventional
XRF spectrometers, with the excellent spatial resolution of the micro-XRF
ones, obtaining final intermediate (at least) performances. In this section,
first of all, a preliminary feasibility study is presented, carried out to both
learn how to work with X-ray tube and polyCOs, and to understand the
optimum operating and instrumental parameters to adopt for the prototype

73
realization. Then, the criteria for the selection of each component of the
prototype, and their characterization, are illustrated. Finally, the results of
the validation tests of the system performances are presented, in order to
see if and how our starting goal has been achieved.

5.1 Experimental set up

The measurements were carried out at XLab Frascati [59] (INFN-LNF),
in the cabinet properly shielded for X-rays radiation (Fig. 5.1) of XENA
(X-ray Experimental Station for Non-destructive Analysis) [33, 60].

Figure 5.1 Left: XENA experimental station. Right: set of images taken with the
CCD at various distances from the lens exit.

For the feasibility study, as X-ray source a W anode Oxford Apogee

tube (50 kV) was used. For the primary beam characterization, the current
was set at its minimum (⇠ 1 µA) to avoid detector damages and signal
saturation, while for the XRF analysis it was put at 1 mA. This tube was
chosen in order to simulate the future prototype, for which a source with
same anode and voltage has been considered.
A Bruker Si-Drift detector (SDD) with active area of 10 mm2 , thickness
450 µm, FWHM 175 eV at 5.9 keV, peaking time 1 µs, Be window, internal
7 mm2 Zr collimator, and external Pb collimator for direct measures of the
primary beam, was used. The acquisition time was 120 seconds.
A Unisantis full lens optimized for Cu K↵ (⇠ 8 keV) with IFD 56.5 mm,
OFD 44 mm, 12 cm length, and output focal spot size 100 µm was used.
This lens was chosen in order to observe how a conventional optics for a low-
medium energy range modifies the primary beam. For the polyCO alignment
(section 2.2), an Ortec 3 kV scintillator and a set of motors governed by a
Newport MM4006 Controller were used. The entire procedure was remotely
operated by a LabView code integrated in the Vitruvio system [33], an
homemade software for the laboratory control. The nominal OFD and the
spot size were verified by means of a CCD Photonic Science camera FDI
1:1.61 (section 2.2), with an active area of 14.4x10.8 mm2 and a spatial
resolution given by the pixel size 10.4x10.4 µm2 , controlled by the software
package Image-Pro Plus 6.0. With the tube operating at ⇠ 43.5 kV and ⇠

74
 type thickness [µm] composition absorption edges [keV]
steel 35 Fe (74%) 7.2
Cr (18%) 6
Ni (8%) 8.3
copper 30 Cu 9

Table 5.1 Filters description.

4 µA, some images were taken at various distances from the lens exit (Fig.
5.1, right), each one for an acquisition time of 200 ms. Image n 3, taken at
46 mm (the position closest to the nominal OFD value of 44 mm), reveals
the better focusing distance, with a spot size ⇠ 100 µm.
Two types of filter, a stainless steel and a copper sheet (Tab. 5.1), were
placed before the lens to relatively enhance the high energy fraction of the
exciting spectrum.
The various primary spectra were registered by the detector placed at
39 cm in front of the lens exit (Fig. 5.2).

Figure 5.2 Left: geometry of the direct measurements of the primary beam (a),
the focused (b) and the focused/filtered ones (c). Right: source-optics layout, inside
the XENA station; it is possible to see also the lens holding and alignment system.

A set of reference materials (for both homogeneous and multilayer ma-

trices) was used. It includes: a silver standard sheet (Ag 92.5%) with a
thickness of 1 mm to estimate the incident flux; 10 silver standard alloys
(Tab. 3.3, ‘INFN’ series); 6 silver standard sheets (same Ag substrate)
with di↵erent gilding thicknesses (1.967 µm, 2.700 µm, 4.143 µm, 4.440 µm,
5.870 µm, 7.300 µm), realized by sputtering at Laboratorio di trattamento
e deposizione Film sottili of ENEA-Casaccia; an enameled silver standard
plate (same Ag substrate, and a red enamel layer of 0.99 mm) realized
with the cloisonné technique at Scuola dell’Arte della Medaglia dell’Istituto
Poligrafico e Zecca dello Stato (SAM - IPZS) and 3 á-jour (without sub-
strate) enamel samples (yellow, red, and black, Tab. 5.2); 6 bronze standard
alloys (Tab. 3.2, and another with Pb 3.39%, Sn 2.34%, Sb 0.14%); a 50
cent coin (Cu 89%,Al 5%, Zn 5%, Sn 1 %); 3 stainless steel standard alloys
(Tab. 3.3) and 2 PVD coated (Mo and TiTiN) stainless steel substrates

75
(Tab. 3.4); 3 standard glasses (Tab. 3.5); thin standard samples (Tab. 5.3);
and a marble sample treated with titanium dioxide (TiO2 ). The incident
and take-o↵ angles were fixed at 90 and 45 , respectively (Fig. 5.3).
element (wt%) red enamel yellow enamel black enamel
K 12.79 3.73 6.72
Ca 0.16 0.39 0.09
Cr 0.27
Mn 2.56
Fe 0.07 0.78 1
Co 1.31
Ni 0.45
Cu 0.01
Zn 8.18 0.99
Cd 0.6
Sb 3.72
Ba 9.42 0.05
Pb 47.74 33.66

Table 5.2 Enamels composition given by SEM analysis. The enamel samples have
been realized at Scuola dell’Arte della Medaglia dell’Istituto Poligrafico e Zecca
dello Stato (SAM - IPZS), under the supervision of Rosa Maria Villani and Valeria
Sicilia.

element thickness (µm)

silver 2
copper 75
iron 1
molybdenum 20
tin 2
titanium 1
tungsten 3

Table 5.3 Thickness of the thin standard samples.

Figure 5.3 Geometry of XRF acquisition system (example for a gilded silver sam-
ple).

5.2 Feasibility study

The preliminary step for the realization of a polyCO based micro-XRF pro-
totype for the detection of high energy fluorescence lines was a feasibility
study [62, 63] aimed at characterizing the primary beam focused by such
optics and evaluating its efficiency in exciting the K-lines of our interest.
For these purposes the following experimental activities have been carried

76
out:
- characterizing the X-ray tube spectrum transmitted by a common full lens
(optimized for a low-medium energy range);
- exploring polycapillary-filter combinations for an empirical beam harden-
ing;
- testing the applicability for the XRF analysis of di↵erent matrices and the
coating thickness evaluation.

5.2.1 Experimental results

Characterizing the primary beam
In order to characterize the beam transmitted by the focusing lens, which
di↵ers from the source primary beam, some direct measurements were car-
ried out by placing the SDD detector in front of the tube, both with and
without the optics. We registered these spectra in order to understand how
the polycapillary lens modifies the primary beam, and to determine if the
radiation behind the optics could excite the fluorescence K-lines at high
energies. Additionally, the exciting beam characteristics, in particular the
incident weighted energies, are necessary for the quantitative analysis based
on the Fundamental Parameter method (section 1.4). In the FP method
the real primary beam impiging on the sample surface must be known, and
it can be obtained by correcting the registered spectrum for the detector
efficiency (section 5.30).

Figure 5.4 Comparison between the primary spectra emitted by the tube and
transmitted by the lens. a) Real spectra, corrected for the detector efficiency; b)
spectra normalized with respect to the total count rate (considered 1).

In the primary spectrum both the bremsstrahlung and the anode W L-

lines are well recognizable (Fig. 5.4). W K-lines (K↵ ⇠ 59 keV) are not
excited because of the tube low voltage (50 kV). The polyCO attenuates
the overall spectrum intensity with respect to the unfocused beam, as vis-
ible from the comparison between the real intensities shown in Fig. 5.4.a.
By comparing the normalized spectra (Fig. 5.4.b), the modification of the

77
spectrum shape can be observed. In particular, the polycapillary lens re-
duces the bremsstrahlung component at high energies and its maximum is
shifted towards lower values (from ⇠ 19 to ⇠ 14 keV). The polyCO resulted
to have a good transmission efficiency in the energy range 6-20 keV (Fig.
5.5), with a maximum around 12 keV.

Figure 5.5 An estimation of the lens transmission efficiency as a function of the

energy. The values are obtained from the ratio between the intensities of the unfo-
cused and focused beams (shown in Fig. 5.4.a). These data should be considered
only for qualitative observations, as for a better estimation the unfocused beam
should have been recorded at the entrance of the lens (but it would have lead to
detector saturation problems).

Beam filtering
The presence of the W L-lines in the exciting beam may a↵ect the qualitative
and quantitative analysis of those elements with fluorescence lines in the
same energy range (⇠ 8-12 keV). Cutting o↵ the W L-lines and the low
energy region of the spectrum will also relatively enhance the high energy
fraction necessary to excite the K-lines of the elements of interest. Therefore,
a set of filters has been tested. Direct measurements were carried out (Fig.
5.2.c), and the spectra of the focused and filtered beams are shown in Fig.
5.6.
The intensity of the spectra have been normalized in order to be com-
pared, as the tube current was di↵erent for the measures because of the
attenuation operated by the filters and the lens. The steel filter eliminates
only the W L↵1 (8.4 keV), while the copper filters the other W K-lines.
Therefore, the optimum solution seems to be a combination of both (Fig.
5.7), and it will be used for the XRF measures. On the other hand, using 2
filters will further reduce the overall spectrum intensity.

78
Figure 5.6 Spectra of the focused beam filtered with various materials are shown.
The intensities are normalized with respect to the total count rate (considered 1).

Figure 5.7 Spectra of the primary beam (black), the polyCO focused beam (red),
and the focused/filtered one (blue). The dashed lines indicates the position of the
relative bremsstrahlung maxima. The steel/Cu filter allows enhancing the high
energy fraction of the focused beam (⇠ 20 keV). The intensities are normalized
with respect to the total count rate (considered 1).

XRF measurements
First of all, some XRF measurement on the 50 cent coin and the marble
sample, with and without the filter (Fig.5.8-5.9), were carried out in order to
estimate its real contribute to the detection of the medium-high Z elements
K-lines. The filter e↵ectively improves the signal-to-noise ratio (SNR) for
elements such as Sr (K↵ 14 keV) and Sn (K↵ 25 keV). It also strongly
reduces the background in the low energy range (⇠1-18 keV) and the W
L-lines scattered from light matrices (as in the marble case). On the other

79
side, without the filter the presence of the W L-lines better excites the lighter
elements: this aspect will be further investigated in the section dedicated to
the prototype components and validation.

Figure 5.8 XRF spectra of the 50 cent coin with (red) and without (black) filter.
The intensity have been normalized with respect to the Cu K↵ line, in order to
appreciate the di↵erences in the background (in the real spectra, the Cu K-lines
intensity is highly reduced by the use of the filter). The filter improves the SNR
for the Sn K↵ from 0.5 to 9.5.

Figure 5.9 XRF spectra of the marble sample, treated with TiO2 , with (red) and
without (black) filter. The intensity have been normalized with respect to the Ca
K↵ line. The filter improves the SNR for the Sr K↵ from 0.2 to 112. It also removes
the scattered W L-lines. On the other hand, without the filter we have better SNR
for the light elements (Ca K↵ SNR 18 instead of 14, Ti K↵ SNR 39 instead of 9),
and it is possible to detect also the fluorescence from the Air (Ar K↵) and probably
even the Sr L-lines.

80
 Once fixed the optimum configuration with the lens and the filter, an
XRF analysis on di↵erent standards was carried out to deeper verify the
efficiency in the high energy K-lines excitation.
An XRF spectrum of the bronze standard was recorded, both for calibra-
tion purposes and for estimating the capability of exciting the Sn K-lines. It
is compared (Fig. 5.10) with its spectrum registered with the XRF system
(ITABC) described in chapters 3 and 4. By this way, the di↵erent perfor-
mances in the excitation of elements, such as tin and antimony, between a
polyCO system (‘pXRF’) and a portable XRF spectrometer with high en-
ergy resolution but poor spatial resolution (‘MXRF’) can be observed. The
‘MXRF’ tube has a voltage of 60 kV, while we are working with 50 kV.
From the spectra we can observe that the two systems provides similar
results for the Cu K-lines. For the Sn K↵ the ‘pXRF’ gives a SNR 39 and
a net count rate 23.5, while ‘MXRF’ provides a SNR 35 but a net count
rate 130. For the Sb K↵ ‘pXRF’ gives a SNR of 0.44 and a net count rate
1.1, while ‘MXRF’ provides a SNR 4 and a net count rate 10. For both
the elements the Limits of Detection (L.O.D.) are of an order of magnitude
greater, but they are still detectable.

Figure 5.10 XRF spectra of the bronze standard registered with ‘pXRF’ (red)
and ‘MXRF’ (black).

Then, a first qualtitative comparison between the XRF spectra of the

gilded and enamelled standards given by ‘pXRF’ and ‘MXRF’ is made. Due
to the lack of a pointing system for precise positioning and repeatability
estimation, only a single run of measurements has been performed. Due
to the di↵erent operative conditions, the spectra have been normalized to
compare the relation between the di↵erent fluorescence lines (Fig. 5.11-
5.12.right).
The primary beam of ‘MXRF’ has a greater high energy fraction that
allows a more efficient excitation of Ag (22 keV) and Ba (32 keV) K-lines.
Although it clearly has better experimental conditions, Fig. 5.11 shows that

81
the polyCO still provides a good excitation on the substrate Ag K-lines. As
regards the barium in the red enamel, the polyCO reduces the SNR fom 13
to 5, as expected.

Figure 5.11 XRF spectra of the gilded (left: sample with gilding thickness 7.2
µm) and enamelled (right) silver samples collected with ‘pXRF’ (red) and ‘MXRF’
(black). The intensity have been normalized with respect to the total count rate
(considered as 100) in order to observe the di↵erent ratios between the fluorescence
lines.

Successively, the XRF spectra of the gilded silver standards were pro-
cessed by the PyMCA software wiht the method for the coating thickness
determination (chapter 3), in order to verify if the counts on Ag K-lines
are still sufficient for this estimation. From the results (Fig. 5.12) we can
conclude that the method is also reliable for this polycapillary-based setup.

Figure 5.12 Left: gilding thicknesses estimated from the XRF spectra on the
six gilded silver standards. The dashed line accounts for the ideal curve calcu-
lated=nominal. Right: zoomed area of the spectra shown in Fig. 5.11 for the
enamelled standard, with ‘pXRF’ (red) and ‘MXRF’ (black).

Having only one value for each standard, the error of the method have
not been estimated statistically. However, an average relative error < 10%
can be observed, except for the two cases (gilding thickness between 4-5 µm)
for which an error around 16% was found. This higher uncertainty could

82
be due to an incorrect positioning of the sample, as the sample-detector
distance is an important parameter in this procedure. The results could be
improved whereas a pointing system of the beam will be realized.
By a deeper observation of the spectra of the enameled sample (Fig.
5.12) we can see that the polyCO provides better SNR for K K↵ (1 vs 0.5)
and Ti K↵ (1.3 vs 0.8). From this observation, and the previous measures on
the marble sample with and without the filter, we can assume that without
the filter the results on the light elements would be even better, making this
alternative configuration a suitable solution for the glass matrices analysis.
This aspect will be deeply investigated in the following sections.
This preliminary study has demonstrated that exciting high energy flu-
orescence K-lines by using a common X-ray source with a maximum voltage
of 50 kV combined a polycapillary optics is possible. By testing a polyCO
optimized for Cu K↵ a reduction in the detection efficiency for the elements
of our interest has been observed, but this aspect was in part solved by a
proper beam filtering. Hence, we can reasonably assume that, by choosing
a lens optimized for higher energies, better results can be achieved. In addi-
tion, some tests comparing both the configurations (with and without filter)
suggest that the latter option could be still usedfor the characterization of
light matrices, such as glasses.

5.3 Selection and experimental characterization of

the system components
The di↵erent components have been chosen in order to satisfy all the re-
quirements that the final prototype will have to fulfill. In particular, an
excitation system (X-ray source and optics) able to excite the fluorescence
K-lines of the elements of our interest and a detector able to register such
signals have been selected. All the components have been chosen upon their
nominal parameters, however some aspects of the instrumentation has to
be experimentally characterized in order to evaluate their real behavior and
performance. For this purpose each component has been characterized in
the laboratory station XENA used in section 5.2, before the final design and
assembling of the prototype.

5.3.1 Transmission anode X-ray tube

To further improve the high flux beam focused by a polyCO, a transmission
anode tube has been chosen. It is characterized by a strongly reduced focus-
window distance allowing very close coupling of any optical component to
the tube anode (Fig. 5.13), allowing an easier design and assembling with
the optics. In addition, the transmission anode produces higher flux beam
and the attenuation of the lower energy range of the primary spectrum is

83
reduced.

Figure 5.13 Scheme of a transmission target X-ray tube.

Nowadays, attempts of making portable micro-XRF spectrometer for

cultural applications by means of an end-window tube have regarded only
its combination with a collimating pinhole, which can exploit the higher
intensity emitted by this kind of anode tube [61]. However, combining such
sources with a polycapillary optics would further improve the focused beam
intensity leading to shorter acquisition times, which is an important aspect
to consider when planning an in situ campaign.
A Moxtek transmission W anode X-ray tube (Fig. 5.14, Tab. 5.4) has
been selected, with the following parameters: 10-50 kV, 0-200 µA, focal
spot size 400 µm, 0.25 mm thick Be window, 92 emission solid angle, and
a total weight of 950 g (power supply and controller included, important for
the portability). The anode material (thickness 0.6 - 1.1 µm) is deposited by
sputtering on the internal side of the Be window. It is cooled by conduction
and its maximum operating anode shield temperature is 100 C. The target
is recessed of ⇠ 2.29 mm from the front end, but with the lens (e.g. a micro-
lens) of an input diameter smaller than the external Al collimator diameter
(4.5 mm) it is possible to get closer to the target, if necessary.

Figure 5.14 Moxtek tube and end window section.

84
 parameter avg. counts std. dev. RSD (%)
Stability 66910 400 0.60 (specification: < 1)
Repeatability 28639 162 0.57 (specification: < 1)

Table 5.4 Nominal stability and repeatability given by Moxtek for our specific
tube. They measured the stability at 20% detector deadtime, 50 kV, 250 samples
at 30 s intervals, and the repeatability at ‘15 s on - 5 s o↵’ intervals.

First of all, although the tube was declared properly shielded for use in
security chambers, we found out that also for our tests in the XENA cabinet
(shielded with lead panels and leaded glasses) an additional shielding was
required. In particular, the back of the tube, from which the high voltage
cables exit and go to the power supply, is just closed with some plastics,
therefore the stronger radiation emission (unwanted) comes from there. For
the characterization measurements in the laboratory station a first brass
shielding (Fig. 5.15) has been realized, but for the final prototype a “lighter”
version of it has to be considered. Due to the fact that the maximum tube
operating temperature is 100 C, but it is thought to work without any
additional shielding, in order to monitor the e↵ective temperature, also a
hole for a temperature sensor has been considered in the design.

Figure 5.15 Technical design and picture of the brass shielding.

Once resolved the radiosafety issue, the primary beam , produced by the
tube at its maximum voltage 50 kV (at which it will work for the XRF anal-
ysis) and minimum current (1 µA), was characterized by a direct measure of
the spectrum, for an acquisition time of 120 seconds, with the same Bruker
SDD detector used in section 5.2. As for the preliminary study, the tube W
anode fluorescence L-lines are visible (Fig. 5.16).

85
Figure 5.16 Primary spectrum emitted by the X-ray tube and corrected for the
detector efficiency.

5.3.2 Polycapillary lens

A Unisantis polycapillary lens optimized for the Mo K↵ line (17 keV, nom-
inal transmission 35%) has been selected. Its geometrical parameters (Fig.
5.17) are: Di 5.2 mm, Dmax 6.8 mm, Do 4.6 mm, L 111.5 mm, channel
internal diameter d ⇠ 8 µm. The size of the input spot (Si) collected by
the lens, for the energy of our interest (25 keV), has been estimated to be
149.61 µm (by the Eq. 2.8), which for the alignment procedure is conve-
niently smaller than the focal spot on the tube anode. The ✓c for X-ray
photons of 25 keV is 1.2 mrad, equivalent to 0.069 (by the Eq. 2.4).

Figure 5.17 Schematization of the lens, with the geometrical parameters indicated.
Di: input diameter. Do: output diameter. Dmax: maximum lens diameter. Si:
input spot size. So: output spot size.

The lens has been experimentally characterized as regards its IFD, OFD
and spot size. The IFD and OFD were determined according to the proce-
dures described in section 2.2 using the reflection W-anode tube, the Ortec
scintillator and the CCD camera used in section 5.2. The polycapillary IFD
and OFD resulted to be ⇠ 65 mm and ⇠ 43 mm, respectively (Fig. 5.18).
By considering the spot FWHM at the OFD distance and the CCD camera
pixel size, the spot size resulted to be ⇠ 145.6 µm.
With this geometry, the solid angle captured by the lens is 5.4 x 10 3 sr,
while a pinhole collimating the same spot size at the same distance collects
a solid angle of 3.84 x 10 7 sr. According to the Eq. 2.9, this solid angle

86
Figure 5.18 a) Counts as function of the distance source-lens, for the IFD deter-
mination. The optimum distance is comprised between 62 and 68 mm, indicating
also the lens depth of field. The two lines are related to the two angular alignment
positions. b) Graph related to the OFD determination. It reports both the spot
intensity and its sigma values (FWHM) as functions of the distance lens-camera.
The two sigma curves are related to the gaussian fits in the two axial directions of
the spot.

and the lens nominal transmission efficiency should result in a gain factor
of 7 x 107 for an energy of 17 keV.
To experimentally verify also the gain factor in the excited fluorescence
signal with respect to the pinhole, two XRF spectra of a reference glass
sample (Fluxana, Tab. 3.5) have been recorded. A di↵erent detector was
used for this purpose, a SDD from XGLab with an active area of 30 mm2 and
a polymeric window (as it is optimized for low energy). The acquisition time
was 120 s, and the reflection W anode tube was set at 50 kV and 500 µA.
For both the configurations, polyCO and pinhole, the sample was placed at
the same distance from the source. Fig. 5.19 shows the comparison between
the two XRF spectra. The better excitation provided by the lens, which
allows to detect elements otherwise not visible with the pinhole, is evident.
The polyCO provides an excitation gain of 3 orders of magnitude on, e.g.,
Ti K↵ (4.5 keV) and of 2 orders on Mo K↵ (17 keV).

Figure 5.19 XRF spectra of a reference glass, excited using a polycapillary optics
and a lead pinhole.

87
 Unfortunately, empirically determining the transmission efficiency as a
function of the energy was not possible, as it is experimentally complicated
to measure the beam intensity at the entrance of the lens, because of the
detector saturation.
The next step was characterizing the combination of the optics with the
selected transmission tube through a direct measure of the beam transmitted
by the lens. The optics has been aligned with the Moxtek tube (Fig. 5.20.a),
and then the SDD detector was placed in front of it with the external Pb
collimator to avoid saturation (Fig. 5.20.b). The tube settings (50 kV,
minimum current) were the same as for the primary beam characterization,
but the distance source-detector was di↵erent. Although this spectrum is
not quantitatively comparable with the primary one, we can observe how the
lens conveniently reduces the low energy fraction of the beam (Fig. 5.21),
being optimized for a higher energy range.

Figure 5.20 a) Alignment of the lens with the transmission tube, by means of the
Ortec scintillator. b) Direct measure of the transmitted beam.

Figure 5.21 Spectra of the tube (red) and focused by the polyCO (black). The
acquisition time was 120 s.

88
Figure 5.22 Spectrum of the beam focused by the optics. The intensity is in
logarithmic scale, to better appreciate presence of the ‘step’ at 37.4 keV.

When deeply observing at the transmitted beam, a sort of step appears

around 37.4 keV (Fig. 5.22). It seems related to some absorption e↵ect
taking place in the system, and by database the energy value corresponds
to the absorption edge of Ba K-lines. To determine if the barium is present
in the polycapillary glass, the lens was analyzed by XRF with both a micro-
XRF system (the one described in Chapter 4: W anode, 50 kV, 0.1 mA, 200
s) and our experimental set up so far arranged (transmission tube at 50 kV
and 0.2 mA, SDD detector, 120 s; Fig. 5.23). In the spectrum registered with
the micro-XRF system (Fig. 5.24.a), it is possible to observe the presence of
Si, K, Ca, As, Rb and Sr, all common elements of glass matrices. Ba L-lines
are visible, but the K-lines are not well defined due to the low excitation
efficiency of the system. In the spectrum measured with our set up (no
optics) the presence of the barium in the lens glass is confirmed by the
detection of both its K- and L-lines (Fig. 5.24.b). It can be explained by
the fact that, in some cases, barium is used to increase the refraction index
of the glasses.

Figure 5.23 Set up for the XRF analysis of the polycapillary lenses with the XENA
layout.

89
Figure 5.24 XRF spectra of the polycapillary glass obtained with a) the micro-
XRF system and b) our experimental set up (Fig. 5.23). In (a) the scattered Mo
anode K-lines are visible. In (b), in addition to the scattered W anode L-lines, the
atmospheric Ar K↵ and the Zr K-lines from the detector internal collimator are
detected.

If this little portion of the primary beam, in the high energy range, is
absorbed by the lens glass, then the polyCO acts, in part, as an absorber
instead that a focalizer. This behavior could be due to some defects present
in the optics. To further investigate this phenomenon, an image with a CCD
camera very close to the lens exit (distance ⇠ 1.6 mm) was taken. The tube
was set at 50 kV and 30 µA, and the exposition time was 4 s. In the image
(Fig. 5.25.a) some dark spots can be observed where the radiation is not
well transmitted: this could be due to the presence of some glass powder
occluding the channels, deposited during the lens cutting process.

Figure 5.25 a) CCD image of the transmitted beam. b) Layout of the spatial
scanning.

A spatial scanning along the lens exit section (Fig. 5.25.b) was carried
out with the SDD detector (equipped with the lead collimator to spatially

90
select the beam registered), to study the energy distribution in the trans-
mitted beam. The acquisition time was 120 s, and the tube voltage 50 kV.
By selecting the intensities of di↵erent energy ranges (Fig. 5.26), we can
observe that, in general, the high energy fraction is mainly transmitted by
the lens inner channels (as expected, having higher curvature radii). How-
ever, the presence of some defects is confirmed by the sudden decrease of
the radiation intensity (green circle) in a region of the lens. In the same po-
sition (B) the transmitted spectrum has also a very di↵erent shape from the
rest (Fig. 5.27): the lower energy background strongly increases probably
because, in that point, it is scattered by the glass matrix instead of being
focused.

Figure 5.26 Intensities of the low (as W L-lines) and high energy ranges in the spa-
tial scanning along the lens exit section. The dashed lines indicated an hypothetical
simmetric trend without defects in the lens.

Figure 5.27 Comparison between two transmitted spectra taken at the exit of the
lens, in position A and B (Fig. 5.26).

5.3.3 Beam filtering

Some tests on the copper and stainless steel filters have been repeated. The
measurements were carried out with the same SDD detector placed in front
of the lens, for an acquisition time of 120 s. The transmission tube was set

91
at 50 kV and 200 µA, with the filters between the source and the optics.
Although a combination of both the filters, in the preliminary study, was
taken into consideration, in order to reduce the attenuation of the overall
beam intensity the use of a single filter would be recommendable. From
this point of view, the stainless steel filter (35 µm) seems to be the best
choice (Fig. 5.28), as it better cuts o↵ the anode W L-lines (although not
completely) and at the same time provides the higher intensity in the en-
ergy range 20-30 keV: 91843 total counts respect to 23687 from the Cu 100
µm and 57554 from the s.steel(35 µm)+copper(25 µm). By removing the
lower energy fraction (< 15 keV) of the beam, the filter allows reducing the
spot size, as this is inversely proportional to the energy (higher energies are
transmitted only by the inner channels), as observed with the CCD camera
(Fig. 5.28). The images where taken at a distance shorter than the OFD,
in order to better appreciate the influence of the energy.

Figure 5.28 Left: comparison between the spectra for di↵erent filters. Right:
CCD images of the outcoming spot with and without the stainless steel filter.

Then, the contribute of the stainless steel filter in the XRF analysis has
been tested. XRF spectra of a standard bronze alloy (section 5.1) have been
taken with and without the filter (Fig. 5.29). The acquisition time was 120
s, and the transmission tube was set at 50 kV and 0.2 mA. The filter strongly
reduces the background increasing the SNR on Pb L↵ from 1 to 19 and on
Sn K↵ from 5 to 13, without a↵ecting the excitation of fluorescence lines at
high energies suchs as the Sn K↵, whose intensity remains practically the
same. On the other hand, without the filter the W L-lines provide a very
efficient excitation of the lower energy fluorescence lines, in this case the Sn
L-lines and the Pb M-lines. According to these observations, the prototype
can operate in two di↵erent but easily exchangeable configurations, with and
without filter, in accordance with the elements of interest under analysis.

92
Figure 5.29 Left: experimental set up (geometry: 90 and 45 ). Right: XRF
spectra of the bronze alloy, with and without the filter.

5.3.4 Detector
A Ketek VITUS 20 detector of the SI-Drift type, with energy resolution 139
eV at 5.9 keV, active area 20 mm2 , thickness 450 µm, and peaking time of
1-2 µs has been selected. It has been chosen because of its portability, very
good energy resolution, and capability of accepting high counting rates.

Figure 5.30 Ketek VITUS 20 detector.

Figure 5.31 XRF spectra of the reference glass registered with a ‘low energy’
and a ‘high energy’ detector. It can be observed that only the second one allowed
detecting the K-lines of elements like Ba, La and Ce.

To justify the need for a detector optimized for high energies (Be window,

93
proper electronic acquisition system), an XRF spectrum registered with it
for the Fluxana glass standard sample (Tab. 3.5) is compared (Fig. 5.31)
with one given by a detector optimized for low energies (a SDD from XGLab,
active area of 30 mm2 , polymeric window). In both cases the acquisition
time was 200 s and the selected polycapillary lens was used. The limit in
the detectable energy range of the other detector ( 25 keV) is evident.
Optimizing the source section (tube and optics) of the XRF system for
the excitation of high energy fluorescence lines is important, as well as the
capability of detecting such signals.
The choice of a detector with an active area larger than that of the SDD
used in the feasibility study (7 mm2 ) is due to the possibility of increasing
the counting rate, and the general sensitivity of the system. By comparing
the XRF spectra (Figs. 5.32-5.35, Tab. 5.5) collected with both of them on
di↵erent metal matrices, in the same operating conditions (50 kV, 200 µA,
200 s, steel filter applied), it is clearly possible to observe the improvement in
the signal detection and sensitivity. This helps to overcome the unavoidable
intensity decrease due to the polyCO optics with respect to an unfocused
XRF analysis.

Figure 5.32 Cu K↵ (8.05 keV) and Au L↵ (9.7 keV) calibration curves for silver
alloys. For both the elements, the curve slopes obtained with the 20 mm2 detector
are ⇠ 8.6 against ⇠ 2.6 from the 7 mm2 one.

Figure 5.33 XRF spectra of one silver standard sample (Cu 9%, Au 4%).

94
Figure 5.34 Pb L↵ (10.5 keV) and Sn K↵ (25.27 keV) calibration curves for bronze
alloys. For both the elements, the curve slopes obtained with the 20 mm2 detector
are ⇠ 4.5 against ⇠ 1.1 from the 7 mm2 one.

Figure 5.35 XRF spectra of one bronze standard sample (Pb 3.39%, Sn 2.34%,
Sb 0.14%).

active area 7 mm2 active area 20 mm2

element energy (keV) cps per unit cps per unit
Cr 5.4 3 11
Fe 6.4 2 8
Ni 7.5 2 6

Table 5.5 Average values of cps per unit for stainless steel standards, for their
consituent elements. With 3 standard of similar composition, it was not possible
to show a calibration curve as Figs. 5.32 and 5.34.

5.4 Experimental validation of the prototype

Once characterized each component of the final prototype, the next step
has been the empirical validation of the analytical performances of the as-
sembled system (‘phEMIX’, portable High Energy Micro-Xrf spectrometer),
although not in the final layout. XRF measures on various standard ma-
terials have been carried out in the XENA (XLab Frascati) experimental

95
station. The transmission X-ray tube, coupled with the selected polycap-
illary lens, was set at 50 kV and 200 µA, and the Ketek VITUS 20 SDD
detector was used, placed at 10 mm from the sample and with an acquisition
time of 200 s. The incident and take-o↵ angles were fixed at 90 and 45 ,
respectively.
The reference materials, analyzed to examine the elemental sensitivity
and L.O.D., were: silver standard alloys, bronze standard alloys , a 50 cent
coin, stainless steel standard alloys, and 3 standard glasses (see in the Ex-
perimental setup). On the silver and bronze alloys the measurements were
carried out with the filter, while on the stainless steel alloys and glasses
also the configuration without filter was used, as the unfiltered beam can be
useful to analyze only light matrices and elements.
The results obtained with pHEMIX are compared with the elemental
sensitivities and L.O.D. of the micro-XRF Unisantis system (‘mXRF’) and
the XRF ITABC spetrometer (‘MXRF’), with their default operative set-
tings described in the section dedicated to the case study.
Then, with the purpose of an early attempt of quantitative analysis (of
both the homogeneous and multilayered samples) by means of the latest
PyMCA version (section 1.4.2, thickness determination procedure described
in section 1.4.2, and chapter 3), some thin standard samples have been
analyzed (Tab. 5.3) in order to estimate the flux.
Finally, to investigate the prototype capability in detecting light ele-
ments (Z  14), early observed in the feasibility study, some XRF spectra
of unknown light matrices samples have been taken. The samples analyzed,
in addition to the 3 standard glasses already mentioned, were: a mechanical
anticorodal (aluminium alloy) component, an archaeological pottery frag-
ment, a spinel (MgAl2 O4 ) mineralogical sample, an homemade NaCl sam-
ple, 3 enamel samples (Tab. 5.2), and 4 roman glass mosaic tesserae (with,
blue, green, and yellow).

Figure 5.36 Experimental set up for the measurements with the helium flux.

To further improve such elemental sensitivity by reducing the signal at-

tenuation from the air, an helium flux has been applied in the path sample-
detector by means of a plexiglas collimator (aperture 4.8 mm) attached
to the detector (Fig. 5.36). With this configuration, the distance detector-

96
sample changes from 10 to ⇠ 15 mm. The XRF spectra have been registered
both with and without the helium flux, but same experimental layout (He
collimator).

5.4.1 Sensitivity and Limits of Detection

Silver alloys
For silver matrices, the sensitivity and L.O.D. regarding Cu K-lines and
Au L-lines have been evaluated. The comparison with mXRF and MXRF
is made in terms of cps. From the calibration curves (Fig. 5.37) and the
relative slopes (Tab. 5.6), we can observe that the mXRF provides the best
results, also thanks to its unfiltered primary beam, while pHEMIX shows the
worst performance with a resulting sensitivity a little lower than MXRF. The
average cps per unit given by pHEMIX for the Ag K↵, the major constituent
(Fig. 5.38), whereas with mXRF is 2 cps and with MXRF 62 cps. MXRF has
the best performance, as expected, but with pHEMIX a little improvement
respect to mXRF has been achieved.
However, as regards the L.O.D. (Tab. 5.7) pHEMIX provides results
comparable with the mXRF spectrometer and better than the MXRF one.
This improvement respect to the MXRF is in part due to the longer ac-
quisition time (200 s instead of 120 s), which reduces the problem of the
lower sensitivity. All the systems have L.O.D. of the order of hundreds of
ppm. In conclusion, for silver alloys, we can assess that pHEMIX has from
one side the good performances of the mXRF system for medium energy
fluorescence lines (Cu K-lines and Au L-lines) and, on the other side, little
improved sensitivity at high energies (Ag K-lines).

Figure 5.37 Cu K↵ (8.05 keV) and Au L↵ (9.7 keV) calibration curves for the
three XRF spectrometers, for silver alloys.

Cu K↵ Au L↵
system slope slope
pHEMIX 8.2 8.9
MXRF 8.9 12.2
mXRF 34.1 24.8

Table 5.6 Slopes of the calibration curves shown in Fig. 5.37.

97
Figure 5.38 XRF spectra obtained with the three systems for one of the silver
alloys standards (Ag 87%,Cu 9%, Au 4%).

Cu K↵ Au L↵
system L.O.D. (wt%) L.O.D. (wt%)
pHEMIX 0.025 0.026
MXRF 0.085 0.053
mXRF 0.017 0.022

Table 5.7 Average L.O.D. estimated for Cu K↵ and Au L↵ for the three systems.

Bronze alloys
In this case the sensitivity and L.O.D. have been evaluated with respect
to the Pb L-lines and Sn K-lines (Fig. 5.39 and Tab. 5.8). As regards
the Pb L-Lines, the results are similar to those for the Au L-lines in the
silver alloys. However, for the Sn K-lines pHEMIX presents an improvement
respect to the mXRF one, although the MXRF spectrometer still shows the
best performance, as expected.
As regards the L.O.D. (Tab. 5.9), with pHEMIX the best result on the
Pb L-line is achieved, and even for the Sn K-lines the performance (hundreds
of ppm) is much better respect to the mXRF (thousands of ppm) and closer
to the MXRF. In particular, by comparing the data for a single bronze
standard (Pb 3.39%, Sn 2.34%, Sb 0.14%) (Fig. 5.40 e Tab. 5.10), we can
observe observe that pHEMIX is able to detect the Sb K↵ line while the
mXRF one cannot do it.
For the bronze alloys, we can conclude that pHEMIX provides the best
results in the medium energy range (Pb L-lines) and strongly improves the
performance at high energies (Sn and Sb K-lines) respect to the laboratory
micro-XRF system.
Pb L↵ Sn K↵
system slope slope
pHEMIX 4.8 4.6
MXRF 5.7 57
mXRF 9 1

Table 5.8 Slopes of the calibration curves shown in Fig. 5.39.

98
Figure 5.39 Pb L↵ (10.5 keV) and Sn K↵ (25.27 keV) calibration curves for the
three XRF spectrometers, for bronze alloys.

Pb L↵ Sn K↵
system L.O.D. (wt%) L.O.D. (wt%)
pHEMIX 0.019 0.044
MXRF 0.036 0.013
mXRF 0.026 0.220

Table 5.9 Average L.O.D. estimated for Pb L↵ and Sn K↵ for the three systems.

Figure 5.40 XRF spectra obtained with the mXRF and pHEMIX for one of the
bronze alloys standards.

Pb L↵ Sn K↵ Sb K↵
system L.O.D. (wt%) L.O.D. (wt%)
pHEMIX 0.034 0.04 0.229
MXRF 0.046 0.006 0.035
mXRF 0.039 0.274 -

Table 5.10 L.O.D. estimated for Pb L↵, Sn K↵ and Sb K↵ (26.4 keV) on a single
bronze standard for the three systems.

For a visual overview on the results obtained for the metal alloys (silver
and bronze), in Fig. 5.41 the L.O.D. are reported as a function of the
respective fluorescence lines energies. pHEMIX equals the performances of
the mXRF in the low energy range and even better at high energies (> 25
keV), although in that range the MXRF spectrometer still provides the best
results.

99
Figure 5.41 Distribution of the L.O.D. (wt%) as function of the fluorescence lines
energy in metal matrices, for the three experimental systems.

Stainless steel alloys

In this case both the configurations, with and without the filter, has been
used, as were are dealing with elements (Cr, Fe, Ni) in an energy range that
could benefit from a further excitation by the anode W L-lines. Being the 3
stainless steel standards of similar composition, it was not possible to build
a calibration curve for the elements. Therefore, to compare the sensitivities
of the various systems, the average cps for each elements are reported in
Tab. 5.11. As expected, MXRF shows the better result on the Mo K↵
(17 keV), while pHEMIX with the unfiltered beam provides better results
even respect to the mXRF in the low energy range (Fig. 5.42). In addition,
only pHEMIX in both configurations is able to detect the small amount of
vanadium.
pHEMIX, no filter pHEMIX, filter mXRF MXRF
element cps cps cps cps
v 133 8 - -
Cr 379 11 40 6
Fe 309 8 37 4
Ni 223 6 19 2
Mo 27 16 - 56

Table 5.11 Counts per seconds for each element for the four systems. In the mXRF
case, the values on Mo are not reported, being a↵ected by a huge error due to the
scattering of the anode Mo K-lines.

As regards the L.O.D. (Tab. 5.12 and Fig. 5.43), the filtered pHEMIX
shows results very similar to the mXRF, with values of the order of hundreds
of ppm. The MXRF has the worse performance in the low energy range
(thousands of ppm), but the better in the high energies (tens of ppm).
However, our unfiltered configuration provides the best results in the low
energy range (tens of ppm) and improved ones at high energies (hundreds

100
of ppm). In addition, the use of the filter does not a↵ect at all the L.O.D.
on the Mo K↵.

Figure 5.42 XRF spectra obtained for one of the stainless steel standards, with
the four systems. On the left it is possible to see that the mXRF provides the more
intense signals on Cr K↵, Fe K↵ and Ni K↵, but has the worst energy resolution.
MXRF is the less efficient in the same energy range. pHEMIX provides spectra
well resolved both with and without the filter, and in the last case (right) also the
most intense fluorescence lines.

V K↵ Cr K↵ Ni K↵ Mo K↵
system L.O.D. (wt%) L.O.D. (wt%) L.O.D. (wt%)
pHEMIX, no filter 0.009 0.004 0.006 0.017
pHEMIX, filter 0.028 0.028 0.037 0.017
MXRF - 0.11 0.164 0.006
mXRF - 0.046 0.102 -

Table 5.12 L.O.D. estimated for the various constituents of the stainless steel
alloys, for the four systems.

Figure 5.43 Distribution of the L.O.D. (wt%) as function of the fluorescence lines
energy in stainless steel matrices, for the four systems.

101
Glass matrices
Also in this case a calibration curve could not be built, dealing with only
three standard with not a significant variation in the constituent element
amounts. Therefore, to compare the sensitivities of the various systems, the
cps relative to the measure on one standard (Fluxana) for the more signif-
icant elements are reported in Tab. 5.13. We can observe that pHEMIX,
without the filter (Fig. 5.44), provides the better results for the element
with Z  34, but is the worst for the others. However, the range of de-
tection is extended at both high energies (respect to the mXRF) and low
energy (respect to both mXRF and MXRF), as it is the only one allowing
the detection of Si K↵ (even with the filter). This is confirmed also by the
average L.O.D. estimated on the three standards for the most significant
elements (Tab. 5.14 and Fig. 5.45).
We can conclude that, as regards the analysis of glass matrices, pHEMIX
represents a good compromise between the performances of mXRF and
MXRF, and even improves the energy range of detection at low energies.
pHEMIX, no filter pHEMIX, filter mXRF MXRF
element cps cps cps cps
Si 24 1 - -
K 107 3 3 2
Ca 211 4 9 6
Ti 425 10 23 15
Se 26 2 2 6
Sr 166 70 293 314
Y 71 31 133 139
Cd 10 7 3 248
Ba 8 7 - 406

Table 5.13 Counts per seconds for the most significant elements in the glass stan-
dard Fluxana, for the four systems.

Figure 5.44 Comparison between the spectra of the lead glass, obtained with our
system in both the configurations. It is evident the improvement in the detection
of the light elements without the filter.

102
 pHEMIX, no filter pHEMIX, filter mXRF MXRF
element L.O.D. (wt%) L.O.D. (wt%) L.O.D. (wt%) L.O.D. (wt%)
Si 0.382 6.293 - -
K 0.034 0.35 0.438 3.453
Ca 0.015 0.178 0.148 0.558
Ti 0.005 0.035 0.039 0.349
Fe 0.001 0.005 0.006 0.037
Pb la 0.019 0.016 0.017 0.04
Se 0.011 0.04 0.049 0.024
Sr 0.006 0.006 0.003 0.003
Y 0.004 0.004 0.002 0.002
Cd 0.018 0.016 0.035 0.002
Sb 0.039 0.036 0.033 0.013
Ba 0.127 0.078 0.148 0.019
Pr 0.042 0.02 - 0.013
Nd 0.044 0.157 - 0.099

Table 5.14 L.O.D. estimated for the most significant elements of the glass stan-
dards for the four systems.

Figure 5.45 Distribution of the L.O.D. (wt %) vs the energy fluorescence lines,
for some elements of interest in the glass matrices, for the four systems.

5.4.2 Low-Z elements detection: He flux tests

To investigate the possibility of further improvements in the detection of
low-Z elements by the pHEMIX configuration without filter, which has been
already proved to be more efficient than mXRF and MXRF in this energy
range, some XRF spectra on a set of both standards and ‘unknown’ samples
of light matrices have been collected. The measurements have been carried
out with (HE) and without (AIR) the helium flux, both in the same con-
figuration: no filter, He collimator applied, distance detector-sample ⇠ 1.5
mm. By this way it is possible to observe the net contribute of the He flux.
Then, the results obtained for the standard samples are compared with
those achieved in the original unfiltered configuration (previous section),
which represents the default operative condition when working without he-
lium. This comparison is made in order to understand if the He flux ef-
fectively improves the performances with respect to the pHEMIX normal

103
configuration, in order to eventually justify its application and relative op-
erative complications (carrying helium cylinder in situ, safety issues, etc.).
In all the spectra here presented the anode W L-lines will be visible, as
the unfiltered beam is used, and the attention will be focused only in the
low energy range ( 8 keV).

Sodium detection
First of all, in order to see if the helium flux can allow detecting very low-
Z elements such as Na (K↵ 1.04 keV) an XRF spectrum on a cooking salt
(NaCl) sample has been recorded (Fig. 5.46). In the spectrum the Cl K-lines
(K↵ 2.6 keV) are clearly visible (312 cps, SNR 74), with such an intensity
that also the escape peak is registered. Although the low SNR (1.1), also
the Na K↵ is detected, with 2 cps. Thus, the He flux e↵ectively helps to
detect light elements, as sodium cannot be observed neither with the MXRF
or even the mXRF.

Figure 5.46 XRF specrum of the NaCl sample, measured with the He flux.

Pottery matrix
The matrix of archaeological pottery is usually characterized by the presence
of light elements such as Si (K↵ 1.7 keV), K (K↵ 3.3 keV) and Ca (K↵ 3.7
keV). From the comparison between the XRF spectra (Fig. 5.47 and Tab.
5.15) we can observe that the He flux improves the sensitivity only on Si
K↵, and obviously eliminates the fluorescence of argon (K↵ 2.9 keV) from
the air path.
HE AIR
element cps SNR cps SNR
Si 5 3.9 1 1.2
K 9 5.3 8 5.1
Ca 36 22.2 32 17.1
Ti 6 2.4 6 3.5
Mn 5 2.1 5 2.9
Fe 322 82.4 322 84.8

Table 5.15 Counts per seconds and SNR for the most significant elements in the
pottery matrix, obtained with and without the He flux.

104
Figure 5.47 XRF specra of the archaeological pottery sample, measured with and
without the He flux.

Mineralogical matrix
The analyzed spinel sample is characterized by the presence of Mg (K↵ 1.25
keV), Al (K↵ 1.4 keV), and Si. From the comparison between the XRF
spectra (Fig. 5.48 and Tab. 5.16) we can observe that the He flux only very
slightly improves the sensitivity on the Al K↵ and Si K↵, while curiously
the results on the other elements (Ca, Ti, V, and Cr) seems even better
without it. In addition, without the He flux another line appears (labeled
with ‘?’) where the Mg K↵ should be, but the strange shape of the peak
can suggest that it is due to some other e↵ect.

Figure 5.48 XRF specra of the spinel sample, measured with and without the He
flux.

HE AIR
element cps SNR cps SNR
Al 0.9 0.8 0.4 0.5
Si 1.6 1.3 1 1.2
Ca 3 2 5 6.8
Ti 0.7 0.9 1.5 1.7
V 0.2 0.1 1.6 2.2
Cr 0.4 0.6 1 1.7

Table 5.16 Counts per seconds and SNR for the most significant elements in the
spinel matrix, obtained with and without the He flux.

105
Enamel matrix
As regards the enamel samples, we focused only on the Si K↵ and K K↵,
which are characteristics of the majority of the glass matrices. In all the
three samples (Figs. 5.49-5.51, Tab. 5.17) we can observe that the He flux
improves the detection on both the elements, but not other changes are
evident (except for a higher intensity on the Pb M-lines for the yellow and
black enamels).

Figure 5.49 XRF spectra of the red enamel sample, measured with and without
the He flux.

Figure 5.50 XRF spectra of the yellow enamel sample, measured with and without
the He flux.

Figure 5.51 XRF spectra of the black enamel sample, measured with and without
the He flux.

106
 HE AIR
Si K Si K
element cps SNR cps SNR cps SNR
red 12 4.4 179 17.7 2 1.5 135 17.4
yellow 8 1.8 12 0.8 1.6 0.7 8 0.6
black 10 2 37 10.2 2 1.7 27 8.8

Table 5.17 Counts per seconds and SNR for Na K↵ and Si K↵ in the enamel
matrices, obtained with and without the He flux.

Glass matrix
Archaeological glass mosaic tesserae are usually a sodic glass type or a mixed
one (Na base, with K in trace, as it seems to be in this case), therefore we
focused only on Na K↵ and Si K↵. In all the samples (Figs. 5.52-5.55,
Tab. 5.18) we can observe that the He flux improves the detection of the
Si K↵, and seems to allow even the Na K↵ detection. A strange behavior
is observed without the filter, in all the cases, near the energy of the Mg
K-lines, as in the spinel sample. If the Mg was in the glass matrix, we should
observe it with the filter, while this ‘peak’ (labeled with ‘?’) is probably due
to some other e↵ects maybe related to the presence of the He collimator,
still unclear.

Figure 5.52 XRF specra of the with glass tessera sample, measured with and
without the He flux.

Figure 5.53 XRF specra of the with blue tessera sample, measured with and
without the He flux.

107
Figure 5.54 XRF specra of the with yellow tessera sample, measured with and
without the He flux.

Figure 5.55 XRF specra of the with green tessera sample, measured with and
without the He flux.

Na Si Si
HE HE AIR
element cps SNR cps SNR cps SNR
white 2 1.6 27 7.9 5 2.4
blue 147⇤ 6 29 9.7 6 3.1
yellow 3 1.7 21 8.2 3 1.8
green 1 0.9 25 7.8 5 2.9

Table 5.18 Counts per seconds and SNR for Na K↵ and Si K↵ in the tesserae
glass matrices, obtained with and without the He flux. ⇤ Such high value on Na is
probably an outlier.

Comparison with the no-He configuration

Here we compare the XRF spectra for 2 glass standard (lead glass and
BRC3) measured in the He configuration (with and without the helium flux)
with those collected in the section dedicated to the study of the L.O.D. of
pHEMIX (default configuration, without filter, here referred to as ‘pHEMIX,
no filter’). We found out that, although in the same conditions the He flux
improves the sensitivity on the Si K↵ and a bit also on the K K↵, pHEMIX
provides much better results (Figs. 5.56-5.57): the overall intensity of the

108
spectra is much higher, on the K K↵ we have double cps, and on the Si
K↵ a little but still distinguishable improvement is observed. This could be
explained by the fact that the contribute of the He flux is strongly attenuated
by the longer detector-sample distance and the presence of the He collimator,
which reduces the detector active area (although the collimator matrix is not
a strong absorber, when dealing with the fluorescence of low-Z elements such
as Si and K it becomes important).

Figure 5.56 XRF spectra of the glass standard BRC3, measured with and with-
out the He flux, and compared with the spectrum from the ‘pHEMIX, no filter’
configuration.

Figure 5.57 XRF spectra of the lead glass standard, measured with and with-
out the He flux, and compared with the spectrum from the ‘pHEMIX, no filter’
configuration.

In the case of the Al alloy (Fig. 5.58), the He flux provides the highest
cps on the Al K↵, but with the ‘pHEMIX, no filter’ we achieve almost
comparable results. In the end, we can conclude that the contribute given
by the helium flux (at least with the present configuration) does not justify
its employment in favour of the default pHEMIX configuration, as with the
last one we achieve comparable and even better performances.

109
Figure 5.58 XRF spectra of the Al alloy, measured with and without the He flux,
and compared with the spectrum from the ‘pHEMIX, no filter’ configuration. On
the Al K↵ we have: 9 cps (AIR), 97 cps (HE), 76 cps (pHEMIX, no filter).

5.4.3 Quantitative analysis

The final step of this study is a first attempt of quantitative analysis of
the XRF spectra collected with pHEMIX on the standard materials in the
section dedicated to the L.O.D. estimation. In particular, the latest version
of PyMCA, validated in chapter 3 (with the MXRF system), has been ap-
plied for the data treatment. By this way the suitability of the pHEMIX
system for quantitative analysis application and the capability of the soft-
ware to manage the particular shape of the primary beam focused by the
polycapillary lenses (with and without filter) will be evaluated.

Flux overview
An important parameter to be considered when using PyMCA for quanti-
tative analysis is the flux, usually determined by means of some standards.
Here we observe the flux values estimated on a set of thin samples (Tab.
5.3), with and without the filter. The flux changes for every material, and
for each one is determined by referring to the fluorescence line intensity. In
the configuration with the filter, a negative correlation (Fig. 5.59) with the
samples densities (but not with the fluorescence energies or the thicknesses)
is observed. When both the K- and L-lines of the element are detected (Mo,
Ag, Sn), the calculated flux is equal for both the group of lines.
As regards the configuration without filter, the results are di↵erent. Ba-
sically, two main ranges of flux are found (Fig. 5.60), one for the fluorescence
lines with energies lower than the anode W-lines (and therefore much more
excited by the unfiltered beam), and the other for the higher energies. Con-
sequently, when both K and L-lines are present, also in the sampe sample
two di↵erent flux values are found. The only exception is represented by the
iron, which shows a di↵erent behavior also with the filter: maybe it is due
to something in the sample holder a↵ecting the analysis.

110
Figure 5.59 Flux values as function of the sample densities. Measurements with
the filter.

Figure 5.60 Flux values as function of the sample densities. Measurements with
the filter. In this case the tungsten sample was not analyzed, for obvious reasons,
and also the Cu K-lines were strongly disturbed by the anode fluorescence.

Therefore, the flux to use has to be carefully chosen for the di↵erent
matrices under analysis.

Homogeneous matrices: quantitative analysis

The quantitative analysis has been performed only on the metal standards
alloys. As already observed in Chapter 3, PyMCA does not provide very
reliable results for the glass standards used, maybe due to a complication in
its calculations given by the huge amount of elements present in trace in each
of them. Therefore, we decided to not analyze them in this section, as the
procedure probably needs to be revised, otherwise it would only introduce
additional errors in the quantification.

111
 Bronze alloys
As already mentioned, for the bronze and silver alloys only the configu-
ration with the filter was used. From the results (Figs. 5.61-5.62 and Tab.
5.19) we can observe that very good performances are achieved on Pb, and
in particular on Sn, as one of the main goal was to realize a system useful
for the analysis of elements with medium-high Z. Also the quantification on
Zn is good, and even the results on the copper (the major constituent) are
improved respect to those provided by the previous PyMCA versions.

Figure 5.61 Calculated values of Pb and Zn. The dashed line accounts for the
ideal curve calculated=nominal. For the Pb, except for an outlier, the maximum
relative error is ±10%, and the absolute errors are < ±0.05 wt%. For the Zn, the
relative errors are < ±20% and the absolute errors < ±0.5 wt%: in this case the
results for the samples with very low amounts of Zn (±0.09 wt%) are not reliable,
as we have an overlapping between the Cu K (from the matrix) and the Zn K↵.s

Figure 5.62 Calculated values of Sn. The dashed line accounts for the ideal curve
calculated=nominal. The optimal excitation of the Sn L-lines allowed performing
the quantitative analysis also on them, and the calculated values are comparable
with those obtained from the K-lines, although these seems the best. Regarding
the results from the Sn K-lines, the maxima relative and absolute errors are ±11%
and ±0.68 wt%, respectively.

112
 Cu wt% nominal value Cu wt% calculated value err% err (wt%)
87.4 91.51 5 4.11
87.7 83.94 -4 -3.76
87 82.17 -6 -4.83
87.1 83.87 -4 -3.23
86.4 85.98 -0.5 -0.42
89 109.1 23 20.1
94.04 111.6 19 17.56

Table 5.19 Calculated values of Cu.

Silver alloys
As regards the silver alloys, a greater variation in the results is observed
(Fig. 5.63), although no trends of systematic errors are present. As for the
bronze alloys, also in this case the quantification on the silver (the major
constituent), performed on its K-lines, results acceptable (Tab. 5.20).

Figure 5.63 Calculated values of Cu and Au. The dashed line accounts for the
ideal curve calculated=nominal. For the Cu, except for an outlier, the maxima
relative and absolute errors are ±35% and ±2.314 wt%, respectively. The optimal
excitation of the Au M-lines allowed performing the quantitative analysis also on
them, and the calculated values are comparable with those obtained from the L-
lines, although these seems the best. Regarding the results from the Au L-lines,
the maxima relative and absolute errors are ±25% and ±2.39 wt%, respectively.

Ag wt% nominal value Ag wt% calculated value err% err (wt%)

98 125.6 28 27.6
96 104.5 9 8.5
90 101.8 13 11.8
85 94.35 11 9.35
86 96.79 13 10.79
87 85.06 -2 -1.94
89 81.46 -8 -7.54
87 90.87 4 3.87
98 115.9 18 17.9
92 92.11 0 0.11

Table 5.20 Calculated values of Ag.

Stainless steel alloys

In this case the results for both the configurations, with and without
the filter, are presented (Tab. 5.21). In general, both the solutions result

113
efficient for the analysis of Cr, Mn, Fe, and Ni. However, without the filter
the best results are achieved, even of V (in trace) and Mo.
filter no filter
element nominal wt% calculated wt% err% err (wt%) calculated wt% err% err (wt%)
V 0.07 0.05 -23.0 -0.016 0.08 7.6 0.005
Cr 18.60 18.37 -1.2 -0.230 18.69 0.5 0.090
Mn 1.69 1.74 3.3 0.056 1.66 -1.6 -0.027
Fe 69.86 68.69 -1.7 -1.170 70.24 0.5 0.373
Ni 8.73 8.95 2.4 0.213 9.27 6.2 0.538
Mo 0.43 0.24 -43.9 -0.187 0.37 -12.8 -0.054

Table 5.21 Calculated values for the various constituents of the stainless steel
standards. Having the three standards a comparable composition, average values
are considered.

We can conclude that the combination of pHEMIX and the latest PyMCA
version can provide good results for the quantitative analysis of metal alloys.

Multilayered matrices: quantitative analysis and coating thickness

determination
Gilded silver sheets
Also in this case only the configuration with the filter was employed. The
same gilded standards of the feasibility study were analyzed. First of all,
the gilding thickness was determined for all the samples (Fig. 5.64.a): very
good results were found for four standards (relative errors < ±5%), but for
two of them (relative errors -11% and -25%, respectively) the higher errors
are probably due to some bad positioning of the samples (due to the lack of
a pointing system). For these two cases the errors in the coating thickness
clearly propagate in the quantitative analysis of the substrate silver alloys
(Ag 92.5%, Cu 7.5%).

Figure 5.64 a) gilding thickness calculated values. The dashed line accounts for
the ideal curve calculated=nominal. b) flux calculated values; as expected, also
for the flux we have two outliers, related to the errors in the coating thickness
determination. From these values it is possible to obtain a calibration curve to find
the proper flux for the coating thickness found.

114
 The flux values to be used in PyMCA have been determined by taking
into account the di↵erent densities of each sample, influenced by the various
gilding thicknesses (Fig. 5.64.b). Except for the last two samples, very
good results on both copper (relative errors < ±10%) and silver (relative
errors < ±3%) are obtained. The errors on the copper amount for the last
two standards are due to both the errors in the gilding thickness estimation
and the very low Cu K-lines intensity, strongly absorbed by the increasing
coating thickness.
Cu Ag
standard thickness (µm) calculated wt% err% calculated wt% err%
1.967 7.956 6.1 92.42 -0.09
2.7 7.595 1.3 91.95 -0.59
4.143 7.97 6.3 90.32 -2.36
4.44 8.198 9.3 90.36 -2.31
5.87 2.025 -73.0 83.63 -9.59
7.3 1.475 -80.3 72.61 -21.50

Table 5.22 Calculated values of Cu and Ag. The last two rows should not be
considered, as related to the errors in the thickness determination.

PVD coatings on stainless steel alloys

For these samples both the configurations, with and without filter, were
used, and the results are presented (Tabs. 5.23-5.24). The determination of
the coating thickness result to be not as good as for the gilded silver sheets,
and the worst results are for the TiTiN layer, probably because of the low
attenuation of the Fe K↵. There is no di↵erence between the values obtained
with and without filter. Although the errors in the coating thickness deter-
mination, the results of the quantitative analysis can be considered quite
acceptable, but unlike for the uncoated stainless steel standards this time
the better performance is achieved with the filter.
FILTER NO FILTER
coating (µm) calculated thickness (µm) err% calculated thickness (µm) err%
Mo 3.2 37 3 29
element calculated wt% err% calculated wt% err%
Cr 18.15 -0.7 18.46 1.0
Mn 1.278 -23.2 1.128 -32.2
Fe 61.06 -12.1 67.1 -3.4
Ni 7.614 1.5 8.453 12.7

Table 5.23 Calculated values for the Mo coating and the substrate composition.

FILTER NO FILTER
coating (µm) calculated thickness (µm) err% calculated thickness (µm) err%
TiTiN 4 64 3.9 60
element calculated wt% err% calculated wt% err%
Cr 19.78 8.2 19.32 5.7
Mn 1.608 -3.4 1.437 -13.6
Fe 75.41 8.6 77.88 12.1
Ni 9.462 26.1 9.856 31.4

Table 5.24 Calculated values for the TiTiN coating and the substrate composition.

115
5.5 Mechanical design
In the final prototype (Fig. 5.65.b), the measuring head (meaning the poly-
capillary lens as the source, the detector, and a pointing system consisting
of a couple of laser) must allow getting close to the surface of the object
under analysis, also when it is not conveniently flat (as for the “3D” stat-
ues). Due to its portable nature, the spectrometer will be frequently moved,
therefore to ensure the alignment between the lens and the detector, they
should be immovable, by fixing the entire measuring head. For this purpose,
we decided to apply an alignment device to the X-ray tube instead that to
the lens. By this way, the lens, the detector and the laser will have to be
aligned only once and then fixed, while it will be possible to eventually re-
align the source every time it will be required. To align the tube, an optical
component from the Siskiyou has been chosen (Fig. 5.65.a), characterized
by 5 degrees of freedom (xyz✓ ), and the possibility to lock the positions.
It can hold the tube head, including its final shielding.

Figure 5.65 a) Siskiyou component, b) design of the protoype measuring head.

116
Conclusions

Various aspects of the XRF spectrometry, with a particular attention to its

application in the cultural heritage field, have been discussed in this work.
The experimental parts focused on the data treatment, and the feasibility
of a portable micro-XRF spectrometer for the investigation of large and
immovable objects characterized by medium- and high-Z elements.
First of all, the latest PyMCA version for the quantitative analysis of
various matrices has been tested. The code presents two di↵erent imple-
mented functions: a Monte Carlo (MC) simulation plug-in integrated with
the XMI-MSIM software, which calculates correction coefficients for various
e↵ects taking place in the matrix (such as Compton scattering), and a SE
function that considers the secondary fluorescence in the fit processing. The
XMI-MSIM plug-in has been tested only for homogeneous matrices (metals
and glasses), as it is not implemented for multilayered samples yet. For
metal matrices, such as silver and bronze alloys, an evident reduction on
the quantification errors was observed. However, this function has to be run
every time a fit is performed and the procedure is time consuming, in par-
ticular, if an advanced and powerful computer is not available it can take
15-30 minutes every time. When dealing with large amounts of data, as
usual in an investigation campaign, this aspect can prevent its application.
On the other side, the SE function is much faster. Hence, the respective
performances have been compared as regards stainless steel alloys, where
the secondary enhancement e↵ects between Cr, Fe and Ni are appreciable,
and some glass matrices. As regards the steel alloys, the SE function pro-
vides the most reliable results, with maximum relative errors ⇠ 10%. For
the glass standards, good results have been observed for a lead glass matrix
with both the options (maximum relative errors ⇠ 10%.). In particular, the
SE function provides very good results (relative errors < 4%) even for K and
Ca, which usually present some quantification problems in the spectra reg-
istered with conventional portable XRF systems. Unlike, for glass matrices
containing several elements in trace amounts the results are not satisfying at
the moment: maybe the presence of a high amount of variables induces some
additional errors and/or complications for the algorithms. Successively, only
the SE function was applied for the analysis of the coated steel samples, as
it resulted to be the best option for this kind of matrix. The determination

117
of the coating thicknesses was based on the attenuation of the substrate
iron fluorescence, and resulted to work well for a Mo upper coating (max
relative error 11%), less for a TiTiN layer. Despite of this, in both cases the
quantitative analysis of the steel substrate gave very good results (relative
errors < 4%). This method could be useful also to monitor the deposition
of thin coatings, in the research and industrial field.
In the presentation of the case study the advantages and disadvantages
of portable XRF and micro-XRF spectrometers have been illustrated. A
portable XRF optimized for the excitation of high energy fluorescence lines
is fundamental for the analysis of high-Z elements, but is characterized by
a poor spatial resolution that can often preclude its application to the anal-
ysis, e.g., of enameled silver plates finely detailed. On the other hand, a
transportable micro-XRF system (a laboratory instrument) combined with
a polycapillary optics is perfect for this kind of objects, and the exciting
spectrum is well suited for the analysis of glass matrices (characterized by
low-Z elements). Thus, the presence of the optics strongly reduces its ca-
pability of detecting high-Z elements K-lines (such as Ba), and the sample
chamber (122x116x78 mm) limits its application to small-sized objects.
Our main goal was combining the strength keys of both and reducing the
respective limits in a unique portable system, or at least achieving a com-
promise between their performances. To realize such a novel spectrometer
(‘pHEMIX’, portable High Energy Micro-Xrf spectrometer), the instrumen-
tal components have been carefully selected. A polycapillary optics with
a transmission optimized for Mo K↵ (17 keV), a working energy range up
to ⇠ 40 keV and a spot size of ⇠ 145 µm was chosen, and coupled with a
transmission W anode tube (50 kV, 200 µA). The SDD detector was selected
according to its very good energy resolution (130 eV at 5.9 keV) and ca-
pability of accepting high counting rates (active area 20 mm2 .peaking time
1-2µs). Two di↵erent operating configurations can be easily and usefully
employed: with and without filtering the primary beam. A stainless steel
filter, easily removable, cuts o↵ the tube anode W L-lines, strongly reducing
the noise in the registered XRF spectra (in the low-medium energy range),
and relatively enhances the sensitivity for the heavier elements, although
the overall spectral intensity is reduced (still avoiding e↵ects of detector sat-
uration). By removing the filter, the anode W L-lines strongly increase the
excitation of the low-Z elements, important in the analysis of glass matrices.
The system obtained by assembling the selected components has been
validated, in particular in terms of Limits of Detection (L.O.D.) in function
of the fluorescence lines energies, for metal and glass matrices. The perfor-
mances have been compared for those of the portable XRF and transportable
micro-XRF spectrometers used in the case study, which should have the best
performances at high and low energies, respectively. As regards the metal
matrices, the results can be divided for three energy ranges: low (5-8 keV:
e.g. K-lines of V, Cr, and Ni), medium (8-17 keV: e.g. K-lines of Cu, and

118
L-lines of Au and Pb), and high (17-27 keV: e.g. K-lines of Mo, Sn, and Sb).
pHEMIX provides L.O.D. of the order of hundreds of ppm in all the ranges.
In particular, in the low energy range it presents the best performances, even
better than the laboratory micro-XRF as it is the only one able to detect
the V K↵ (4.9 keV) in trace amounts. For the medium energies, pHEMIX
and the micro-XRF system shows the best, and similar, results. In the high
energy range, the portable XRF is the most efficient one, but our system
L.O.D. are of an order of magnitude better than the micro-XRF ones.
In the glass matrix case, pHEMIX equals the L.O.D. of the other two in-
struments in an energy range comprised between 10 and 26 keV. In addition,
it extends the upper limit of the detection range respect to the micro-XRF
system, allowing to register the fluorescence of even Pr and Nd (37 keV)
with L.O.D. of thousands/hundreds of ppm, although not as well as the
portable XRF. Furthermore, it has the best performances for energies < 5
keV, being the only one able to detect the Si K↵ (1.7 keV), and even Al and
Na.
Finally, the data treatment for the metal standard alloys, both homo-
geneous and multilayered, has shown that the spectra collected with this
experimental layout can be reliable also for the quantitative analysis.
In conclusion, the portable micro-XRF system assembled equals the per-
formances of its laboratory version for a medium energy range, has better
performances at high energies up to 32-37 keV (while others portable com-
mercial polycapillary based micro-XRF spectrometers work up to Sb K↵,
27 keV), although worst than a non-focused XRF device, and extends the
low energy detection range even without the need of vacuum or helium flux
conditions. These parameters make the system proposed quite versatile, an
important aspect to be considered when planning an investigation campaign.

119
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