Material science, Cultural heritage and Environmental control 0 2 Copyright © 201 7 by Damiano Martorelli All rights reserved . No part of this… [611952]

DAMIANO MARTORELLI

XRF/XRD COMBINED
SPECTROSCOPY
WITH ANALYSIS SOFTWA RE
for material cha racterization
in the fields of
Material science, Cultural heritage
and Environmental control

0

2 Copyright © 201 7 by Damiano Martorelli

All rights reserved .

No part of this publication and work can be reproduced in any form without the written permission of the Author .

Foreword

3 To my parents

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4

Foreword

5 FOREWORD

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6 SUMMARY

FOREWORD ________________________________ ________________________________ ________________ 5
SUMMARY ________________________________ ________________________________ _________________ 6
1. INTRODUCTION ________________________________ ________________________________ ________ 8
2. X-RAYS ________________________________ ________________________________ ________________ 9
2.1 A BIT OF HISTORY ________________________________ ________________________________ _____ 9
2.2 GENERAL PROPERTIES AN D PRODUCTION ________________________________ ____________________ 10
3. X-RAY DETECTORS ________________________________ ________________________________ _____ 12
3.1 DIRECT AND INDIRECT D ETECTION ________________________________ _________________________ 12
4. CALIBRATION OF XRF D ETECTOR ________________________________ _________________________ 13
5. CASE STUDY: VENETIAN SESINI ________________________________ ___________________________ 14
5.1 THE HISTORICAL CONTEX T ________________________________ ______________________________ 14
5.2 AIM OF THE PROJECT ________________________________ ________________________________ __ 16
A. APPENDIX – SDD DETEC TOR BY KETEK ________________________________ _____________________ 19
A.1. SDD BOX GEOMETRY ________________________________ ________________________________ _ 20
A.2. SDD GEOMETRY ________________________________ ________________________________ ____ 20
A.3. OPERATION REQUIREMENT S ________________________________ _____________________________ 22
A.4. AXAS -D DETECTOR BEHAVIOUR ________________________________ __________________________ 23
B. APPENDIX – BRAVAIS L ATTICES ________________________________ __________________________ 25
C. APPENDIX – ATOMIC EL EMENTS ________________________________ __________________________ 27
C.1. BERYLLIUM ________________________________ ________________________________ ________ 27
C.1.1. Production ________________________________ ________________________________ __ 28
C.2. ALUMI NIUM ________________________________ ________________________________ _______ 29
C.2.1. Production ________________________________ ________________________________ __ 29
C.3. SILICON ________________________________ ________________________________ __________ 30
C.3.1. Productio n ________________________________ ________________________________ __ 30
INDEX ________________________________ ________________________________ ____________________ 40

Summary

7 INDEX OF FIGURES ________________________________ ________________________________ __________ 42
INDEX OF TAB LES ________________________________ ________________________________ ___________ 43
REFERENCES ________________________________ ________________________________ _______________ 44

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8 1. INTRODU CTION
To be defined

X-rays

9 2. X-RAYS
X-rays are electromagnetic radiation with λ in the range between 10-3 and 10 nm: in the area of
long-wavelength they reach the ultraviolet radiation, while in the short -wavelength side they have in
common a part with -rays.

Figure 2.1
Nowadays we know that X -rays are a part of the electromagnetic spectrum (Figure 2.1), but this
is a result which required a long time to be reached, in the past century.
2.1 A bit of history
The name “X -rays” with the “X” reflects the unknown nature of the
rays first discovered by Wilhelm K. Roentgen (1845 –1923) , for which he
won the Nobel Prize in 1901: Roentgen and his contemporaries have no
idea of the fact that X -rays were part of the electromagnetic spectrum [18].
Without ent ering into the details of the long research history about X –
rays, which is out of the scope of the present research, is worth of
remembering the fact that X-ray spectroscopy dates back to 1909, when
Charles G. Barkla found a connection between X -rays radiating from a
sample and the atomic weight of the sample; the same scientist had already
contributed , in 1905, to the discovery of the polarization of X -rays,
confirmed by other scientists some years later .
Figure 2.2 Wilhelm
Konrad Roentgen
(Wikipedia .c.c.)

2

10
After him, in 1913, Henry G. J. Moseley helped in numbering the
elements using X -rays: he noted that the K line transitions in an X -ray
spectrum moved the same amount each time the atomi c number increased
by one (Moseley, 1913/14).
In the same year, followed the discovery of the diffraction of X -rays by
Max von Laue [25], which opened new frontiers in this field.
Moreover, Moseley is credited with the revision of the periodic tables,
from increasing atomic weight base, to atomic number base thanks to his
studies on X -rays.
He later laid the foundation for identifying elements by establishing a
relationship between frequency (energy) and the atomic number, a basis of X -ray spectrometry (the
so called Moseley’s law ).
2.2 General properties and production
All electromagnetic waves are basically the same: the only difference is wavelength, i.e. the
distance between adjacent wave crests. Wavelengths decrease to the left and get longer to the right
in the diagram above (Figure 2.1).
X-rays are invisible to human eyes , and propagate in straight lines at the velocity of the light, i.e. 3
× 108 m·s-1. This means that in o ur range of interest , they correspond to photons with energy E
~100 eV ÷ 1 MeV, because the wavelength of the photon is correlated to energy through the
Planck's Law :
=ℎ𝑐
𝐸 (2.1)
where E is the energy in kiloelectronvolt (keV), h = 4.135×10−15 eV⋅s is the Planck constant , c the
speed of light and hence hc = 1.2398 keV⋅nm.
X-rays are not affected by electrical and magnetic fields, and can be reflected, diffracted, refracted
and polarized. They are produced when a high energy beam of charged particles (electrons, protons
or -particles) impact upon a specimen, with an interaction with the Coulomb field of the nucleus
of the atoms and the deceleration of the particles.
In this interaction, according to classical electromagnetic theory, the energy lost by the charge
particles as photons generates a radiation with broad band of wavelength: this radiation is called the Figure 2.3 Henry G. J.
Moseley (Wikipedia c.c.)

X-rays

11 “continuum” [18,24] or, in German language, Bremstrahlung (from the German name Strahlung which
means “radiation” and the verb bremsen which means “to brake”) .
Bremsstrahlung (Figure 2.4) is a continuous spectrum of
radiation akin to a “white light” source ; since most particles
have different level of interactions with atoms , so a whole
range of X-ray energies is produced.
What determines the energy of the X -ray photons is the
starting energy of the particles: higher energies are able to
make higher energy photons, and thus “harder”, higher
energy X-rays would be generated.
The typical intensity -energy distribution is showed in
Figure 2.4. Because through Planck law the energy is inversely proportional to wavelength, when we
have the maximum photon energy, we also have the minimum of wavelength min. Increasing the
energy of incident particles, increases the maximum energy of the Bremstrahlung and decrease
proportionally the min.
In an X -ray tube (the typical source of X -rays in a laboratory), the continuum spectrum is then
characterized by the maximum excitation e nergy of electron, as following:
=ℎ𝑐
𝑒𝑉0 (2.2)
where e is the electron charge, is the Planck constant , c the speed of light and V0 is the potential
difference applied to cathode and anode in the tube , where anode is the target material which
produces the continuum .

Figure 2.4 Example of Bremstrahlung

3

12 3. X-RAY DETECTORS
In order to collect data about X -ray interactions with matter, we need instruments called
detectors.
Every detector has a different structure which depends not only on the material used for
production, but also on the type of X -ray radiation we want to collect.
In this chapter, we are going to remind briefly detector principles, and then we will focus on the
types used in the research project.
3.1 X-Ray detection
X-ray detectors are devices used to measure the flux, spectrum, and/or other properties of X –
rays. Detectors can be divided into two major categories:
1. imaging detectors , e.g. photographic plates and X -ray photographic film s, now mostly
replaced by various digitizing devices ;
2. dose measurement devices , e.g. ionization chambers, Geiger counters, and dosimeters , which
are used to measure the local radiation exposure, dose, and/or dose rate , in order to verify ,
for example, radiation protection equipment.
For the scope of this work, we concentrate on the group of detectors which are devoted to
collect and the flux intensity of the X -Rays. All of them use the interaction of X -Ray wit h matter
[26] and, in this context, we can distinguish two classes [7]:
• direct digital detectors , so-called because they directly convert X -Ray photons to electrical
charge and then in a digital image;
• indirect detectors, which have intervening steps , for example first converting X -Ray
photons to visible light, and then an electronic signal.

Calibration of XRF detector

13 4. CALIBRATION OF XRF DETECTOR

5

14 5. CASE STUDY : VENETIAN SESINI
A project where the XRF/XRD combined analysis has been successfully performed is the study
about ancient Venetian coins of XVI Century, called sesini, a type of coins of small value for
everyday commercial transaction, nominally produced in a mixture of copper, silver and lead .
The opportunity has been provided by a closet accidentally discovered during restoration of a
building in the village of Ala, in the Province of Trento (Italy) .
To date, only the Venetian coins of greater value, in go ld and silver, have been investigated as to
their alloy composition and their internal structure [33].
The research investigates, for the first time, the characteristics of the Venetian sesini, using X -ray
spectroscopy because of both the precision of the i nstruments and the non -destructive analysis of
the samples. The aim is to analys e, with these techniques, not only the true alloy composition of
official coins according to the emissions reported in the documents of the period, but also the
structure of co unterfeit coins.
Furthermore, the goal is to investigate the real composition of coin alloy, which may possibly
provide indications on the origin of the raw material and to check whether there have been
variations in time of the alloy composition. The aim is to have a qualitative reference for comparison
in the future with coins from other findings where the wear of these coins does not allow a check of
authenticity. We expect that the alloy composition is not significantly affected by wear and this will
allow accordingly a good precision in identifying good coins from forgeries.
5.1 The historical context
If we look at the beginning of the XVI century, the idea of the nation as a kind of organism with
an economy and distinctive political and legal structures was only beginning to form ; the most
consolidated monarchies were situated on the Atlantic [5,36] .
The political landscape of Italy was dominated by wealthy, powerful, and largely independent
city-states, the most important of them being the Republic of Venice .
In central Europe a vast federation — the Holy Roman Empire — was acquiring legal and
political structures that would remain with it through the eighteenth century. In Figure 5.1, its
boundary is shown by a thick maroon line.

Case Study: Venetian sesini

15 Eastern Europe was characterized by sprawling monarchies, some of them centralized and
expanding — the Ottoman Empire — others more loosely organized, such as Poland -Lithuania.
Two major shifts were about to take place: the first occurred in 1519, when the Spanish
kingdoms of Castile and Aragon, the Low Countries (Flanders and the Netherlands), and Austria fell
to the heir of the Habsburg dynasty, Charles V (1519 -1556); in 1526 the dynasty acquired Bohemia,
Silesia, and Hungary as well.

Figure 5.1 The Europe at the beginning of the XVI century (Source: http://maplists.com )
The second shift involved Turkish expansion: under sultan s Selim I (1512 -1520) and Suleiman I
(1520 -1566), Ottoman power enveloped Wallachia , almost all of Hungary, the Levant (Syria and
Palestine), and Egypt.
Habsburg Charles V of Spain increased Spanish holdings in Italy as Holy Roman Emperor from
1530 to 1558, leaving only Venice and the Papal States outside of Habsburg control (dashed black
line of Figure 5.1).
In this complex political context, under the pressure of the Habsburg dynasty [46], the Republic
of Venice aimed to consolidate its presence in the strategi c territories in northern Italy which were
of recent acquisition , that is, the city of Brescia and all the area in today's eastern Lombardy up to
Bergamo.
For this purpose, during the rule of Doge Francesco Donato (1545 -1553) was mint a new type of
curren cy, called " sesino ", a coin made of a silver and copper mixture , in which the amount of
precious metal is less than half [33]. The Council of Ten ordered its first coinage by decree October

5

16 19, 1547, and it became a divisional coin of small value compared t o contemporary silver coins
called "ducats" and his s ubmultiples [29].
The sesino was a very successful coin in commercial transa ctions and was widely used and
accepted also outside the territories of the Venetian Republic to the point that, unfortunately, many
of northern Italy mints produced forgeries, which were made of a mixture with high content of
copper , and just a subtle difference in the subject depicted on the coin, a n imperceptible difference
to an inexperienced eye.
The most famous forgeries are those produced by the Mint of Frinco (1581 -1601), a fief of the
Mazzetti family in Piedmont; by the mint of Masserano (1584 -1629), by the mint of Passerano
(1581 -1598) and in the mint of the Tiberti family (second half of the sixteenth century).
Clandestine production of coins, not only sesini but also coins of higher value, caused
considerable damage to the economy of the Vene tian Republic in a period already critic as a
consequence of Ottoman expansion in the east and the changing of the commercial trade routes due
to the discovery of the New World [46].
Therefore, the Senate of Venice ordered in a first phase the withdrawal of coins with a
subsequent merger at the mint of Venice with a new impression. This did not discourage the
falsifiers, who adapted quickly.
Thus, i n a second phase the Venetian sesini were abolished by the decree of December 15, 1600,
and emissions were suspended permanently in the course of 1603, and were never resumed.
As evidence of the wide circulation of the Venetian currency, there are several findings, including
recent ones, in archaeological excavations in many areas of the Trentino Alto Adige region (Italy).
5.2 The samples o f the project
As basis materials for this research we use finds from the availability of archaeological funds from
the Trentino province (Italy). The analysis is performed on coins stored in Ala (TN) , coming from a
closet accidentally discovered during restoration of a building (the closet contained a large number
of coins from various periods, including about 60 sesini of different emissions). In the present
research project, we investigate 20 coins of this finding, divided in seven Doge series, ranging from
1554 to 1603 (the whole period of distribution and validity of the sesini).
All the coins have been validated and dated by Beate Marcinik, an expert in numismatics, upon
request of the Municipali ty of Ala (TN), owner of the coins.
In a first step, we have catalogue d and sort ed the coins according to different temporal
emissions.

Case Study: Venetian sesini

17 In the second step, we have analys ed with XRD and XRF spectroscopy every group of coins, to
create a grid of alloy data related to known samples.
5.3 The XRF data

5

18

Appendixes

Appendix – SDD Detector by Ketek

19 A. APPENDIX – SDD DETECTOR BY KETEK
In FBK there is a machine called Phoenix with combined
XRF/XRD technology installed (Figure A.1).
This machine is equipped with a boxed Silicon Drift
Detector ( SDD ), with Peltier cooling , for XRF – EDX –
TXRF Applications , and a controlling software on Windo ws
PC developed in C++ internally at FBK .
The detector is an AXAS -D model produced by Ketek
(Figure A.2). All information and images, where not explicitly
specified, are retrieved from the official Ketek documentation
(as available on the website published at www.ketek.net) .
The short facts for th ese model s of detector by Ketek are:

• Digital system complete with VITUS SDD, reset type
preamplifier and Digital Pulse Processor (DPP) ;
• Detector size 65 mm² collimated to 50 mm² , with 1024
channels ;
• energy resolution down to 123eV FWHM at Mn -Kα;
• Filtering for SDD operating voltages ;
• SDD operating temperature readout ;
• Highly integrated design : alumin ium housings plated
with Nickel. All screws are stainless stee l;
• operable at an ambient temperature of up to +80°C ;
• high count rate capability up to 1,000kcps ;
• efficient integrated Peltier element ;
• no liquid nitrogen cooling required ;
• radiation hardness during more than 10 years standard
count rate exposure ;
• peaking times adjustable via Graphic User Interface (GUI) from 1.32μs to 13.3μs.

Figure A.2 View of the Ketek detector
Figure A.1 Phoenix machine in FBK

A

20 A.1. SDD box geometry
In Figure A.3 is showed the front and the back of AXAS -D model of FBK, with the 100mm
finger on top of which is installed the VITUS SDD detector. In Figure A.4 is detailed the geometry
of the casing .

AXAS -D front with 100mm finger
AXAS -D back with preamplifier output and USB port
Figure A.3 Front and back of the detector casing

Figure A.4 Geometry of the casing
A.2. SDD geometry
KETEK's VITUS Silicon Drift Detectors (SDD) are the state -of-the-art X -ray detectors based
on silicon substrate. Their typical X -ray energy range is between 0.2 keV and 30 keV. They are used
in applications such as EDX, EDS, XRF, TXRF.
Due to their wide operating temperature range they are especially employed for industrial and
automotive applications. In Figure A.5 we can see the SDD detector with and without the housing
(called “TO8 housing”) .

Appendix – SDD Detector by Ketek

21
a) VITUS H50 in TO8 housing with 12.5 μm Be
window
b) Open VITUS H50 with on -chip
multilayer collimator
Figure A.5 SDD detector with ( a) and without (b) the housing.
In Figure A.6 we can see the schemes of SDD construction with ceramic SDD chip carrier,
Peltier cooling element and a multilayer collimator , integrated in a standard TO8 housing.
All VIT US detectors have an on chip collimator which offers a minimum vertical distance to the
radiation entrance plane and therefore a large solid angle. The absorption depth is 450 m, the
maximum input count rate is 1000 kcps (kilocount per seconds).

a) Cross section
b) VITUS H50 Detector Geometry
Figure A.6 Cross section and geometry of Vitus SDD detector model

A

22 A.3. Operation requirements

a)

b)
Figure A.7 a) Pin assignment of VITUS SDD; and b) VITUS Operation Block Diagram
Detector operating voltages are RC low -pass filtered and linearly regulated by KETEK
electronics. KETEK model has moreover reset type charge sensitive pre -amplifier with internal
triggered reset pulses, and short wiring length between detector and pre -amplifier ( Figure A.7).
Table A.1 VITUS SDD operation requirements
SDD Voltages and Currents
Ring1 (R1) -20 V ± 5 V 10 µA typ.
RingX (RX) -130 V ± 20 V 10 µA typ.
Back -60 V ± 5 V <1 nA
Included FET
Drain 3 V ± 0.5 V 3 mA
Source 0 V
Bulk -5 V ± 3 V
Reset 1 V 1 μs
Feedback ramped output
Peltier Element 3.6 V 700 mA max
Temperature Monitor NTC thermistor 10 kΩ @ 25 °C

The operation block diagram of Figure A.7 is showed in more detail in Figure A.8. The diagram
shows the principle of operation of the AXAS -D. It consists of a low voltage p ower supply for 3.3
and 1.2V, a thermoelectric cooler controller for the SDD Peltier, a high voltage (180 V DC) power
supply, a sensor parameters control and measurement unit, the preamplifier and the Digital Pulse
Processor (DPP ) itself. It provides an overvoltage and polarity reversal protection.

Appendix – SDD Detector by Ketek

23
Figure A.8 Operation block diagram of VITUS SDD
The Block Diagram of shows the principle of operation of the Digital Pulse Processor (DPP).
The main clock frequency is 25 MHz, using a 12bit ADC at 40 MSPS. It has both an analogue gain
before digitizing and a digital gain right after the digital filtering, which consists of digital shaping a
digital Baseline Restoration (BLR), a Peak Detection and a digital Pile -Up Rejector (PUR).
Also the SDD operating parameters can be set and read by an additional ADC in combination
with a SPI Interface. The DPP is FPGA based and uses USB 2.0 Interface.

Figure A.9 Block diagram of the Digital Pulse Processor (DPP)
A.4. AXAS -D Detector behavio ur
The diagram of Figure A.11 provides the throughput behaviour of the AXAS -D according to
specification . It shows the dependency of the output count rate with the input count rate for

A

24 different digital peaking times. The lower the peaking time, the higher is the maximum throughput
for a system.
The energy resolution of the digital system is mostly independent from the inpu t count rate , as
we can see in Figure A.10. The graph shows the dependency of the Full Width at half maximum
with the incoming photons (input count rate) for
different digital peaking times.
The graph of Figure A.12 shows the independency
of the peak position of the Mn -K line with the input
count rate for different digital peaking times.

Figure A.11 Throughput behaviour
Figure A.12 Energy resolution with input count r ate
Figure A.10 Peak p osition of Mn -K

Appendix – Bravais lattices

25 B. APPENDIX – BRAVAIS LATTICES
A distinctive property of the crystalline state of the matter is the regular repetition in the three –
dimensional space of an object , i.e. an atom or a molecule [15,41] , which is time -invariant [17].
Each of these ordered repetition can be summarized as primitive cells [1], which defines a lattice
type. In this Appendix we shall descr ibe the possible space lattices based on the so called Bravais
classification , after Auguste Bravais who first listed them in 1850 [15,17 ]: seven crystal classes which
originate fourteen lattices .
Table B.1 Classification of Bravais lattices
Lattice class Parameters Simple
primitive (P) Volume
centered (I) Base centered
(C) Face centered
(F)
Triclinic     
a  b  c

Monoclinic   90°
 =  = 90°
a  c

Orthor hombic  =  =  = 90°
a  b  c

Tetragonal  =  =  = 90°
a = b  c

Cubic  =  =  = 90°
a = b = c

B

26 Lattice class Parameters Simple
primitive (P) Volume
centered (I) Base centered
(C) Face centered
(F)
Trigonal
(Rhombohedral)  =  =  < 120°
a = b = c

Hexagonal  =  =  = 120°
a = b  c

As showed in Table B.1, the unit cells are defined by the relative lengths of the cell edges ( a, b, c )
and the angles between them (α, β, γ) , where a, b and c are the length of lattice vectors a, b and c,
and  is the angle between b and c,  the angle between a and c, and  between b and a. The
volume of the unit cell can be calculated by evaluating the triple product a · (b × c). The volume
formulas of the crystal families are given below in:
Table B.2 Volume formulas of crystal families
Lattice class Volume Example
Triclinic
𝑎𝑏𝑐√1−𝑐𝑜𝑠2𝛼−𝑐𝑜𝑠2𝛽−𝑐𝑜𝑠2𝛾+2cos𝛼cos𝛽cos𝛾 K2Cr2O7, CuSO 4·5H 2O,
H3BO 3
Monoclinic
abc  sin Monoclinic sulphur ,
Na2SO 4·10H 2O
Orthorhombic abc Rhombic sulphur , KNO 3,
BaSO 4
Tetragonal a2c White tin, SnO 2, TiO 2, CaSO 4
Cubic a3 NaCl, zinc blende, copper
metal
Trigonal
(Rhombohedral) 𝑎3√1−3𝑐𝑜𝑠2𝛼+2𝑐𝑜𝑠3𝛼 Calcite (CaCO 3), cinnabar
(HgS)
Hexagonal √3
2𝑎2𝑐 Graphite, ZnO, CdS

Appendix – Atomic elements

27 C. APPENDI X – ATOMIC ELEMENTS
In this Appendix we present a synthesis of the chemical and physical properties of the main
atomic elements encountered in this work.

Figure C.1 Periodic table of the elements containing 118 elements (Source: https://sciencenotes.org)
C.1. Beryllium
Beryllium is a chemical element with symbol Be and atomic number 4. The word comes from the
Latin word beryllium , used by Propertius, Pli ny and others, derived from the Greek beryllos , a
gemstone with blue -green colour, whose origin is certainly Indian as the stone which designates [44].
The main properties are summarized in Table C.1.
Being one of the lightest known structural metals has contributed to beryllium being used in a
wide variety of both nuclear and non -nuclear applications [4]. However, t he commercial use of
beryllium requires the use of appropriate dust control equipment because of the toxicity of inhaled

C

28 beryllium -containing dusts , which can cause a chronic life -threatening allergic disease in some
people called berylliosis [23,35] .
Table C.1 Main atomic parameters of beryllium [4,27,30,31 ,40]
Crystal
structure Atomic
Number (Z) Group Standard atomic
weight (A) Ground -state
configuration 1st Inonization
energy (eV)

HCP 4 alkaline earth
metal 9.01218 2(3) 1s2 2s2 9.3227
Melting
temperature Boling
temperature Density at solid
state (g/cm3) Atomic radius
(empirical) Thermal
expansion
1287 °C 2471 °C 1.85 112 pm 11.3 µm/(m·K)
(at 25 °C)
C.1.1. Production
Beryllium is found in over 100 minerals (according to Mindat.org), but most are uncommon to
rare [43]. The more common minerals containing beryllium are: bertrandite (Be 4Si2O7(OH) 2), beryl
(Al 2Be3Si6O18) (), chrysoberyl (Al 2BeO 4) and phenakite (Be 2SiO 4). Precious forms of beryl are
aquamarine , red beryl and emerald [35].
The extraction of beryllium is a difficult process because of its high
affinity for oxygen at elevated tem peratures [16,19,43] , and its ability to
reduce water when its oxide film is removed; beryllium is most commonly
extracted from the mineral beryl through a sintering process or a melting
process in order to get beryllium hydroxide, which is then converted into
beryllium fluoride or beryllium chloride.
In the first case, aqueous ammonium hydrogen fluoride is added to beryllium hydroxide to yield a
precipitate of ammonium tetrafluoroberyllate , which is then heated to 1,000 °C in order to get
beryllium fluoride. This fluoride, heated to 900 °C with magnesium , forms finely divided beryllium,
and additional heating to 1,300 °C generates the compact metal.
In the second case, beryllium hydroxide is heated to form the oxide, which becomes beryllium
chloride when combined with carbon and chlorine. A final electrolysis process of molten beryllium
chloride is used to obtain the metal.
Figure C.2 Beryl from
South Tyrol (Italy) [9]

Appendix – Atomic elements

29 C.2. Aluminium
Alumin ium, or aluminum (in North American English) , is a chemical element with symbol Al
and atomic number 26 . The word comes from alumen , a Latin word meaning "bitter salt" because
referred to an hydrated salt of the element [6,44] , known since 300 B.C . Sir Humphry Davy was the
first who named the metal aluminum in 1805 ; even if he could not isolate it, he was convinced that it
existed and named it anyway. L ater the name was changed to aluminium to be consistent with other
metal Latin names and t he International Union of Pure and Applied Chemistry (IUPAC ) adopted
aluminium as the standard international name for the element in 1990 but, three years later,
recognized aluminum as an acceptable variant. The IUPAC periodic table uses the aluminium spelling
only.
The main properties of aluminium are summarized in Table C.2. Alumin ium is a silvery -white,
soft, nonmagnetic, ductile metal with many valuable properties [4]. It is light (density 2.70 g/cm3),
nontoxic, and can be easily machined or cast. With an electrical conductivity 60% that of copper and
a much lower density, it is used extensively for electrical transmission lines. Pure alumin ium is soft
and brittle, but can be strengthened by alloying with small amounts of copper, magnesium, and
silicon [22,38] .
Table C.2 Main atomic parameters of aluminium [4,27,30,31]
Crystal
structure Atomic
Number (Z) Group Standard atomic
weight (A) Ground -state
configuration 1st Inonization
energy (eV)

FCC 13 post-transitional
metal 26.9815385(7) [Ne] 3 s2 3s1 5.9858
Melting
temperature Boling
temperature Density at solid
state (g/cm3) Atomic radius
(empirical) Thermal
expansion
660.32 °C 2470 °C 2.70 143 pm 23.1 µm/(m·K)
(at 25 °C)
C.2.1. Production
Aluminium it is the third most abundant element after oxygen and silicon and the most abundant
metal in the Earth’s crust [6]. Aluminium metal is so c hemically reactive that native specimens are
rare and limited to extreme reducing environments [16,19] . Instead, it is found combined in over
270 different minerals. The chief ore of aluminium , used at industrial level, is bauxite , a mixture of
hydrated alumin ium oxide (Al 2O3xH 2O) and hydrated iron oxide (Fe 2O3xH 2O). Another mineral
important in the production of the metal is cryolite (Na 3AlF 6).

C

30 Actually, today more than 95% of alumina worldwide is extracted from bauxite using the so
called Bayer process , which was invented in 1887, just one year after the invention of the
concurrent Hall–Heroult electrolytic process [6,32] .
C.3. Silicon
Silicon is a chemical element with symbol Si and atomic number 14. Its name derives from a
choice of Sir Humphry Davy , which during an attempt to isolate silicon in 1808, proposed the name
"silicium " for silicon, from the Latin silex, -is for flint, and adding the " -ium" ending because he
believed it was a metal. Silicon was given its present name in 1817 by Scottish chemist Thomas
Thomson , who retained part of Davy's name, but added " -on" because he believed that si licon was a
non-metal similar to boron and carbon [6,44] .
The main properties of silicon are summarized in Table C.3. Silicon is a crystalline, gray, and
brittle metalloid with a cubic diamond crystal lattice structure , largely used in semiconductor
industry due to is large energy -band gap (1.170 eV), so ca n it can be used for higher temperature
operations [10,45] . Over 90% of the Earth's crust is composed of silicate minerals, making silicon
the second most abundant element in the Earth's crust [22].
Pure silicon is highly sensitive to irradiation by nuclear radiation such as X -rays and gamma -rays,
creating recombination centers and increasing surface state densities .
Table C.3 Main atomic parameters of silicon [4,27,30,31]
Crystal
structure Atomic
Number (Z) Group Standard atomic
weight (A) Ground -state
configuration Inonization
energy (eV)

Face centered
diamond cubic 14 metal loid 28.0855(3)1 [Ne] 3 s2 3p2 8.1517
Melting
temperature Boling
temperature Density at solid
state (g/cm3) Atomic radius
(empirical) Thermal
expansion
1414 °C 3265 °C 2.3290 111 pm 2.6 µm/(m·K)
(at 25 °C)
C.3.1. Production
From a chemical point of view, owing to its protective film of silicon dioxide, SiO 2, that grows
spontaneously in oxidizing media containing oxygen, silicon is a relatively inert element , but it is

1 Range in isotopic composition of normal terrestrial material prevents a more precise atomic weight being given; the tabulated
value should be applicable to any normal material.

Appendix – Atomic elements

31 easily attacked by hydrogen fluoride, hydrofluoric acid, HF, gaseous halogens (i.e., F 2, Cl 2, Br 2, and
I2), and diluted alkaline solutions [44].
Most silicon is used commercially without being separated, and often with little processing of the
natural minerals. Such use includes industrial construction with clays, silica sand, and stone [16].
Most free silicon is used in the steel refining and aluminium -casting.
Moreover, a relatively small portion of very highly purified silicon is used in semiconductor
electronics . In this type of application, two form of hyperpure silicon are used: p olycrystalline silicon
and m onocrystalline silicon , for which different processes has been refined [22,28,44] .
C.4. Potassium
Potassium is a che mical element with symbol K and atomic number 19. It was first isolated from
potash , the ashes of plants, from which its name derives. In the periodic table, potassium is one of
the alkali metals and symbol is derived from Neo -Latin name , kalium [27,44] .
Table C.4 summarize the main properties of p otassium , which in nature occurs only in ionic salts ;
elemental potassium is a soft silvery -white alkali metal that oxidizes rapidly in air and is extremely
active metal that reacts violently with oxygen in water and air. With oxygen it forms potassium
peroxide, and with water potassium forms potassium hydroxi de. The reaction of potassium with
water is dangerous because of its violent exothermic character and the production of hydrogen gas.
Hydrogen reacts again with atmospheric oxygen, producing water, which reacts with the remaining
potassium.
The only common oxidation state for potassium is +1. Potassium metal is a powerful reducing
agent that is easily oxidized to the monopositive cation, K+. Once oxidized, it is very stable and
difficult to reduce back to the metal. It is found dissolved in sea water and is part of many minerals.
Table C.4 Main atomic parameters of potassium [4,6,27,31]
Crystal
structure Atomic
Number (Z) Group Standard atomic
weight (A) Ground -state
configuration Ionization
energy (eV)

Body centered
cubic ( phase) 19 Alkali metal 39.0983 (1) [Ar] 4s1 4.34066
Melting
temperature Boling
temperature Density at solid
state (g/cm3) Atomic radius
(empirical) Thermal
expansion
63.5 °C 759 °C 0.862 227 pm 83.3 µm/(m·K)
(at 25 °C)

C

32 C.4.1. Produ ction
Potassium salts such as carnallite, langbeinite, polyhalite, and sylvite form extensive evaporite
deposits in ancient lake bottoms and seabeds, making extraction of potassium salts in these
environments commercially viable. The principal source of potassiu m – potash – is mined in many
places around the world.
Several methods are used to separate potassium salts from sodium and magnesium compounds.
The most -used method is fractional precipitation using the solubility differences of the salts at
different te mperatures. Electrostatic separation of the ground salt mixture is also used in some
mines.
C.5. Calcium
Calcium is a chemical element with symbol Ca and atomic number 20. Its symbol derives from
Latin word calx, -is [27,44] which means “lime” .
In Table C.5 are summarized the main properties of calcium, which is a soft grayfish -yellow
alkaline earth metal, fifth-most -abundant element by mass in the Earth's crust [6]. The ion Ca2+ is
also the fifth -most -abundant dissolved ion in seawater by both molarity and mass, after sodium,
chloride, magnesium, and sulphate.
With a density of 1.54 g/cm3, calcium is the lightest of the alkaline earth metals; magnesium
(with 1.74) and beryllium (with 1.85, see Appendix C.1) are denser though lighter in atomic mass.
Free calcium metal is too reactive to occur in nature , and calcium metal is hazardous because of
its sometimes -violent reactions with water and acid s. Calcium has five stable isotopes (40Ca, 42Ca,
43Ca, 44Ca and 46Ca), plus one more (48Ca) that has such a long half -life, it can be considered stable
for many purposes [39].
Table C.5 Main atomic parameters of calcium [4,27,31]
Crystal
structure Atomic
Number (Z) Group Standard atomic
weight (A) Ground -state
configuration Ionization
energy (eV)

Face centered
cubic 20 Alkaline earth
metal 40.078(4) [Ar] 4s2 7.7264
Melting
temperature Boling
temperature Density at solid
state (g/cm3) Atomic radius
(empirical) Thermal
expansion
842 °C 1484 °C 1.55 197 pm 22.3 µm/(m·K)
(at 25 °C)

Appendix – Atomic elements

33 C.5.1. Production
Calcium can be extracted by electrolysis from a fused salt like calcium chloride. Calcium is
relatively soft for a metal; although harder than lead, it can be cut with a knife with difficulty.
Calcium is chemically reactive; when expose d to the air, it rapidly forms a gray -white coating of
calcium oxide and calcium nitride.
C.6. Iron
Iron is a chemical element with symbol Fe and atomic number 26. Its symbol derives from Latin
word ferrum [27,44] .
The main properties of iron are summarized in Table C.6. It is a metal in the first transition series
[14], and the most common element on Earth, forming much of Earth's outer and inner core [22].
Like the other group 8 elements, iron exists in a wide range of oxidation states, −2 to +6,
although +2 and +3 are the most common. Elemental iron occurs in meteoroids and other low
oxygen environments, but is reactive to oxygen and water. Fresh iron s urfaces appear silvery -gray,
but oxidize in normal air to give hydrated iron oxides, commonly known as rust.
Unlike the metals that form passivating oxide layers, iron oxides occupy more volume than the
metal and thus flake off, exposing fresh surfaces again for corrosion [22,44] .
Table C.6 Main atomic parameters of iron [4,6,27,31]
Crystal
structure Atomic
Number (Z) Group Standard atomic
weight (A) Ground -state
configuration Ionization
energy (eV)

Body centered
cubic ( phase) 26 Transition metal 55.845(2) [Ar] 3d6 4s2 7.9024
Melting
temperature Boling
temperature Density at solid
state (g/cm3) Atomic radius
(empirical) Thermal
expansion
1538 °C 2862 °C 7.874 126 pm 11.8 µm/(m·K)
(at 25 °C)

C.6.1. Production
Iron metal has been used since ancient times, giving also its name to an humankind’s age, the so
called Iron Age .
Pure iron is relatively soft, but is unobtainable by smelting because it is significantly hardened and
strengthened by impurities, in particular carbon, from the smelting process.

C

34 With a certain proportion of carbon (between 0.002% and 2.1%) we get steel, which may be up
to 1000 times harder than pure iron.
Crude iron metal is produced in blast furnaces, where ore is reduced by coke to pig iron, which
has a high carbon content. Further refinement with oxygen reduces the carbon content to the
correct propo rtion to make steel.
Steels and iron alloys formed with other metals (alloy steels) are by far the most common metals
because they have a great range of desirable and manageable properties an d iron -bearing rock is
abundant [1,16,20,37] .
C.7. Copper
Copper is a chemical element with sy mbol Cu and atomic number 29 . Its symbol derives from
Latin word cuprum [27,44] . It is a metal in the first transition series [14]: it is soft, malleable, and
ductile with very high thermal and electrical conductivity. A freshly exposed surface of pure copper
has a reddish -orange colo ur.
The main properties of copper are summarized in Table C.7 [22,38] .
Table C.7 Main atomic parameters of copper [4,11,27,31]
Crystal
structure Atomic
Number (Z) Group Standard atomic
weight (A) Ground -state
configuration Ionization
energy (eV)

Face centered
cubic 29 Transition metal 65.546(3) [Ar] 3d10 4s1 7.7264
Melting
temperature Boling
temperature Density at solid
state (g/cm3) Atomic radius
(empirical) Thermal
expansion
1084.62 °C 2562 °C 8.96 128 pm 16.5 µm/(m·K)
(at 25 °C)

C.7.1. Production
Copper production [11,16] .

Appendix – Atomic elements

35 C.8. Silver
Silver is a metallic element with symbol Ag and atomic number 47. The symbol Ag derives from
the Latin word argentum , derived from the Greek ὰργὀς [argòs], which literally "shiny" or "white"
[8,44] .
The main properties of silver are summarized in Table C.8: it is a soft, white, lustrous transition
metal, and exhibits the highest elect rical conductivity, thermal conductivity, and reflectivity of any
metal.
As one of the seven metals of antiquity, silver has had an enduring role in human cultures , and as
a precious metal , was used in many monetary systems for coins alongside gold [2,12,34] .
Table C.8 Main atomic parameters of silver [4,27,31]
Crystal
structure Atomic
Number (Z) Group Standard atomic
weight (A) Ground -state
configuration Ionization
energy (eV)

Face centered
cubic 47 Transition metal 107.8682(2) [Kr] 4 d10 5s1 7.5762
Melting
temperature Boling
temperature Density at solid
state (g/cm3) Atomic radius
(empirical) Thermal
expansion
961.78 °C 2162 °C 10.49 144 pm 18.9 µm/(m·K)
(at 25 °C)

C.8.1. Production
The metal is found in the Earth's crust in the pure, free elemental form ("native silver"), as an
alloy with gold and other metals, and in minerals such as argentite (Ag 2S), pr oustite (Ag 3AsS 3),
pyrargerite (Ag 3SbS 3) and chlorargyrite (AgCl) [8,44] . Silver is also more abundant than gold, but it is
much less abundant as a nati ve metal.
Most part of commercial silver is produced as a by -product of co pper, nickel, gold, lead, and zinc
refining [16,21,22] .
To extrac t the silver from minerals is used , for example, the process of leaching with alkali
cyanides. Another v ery important method is the extraction of silver from galena , which is a mineral
of lead (PbS) mixed with silver (content of silver up to 0.2%) [3,8].
The crude metal obtained, according to the different procedures mentioned, is then refined by
electrolysis.

C

36 C.9. Gold
Gold is a chemical element wit h symbol Au and atomic number 79. Its symbol derives from the
Latin word aurum [42,44] .
The main properties of silver are summarized in Table C.9: in its purest form, it is a bright,
slightly reddish yellow, dense, soft, malleable, and ductile metal. It is a transition metal and one of
the least reactive chemical elements and is solid under standard conditions .
As one of the seven metals of antiqu ity, gold has had an enduring role in human cultures, and as
a precious metal, was used in many monetary systems for coins alongside silver [2,12,21,34] .
Table C.9 Main atomic parameters of gold [4,27,31]
Crystal
structure Atomic
Number (Z) Group Standard atomic
weight (A) Ground -state
configuration Ionization
energy (eV)
Face centered
cubic 79 transition
metal 196.966569 (5) [Xe] 4f14 5d10 6s1 9.2255
Melting
temperature Boling
temperature Density at solid
state (g/cm3) Atomic radius
(empirical) Thermal
expansion
1064 .18 °C 2970 °C 19.30 144 pm 14.2 µm/(m·K)
(at 25 °C)
C.9.1. Production
Gold often occurs in free elemental (native) form, as nuggets or grains, in rocks, in veins, and in
alluvial deposits. It occurs in a solid solution series with the native element silver (as electrum) and
also naturally alloyed with copper and palladium. Less commonly, it occurs in minerals as gold
compounds, often with tellurium (gold tellurides) [13,21,22] .
A significant percentage of the world's gold production comes from the processing of by –
products of copper metallurgy, nickel and lead [44]. Gold extraction is most economical in large,
easily mined deposits : ore grades as little as 0.5 parts per million (ppm) can be economical. Typical
ore grades in open -pit mines are 1 –5 ppm , while ore grades in underground or rock mines are
usually at least 3 ppm. Because ore grades of 30 ppm are usually needed before gold is visible t o the
naked eye, in most gold mines the gold is invisible.
The gold deposits are divided into primary and secondary [44]. Those primaries are of
hydrothermal origin and are present within acidic igneous rocks. The metal is generally as sociated
with various sulphides like pyrite (FeS 2), chalcopyrite (CuFeS 2), arsenopyrite (FeAsS) and others; or
contained in them in a state of great dispersion, which constitute veins and strands in the gangue of
quartz (auriferous quartz, pyrite auriferous).

Appendix – Atomic elements

37 Secondary deposits are alluvial and are derived from erosion of the primary ones. The materials
are generally constituted by quartz conglomerates and loose sands that are transported and
concentrated from the river currents; the metal that is extracted generally occurs in f lakes or in larger
fragments, of different size and mass (even up to a maximum of 100 kg), which are rounded as a
result of the water transport (nuggets).
Gold is extracted by amalgamation, for chlorination and cyanidation [16,22,37,44] , with some
important issues from environmental point of view . After initial production, gold is often
subsequently refined industrially by the Wohlwill process which is based on electrolysis or by the
Miller process, that is chlorination in the melt. The Wohlwill process results in higher purity, but is
more complex and is only applied in small -scale installations.
Other methods of assaying and purifying smaller amounts of gold include parting and
cupellation, or refining methods based on the dissolution of gold in aqua regia.
C.10. Lead
Lead is a chemical element with symbol Pb and atomic number 82. Its symbol derives from Latin
word plumbum [8,44] . It is a post-transition metal [3].
Table C.10 Main atomic parameters of lead [4,27,31]
Crystal
structure Atomic
Number (Z) Group Standard atomic
weight (A) Ground -state
configuration Ionization
energy (eV)
Face centered
cubic 82 post-transition
metal 207.2(1) [Xe] 4f14 5d10 6s2 6p2 7.4167
Melting
temperature Boling
temperature Density at solid
state (g/cm3) Atomic radius
(empirical) Thermal
expansion
327.46 °C 1749 °C 11.34 175 pm 28.9 µm/(m·K)
(at 25 °C)
C.10.1. Production
Lead production [3,16] .

C

38 C.11. Bismuth
Bismuth is a chemica l element with the symbol Bi and atomic number 83. Bismuth metal has
been known since ancient times, although it was often confused with lead and tin, which ha ve some
similar physical properties [22]. The etymology is uncertain, but probably comes from Arabic bi
ismid, meaning having the properties of antimony , or the German words weiße Masse or Wismuth
("white mass"), translated in the mid -sixteenth century to New Latin bisemutum [44].
The main properties of b ismuth are summarized in Table C.11; it is the most naturally
diamagnetic element, and has one of the lowest values of thermal conductivity among metals.
Table C.11 Main atomic parameters of bismuth [4,27,30,31]
Crystal
structure Atomic
Number (Z) Group Standard atomic
weigh t (A) Ground -state
configuration Ionization
energy (eV)
Face centered
cubic 83 post-transition
metal 208.98040(1) [Xe] 4f14 5d10 6s2 6p3 7.2855
Melting
temperature Boling
temperature Density at solid
state (g/cm3) Atomic radius
(empirical) Thermal
expansion
271.5 °C 1564 °C 9.78 156 pm 13.4 µm/(m·K)
(at 25 °C)
C.11.1. Production
Elemental bismuth may occur naturally or as its sulfide and oxide. It is a brittle metal with a
silvery white colo ur when freshly produced, but surface oxidation can give it a pink tinge. Bismuth is
stable to both dry and moist air at ordinary temperatures ; it reacts with fluorine to make bismuth(V)
fluoride at 500 °C or bismuth(III) fluoride at lower temperatures (typically from Bi melts); with
other halogens it yields only bis muth(III) halides [44].
The trihalides (X = F, Cl, Br, I) are corrosive and easily react with moisture, forming oxyhalides
with the formula BiX 3:
2 Bi + 3 X 2 → 2 BiX 3
Bismuth dissolves in concentrated sulfuric acid to make bismuth(III) sulphate and sulphur
dioxide, and reacts with nitric acid to make bismuth(III) nitrate. Moreover, it dissolves in
hydrochloric acid, but only with oxygen present.
The most important ores of bismuth are bismuthinite (Bi 2S3) and bismite (Bi 2O3) [22,44] ; bismuth
is then prepare d by reduction of oxides (the sulphides are transformed into oxides by roasting); large
part of the metal of the trade is obtained also as a by-product in the m etallurgy of lead, copper and

Appendix – Atomic elements

39 tin. Thus it can be separated from the lead by fractional crystallization as a form with it an eutectic
rich in b ismuth w ith a solidification point of about 200 ° C lower than that of lead, o r by electrolysis,
from the tin , for dissolution in hydrochloric acid and reprecipitation in the form of oxychloride by
simple dilution.

0

40 INDEX
A
aluminium; 29
aquamarine; 28
argentum ; 32
AXAS -D; 19
B
bauxite; 29
bertrandite; 28
beryl; 28
berylliosis; 28
Beryllium; 27
bisemutum ; 34
bismuth; 34
Bremstrahlung; 11
C
Charles V; 15
chrysoberyl; 28
collimator; 21
constant
Planck; 10
cooler; 22
copper; 31
cryolite; 29
cuprum ; 31
D
Davy
Sir Humphry; 29; 30
DPP; 22
E
emerald; 28 F
field
Coulomb ; 10
H
Holy Roman Emperor; 15
I
iron; 31
IUPAC; 29
K
Ketek; 19
L
lattices
Bravais; 25
cubic ; 25
hexagonal; 26
mono clinic; 25
orthorhombic; 25
rhombohedral; 26
tetragonal; 25
triclinic; 25
trigonal; 26
law
Moseley's ; 10
Plancks's ; 10
lead; 34
low-pass; 22
M
magnesium; 28

Index

41 P
Peltier; 19
phenakite; 28
Phoenix; 19
PileUp Rejector; 23
plumbum ; 34
pre-ampl ifier; 22
S
SDD; 19
sesini; 14
silicon; 30
silver; 32
spectrometry; 10 spectroscopy; 9
T
tetrafluoroberyllate; 28
Thomson
Thomas ; 30
V
Venice; 14
volume; 26
W
Wallachia; 15

0

42 INDEX OF FIGURES
Figure 2.1 ________________________________ ________________________________ _____________________ 9
Figure 2.2 Wilhelm Konrad Roentgen (Wikipedia .c.c.) ________________________________ _________________ 9
Figure 2.3 Henry G. J. Moseley (Wikipedia c.c.) ________________________________ ______________________ 10
Figure 2.4 Example of Bremstrahlung ________________________________ ______________________________ 11
Figure 5.1 The Europe at the beginning of the XVI century (Source: http://maplists.com) ____________________ 15
Figure A.1 Phoenix machine in FBK ________________________________ ________________________________ 19
Figure A.2 View of the Ketek detector ________________________________ _____________________________ 19
Figure A.3 Front and back of the detector casing ________________________________ _____________________ 20
Figure A.4 Geometry of the casing ________________________________ ________________________________ 20
Figure A.5 SDD detector with (a) and without (b) the housing. ________________________________ __________ 21
Figure A.6 Cross section and geometry of Vitus SDD detector model ________________________________ _____ 21
Figure A.7 a) Pin assignment o f VITUS SDD; and b) VITUS Operation Block Diagram ________________________ 22
Figure A.8 Operation block diagram of VITUS SDD ________________________________ ___________________ 23
Figure A.9 Block diagram of the Digital Pulse Processor (DPP) ________________________________ __________ 23
Figure A.12 Peak position of Mn -K ________________________________ _______________________________ 24
Figure A.11 Throughput behaviour ________________________________ ________________________________ 24
Figure A.10 Energy resolution with input count rate ________________________________ __________________ 24
Figure C.1 Periodic table of the elements containing 118 elements (Source: https://sciencenotes.org) __________ 27
Figure C.2 Beryl from South Tyrol (Italy) [7] ________________________________ _________________________ 45

Index of tables

43 INDEX OF TABLES
Table A.1 VITUS SDD operation requirements ________________________________ _______________________ 22
Table B.1 Classification of Bravais lattices ________________________________ __________________________ 25
Table B.2 Volume formulas of crystal families ________________________________ _______________________ 26
Table C.1 Main atomic parameters of beryllium [22,24,25] ________________________________ ____________ 28
Table C.2 Main atomic parameters of aluminium [22,24,25] ________________________________ ___________ 29
Table C.3 Main atomic parameters of silicon [22,24,25] ________________________________ _______________ 30
Table C.4 Main atomic parameters of iron [22,25] ________________________________ ___________________ 33
Table C.5 Main atomic parameters of copper [9,22,25] ________________________________ _______________ 34
Table C.6 Main atomic parameters of silver [22,25] ________________________________ __________________ 35
Table C.7 Main atomic parameters of gold [22,25] ________________________________ ___________________ 36
Table C.8 Main atomic parameters of lead [22,25] ________________________________ ___________________ 37
Table C.9 Main atomic parameters of bismuth [22,24,25] ________________________________ _____________ 38

0

44 REFERENCES
[1] R. Abbaschian, L. Abbaschian, R.E. Reed -Hill, Physical Metallurgy Principles , 4th ed., Cengage Learning,
Boston, USA, 2009.
[2] F. Barello, Archeologia della moneta , Roma, I, 2012.
[3] D.R. Blaskett, D. Boxall, Lead and its alloys , Ellis Horwood Limited, Chichester, UK, 1990.
[4] F. Borgese, Gli elementi della tavola periodica. Rinvenimento, proprietà, usi , CISU, Roma, I, 1993.
[5] C. Capra, Età moderna , Le Monnier, Firenze, 1998.
[6] F. Cardarelli, Materials handbook , 2nd ed., Springer -Verlag, Tucson, AZ, 2008.
[7] H.G. Chotas, J.T. Dobbins, C.E. Ravin, Principles of digital radiography with large -area, electronically readable
detectors: a review of the basics. , Radiology. 210 (1999) 595 –599.
[8] J. Cierny, Argento e piombo , in: L. Endrizzi, F. Marzatico (Eds.), Ori Delle Alpi, Castello del
Buonconsiglio – Monumenti e collezioni provinciali, Trento, I, 1997: pp. 70 –74.
[9] J. Cie rny, G. Weigerber, Pietre preziose ornamentali utilizzate con maggiore frequenza nella preistoria, in epoca
classica e nell’Alto Medioevo , in: L. Endrizzi, F. Marzatico (Eds.), Ori Delle Alpi, Castello del
Buonconsiglio – Monumenti e collezioni provinciali , Trento, I, 1997: pp. 101 –110.
[10] J.-P. Colinge, C. Coling, Physics of semiconductor devices , 1st ed., Kluwer Academic Publishers, 2002.
[11] W.G. Davenport, M. King, M. Schlesinger, A.K. Biswas, Extractive Metallurgy of Copper , 4th ed.,
Pergamon, Oxfor d, UK, 2002.
[12] A. Finetti, Numismatica e tecnologia , La Nuova Italia Scientifica, Roma, I, 1987.
[13] A. Fuganti, G. Morteani, L’oro nelle Alpi: giacimenti, estrazione e metallurgia , in: L. Endrizzi, F. Marzatico
(Eds.), Ori Delle Alpi, Castello del Buo nconsiglio – Monumenti e collezioni provinciali, Trento, I,
1997: pp. 57 –66.
[14] M. Gerloch, E.C. Constable, Transition Metal Chemistry , 6th ed., VCH Gmbh, Weinheim, D, 1994.
[15] C. Giacovazzo, H.L. Monaco, D. Viterbo, F. Scordari, G. Gilli, G. Zanotti, M. Catti, Fundamentals of
Crystallography , Oxford University Press, New York, 1992.
[16] J.D. Gilchrist, Extraction metallurgy , 3rd ed., Pergamon Press, Oxford, UK, 1989.
[17] M. De Graef, M.E. McHenry, Structure of Materials: An Introduction to Crystallog raphy, Diffraction, and
Symmetry , 1st ed., Cambridge University Press, New York, 2007.
[18] R.E. Van Grieken, A.A. Markowicz, eds., Handbook of X -Ray Spectrometry , 2nd ed., Dekker, New York,
2002.
[19] C.K. Gupta, Chemical Metallurgy. Principles and practi ce, 1st ed., WILEY -VCH Verlag GmbH & Co.
KGaA, Weinheim, D, 2003.
[20] F. Habashi, Handbook of Extractive Metallurgy – Volume I – The metal industry and Ferrous Metals , WILEY –
VCH Verlag GmbH & Co. KGaA, Weinheim, D, 1997.
[21] F. Habashi, Handbook of Extra ctive Metallurgy – Volume III – The precious, refractory, rare earth metals ,
WILEY -VCH Verlag GmbH & Co. KGaA, Weinheim, D, 1997.
[22] C.R. Hammond, The elements , in: Handb. Chem. Phys., 90th ed., CRC Press/Taylor and Francis, Boca
Raton, FL, 2009: pp. 4 –1.
[23] IARC, Arsenic, metals, fibres, and dusts. A review of human carcinogens , 1st ed., IARC – International Agency
for Research on Cancer, Lyon, 2012.
[24] R. Jenkins, X-Ray Fluorescence Spectrometry , John Wiley & Sons Ltd, Canada, 1988.
[25] R. Jenkins, X-ray Techniques: Overview , Encycl. Anal. Chem. (2000) 13269 –13288.
[26] R. Jenkins, R.W. Gould, D. Gedcke, Quantitative X -Ray Spectrometry , Dekker, New York, USA, 1995.
[27] D.R. Lide, ed., CRC Handbook of Chemistry and Physics , 90th ed., CRC Press/Taylor and Francis, Boca
Raton, FL, 2010.
[28] W. Lin, H. Huff, Silicon Materials , in: R. Doering, Y. Nishi (Eds.), Handb. Semicond. Manuf. Technol.,
2nd ed., CRC Press/Taylor and Francis, Boca Raton, FL, 2008: pp. 3 –1.
[29] B. Marcinik, La moneta , in: Paesaggi Pastor. D’alta Quota. Le Ric. Del Progett. Alpes 2010 -2014,
University of Trento, Trento, I, 2015: pp. 105 –106.
[30] J. Meija, T.B. Coplen, M. Berglund, W.A. Brand, P. De Bievre, M. Groening, N.E. Holden, J. Irrgeher,
R.D. Loss, T. Walczyk, T. Prohaska, Isotopic compositions of the elements 2013 (IUPAC Technical Report) ,
Pure Appl. Chem. 88 (2016) 293 –306.

References

45 [31] J. Meija, T.B. Coplen, M. Berglund, W.A. Brand, P. De Bievre, M. Groening, N.E. Holden, J. Irrgeher,
R.D. Loss, T. Walczyk, T. Prohaska , Atomic weights of the elements 2013 (IUPAC Technical Report) , Pure
Appl. Chem. 88 (2016) 265 –291.
[32] E.A. Mitchell, ed., Production of aluminum metal by electrochemistry , 1st ed., American Chemical Society,
Oberlin, OH, 1997.
[33] E. Montenegro, I dogi e le loro monete , Montenegro, Torino, 2012.
[34] B.G. Muniz, Fabricaciòn de la moneda , (2004) 62.
[35] R. Puchta, A brighter beryllium , Nat. Chem. 3 (2011) 416 –416.
[36] G. Ricuperati, Corso di Storia – L’età moderna , Loescher Editore, Torino, 1984.
[37] T. Rosenqvist, Priciples of extractive metallurgy , 2nd ed., McGraw -Hill, Singapore, 1986.
[38] V. Sedlacek, Non-ferrous metals and alloys , 1st ed., Elsevier B.V., Praha, CZ, 1986.
[39] J.F. Shackelford, W. Alexander, Materials Science and Engineering Handb ook, 3rd ed., CRC Press, Boca
Raton, FL, 2001.
[40] L.L. Shreir, R.A. Jarman, G.T. Burstein, eds., Corrosion, Vol. 1 – Metal/Environment Reactions , 3rd ed.,
Butterworth -Heinemann, Woburn, MA, 1993.
[41] R.E. Smallman, R.J. Bishop, Modern Physical Metallurg y and Materials Engineering , Butterworth Heinmann,
London, UK, 1999.
[42] R. Troncon, L’oro, in: L. Endrizzi, F. Marzatico (Eds.), Ori Delle Alpi, Castello del Buonconsiglio –
Monumenti e collezioni provinciali, Trento, I, 1997: pp. 13 –18.
[43] K.A. Walsh, Beryllium chemistry and processing , ASM International, 2009.
[44] www.treccani.it, Enciclopedia Treccani Online , Istituto della Enciclopedia Italiana, 2017.
[45] B.G. Yacobi, Semiconductor Materials An Introduction to Basic Principles , Kluwer Academic Pub lishers, New
York, 2004.
[46] A. Zorzi, La Repubblica del Leone. Storia di Venezia , Bompiani, 2001.