Nuclear Instruments and Methods in Physics Research B 486 (2021) 73–84

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Nuclear Inst. and Methods in Physics Research, B

journal homepage: www.elsevier.com/locate/nimb

Estimation of Ag coating thickness by different methods using a handheld

XRF instrument
J. Brocchieri , E. Scialla , C. Sabbarese *
Department of Mathematics and Physics and Center for Isotopic Research on the Cultural and Environmental Heritage (CIRCE), University of Campania “L. Vanvitelli”
Caserta, Italy

A R T I C L E I N F O A B S T R A C T

Keywords: Precious objects are often made from a thin layer of metal (gold or silver) superimposed on another metal or
Thickness estimation alloy. Non-invasive XRF analysis is widely used on these objects to determine the composition and thickness of
Ag layers the surface layer. Here, silver surface thickness of two-layered metal samples using an ED-XRF handheld spec­
Handheld XRF
trometer is estimated by different methods whose results are compared. These methods involved the relation­
PLS regression
X-ray characteristic lines
ships between the intensities of the characteristic lines of Kα, Kβ, Lα and Lβ of Ag and of elements present in the
substrate (Cu, Fe, Pb) and some of their combinations, as well as the PLS regression. Reference layers were used
to derive the calibration curves of each methodology. PLS method was the most accurate, but the other methods
were also found suitable for the purpose. Applications have been successfully made on an ancient Roman coin
and a modern silver-plated object.

1. Introduction covered by gold or silver [8,9].

Two-layered materials are very common in the field of archaeometry
[1-3]. On the precious artifacts a thin metal layer can overlap a sheet of
another metal or alloy. Determining the nature of two metals and the
thickness of surface layer is useful to reconstruct the complete structure
and to obtain data of historical, artistic and cultural interest. To achieve
these goals, the use of a non-destructive technique is preferred and often
advantageous for cultural heritage. The x-ray fluorescence (XRF) tech­
nique is certainly a useful tool for the preliminary analysis of metal ar­
tifacts [4]. It can be adapted to many analytical problems because it
allows you to determine the elemental composition of the surface layer
of an object and to estimate the concentration of the detected elements.
Based on the attenuation of x-rays, the study of the fluorescence
intensity ratio of characteristic peaks for selected elements present, can
be usefully employed to estimate the thickness of layers [5,6]. A
multivariate statistic method, the ordinary Partial Least Squares
regression (PLS), has also been applied to obtain the overlapping layer
thickness [7].
Although less than gold, silver was also used as a coating material for
decorative reasons. The composition and the thickness of this layer
reveal much about of an object. Several methods for thickness estima­
tion are used. This group has already reported findings on metal samples
The choice of the thickness measurement method depends on the
characteristics of the object studied. For example, several industry sec­
tors require measuring thin film thickness. The potential of energy
dispersive x-ray fluorescence spectrometry for thickness measurements
of thin films of polymeric materials was also investigated using uni­
variate and multivariate statistical tools [10].
Similar methods have been employed by many authors to analyze
silver and gold enameled materials. This is a particular of analysis of the
Ag (or Au) alloy attributed to the Tumbaga manufacturing method
[5,11].
Another case is the study of processional crosses of Borbona where a
wooden core is enriched with gilded and embossed silver sheets [12].
The studies were based on the investigation of X-ray fluorescence and on
the relationship between the intensity of the ratio of two characteristic
lines, one from a substrate element and the other from the surface layer.
In the non-destructive surface analysis of silver objects, especially for
historical silver coins, a common problem is the depletion of Cu from
nearby surfaces which leads to a higher Ag content on the coin surface.
Identification and quantification of Ag and Cu surface enrichments can
be performed using XRF: the peak intensity ratios of Ag Kα/Ag Lα, Cu Kα/
Ag Kα and Cu Lα/Ag Lα and Cu Lα/Ag Lα for coins have been compared
with Ag-Cu standards of similar composition [13].

* Corresponding author.
E-mail address: carlo.sabbarese@unicampania.it (C. Sabbarese).

https://doi.org/10.1016/j.nimb.2020.11.006
Received 4 August 2020; Received in revised form 31 October 2020; Accepted 8 November 2020
0168-583X/© 2020 Elsevier B.V. All rights reserved.
J. Brocchieri et al. Nuclear Inst. and Methods in Physics Research, B 486 (2021) 73–84

Fig. 1. Antoninianus silver coin.

The study arises from the need to determine concentration and

thickness of the silver often due to surface enrichment, using the non-
destructive technique of x-ray fluorescence [14].
Using multi-technique approaches based on the combination of
surface analysis techniques such as FIB-FESEM-EDX, micro-Raman or
VIMP spectroscopy and cross-sectional analysis using EMPA and SEM-
EDX, a set of ancient Antoninian silver coins was studied [15] to char­
acterize the alloy composition and complex microstructures and,
therefore, to complement archaeometry analysis and historical issues (e.
g. surface silvering processes). The Kα/Lα ratio test was introduced [16]
to assess the presence of a surface Ag-rich layer in ancient coins and to
determine the thickness of this layer [17,18].
The aim of the present study is to provide a set of useful procedures
to determine the thickness of a surface layer in silver objects. A portable
ED-XRF instrument has been employed to analyze metal sheets (copper,
iron, lead) covered by various silver layers having thickness ranges be­
tween 0.2 and 15.7 μm. The value of silver thicknesses has been calcu­
lated through the Kα/Kβ and Kα/Lα intensity ratios of the x fluorescence
of Ag and of main characteristic lines of the elements behind the silver;
these ratio values change based on the thickness and relative position of
the element selected for the calculation of the ratio within the layered
Fig. 2. Silver-plated object.
structure. The XRF is a low-penetrating surface technique that is reliable
up to fifteen microns.
The PLS regression has also been employed creating a calibration rich coin (up to 80% of Ag), but gradually was devalued becoming a
model with XRF spectra of some samples given as standards and its bronze coin with a very low content of silver (about 2–3% of Ag).
prediction skills have been tested. Initially, the imperial silver coinage was in great production, with high
The novelty of this study is above all a clear comparison between the content of Ag, but with the worsening of political and economic con­
various methods to verify the consistency of the results and establish the ditions, also the Antoninianus was devalued and copper and tin were
effectiveness of each method. added to silver: the resulting alloy was still similar to silver [19–21]. The
All methods were tested on an Antoninianus coin, minted under silver content can be overestimated. A different approach on how to
different Roman Emperors and belonging to private collection, and a report Ag content was held by the High Empire silver coin researchers
modern object. The coin has a surface enrichment, whereas the other is a Walker and Butcher & Ponting. Butcher and Ponting argue that the
silver-plated. surfaces of the coins that Walker had examined had likely been depleted
of copper during manufacture, during the centuries of burial, and during
2. Material and methods cleaning after their discovery [22]. Towards the middle of the kingdom
of Gallienus the coin had a very low percentage of silver (about 5–10%),
2.1. Reference sample and artifacts but during the minting it was treated with acids in order to remove the
copper from the surface of the coin, which had, therefore, an external
Silver reference foils for calibration were used by covering metal layer of silver; the silver layer, however, was so thin that it quickly
plates (Cu, Fe, Pb). The thickness of silver cover was gradually increased disappeared with use, making the copper below appear. Adding layers of
by using 58 silver foils (Ag99.9% ± 0.3%). The standards have 0.2, 0.4, Ag-enriched copper alloy on the coin surface was common. It was
0.5, 0.6, 1.3, 2.0, 2.6, 3.3, 3.9, 4.4, 4.7, 5.0, 5.6, 6.1, 6.8, 8.3, 9.5, 10.2, necessary to perform due to the difficulties regarding the supply of raw
11.9, 12.6, 13.4, 14.5 and 15.7 μm thicknesses respectively, measured materials and the needs to save Ag. This coin is selected for study as an
by a thickness meter (Mahr Feinprüf Millitron nr. 1234 IC/Z) having a example of an object with surface enrichment.
sensibility of 0.01 μm.
2.1.2. Silver-plated object
2.1.1. Antoninianus silver coin A modern religious icon (Fig. 2) was chosen for the study of a silver-
A silver coin (Fig. 1) belongs to the series of Antoninianus (from 214 plated object. It portrays a child during communion (i.e., in the Catholic
to 274 CE) was introduced by Caracalla (Marcus Aurelius Antoninianus Church, a sacramental-juridical institution). It is made from a sheet of
– hence the name) in an attempt to overcome the serious financial crisis aluminum and iron covered with silver. Its thickness is (542 ± 1) μm.
of the time: it is a currency with a nominal value, corresponding to two
denarii. At the beginning, the Antoninianus denomination was a silver- 2.1.3. Instrumentation
Measurements are made using a XSORT XHH03 (Spectro) handheld

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J. Brocchieri et al. Nuclear Inst. and Methods in Physics Research, B 486 (2021) 73–84

spectrometer equipped with a Rh tube. This instrument is available at

the CIRCE laboratory (http://www.circe.unicampania.it). The X-ray
generator operates at 50 kV with a current of 125 μA. The used Si drift
detector has a 10 mm2 active area and about 160 eV at the Kα line of the
Mn (5.9 keV) energy resolution. It allows changing the current of the X-
ray tube to detect all the elements from Z = 11 (Na) to Z = 92 (U). The
measurement time was 30 s (20 s using a 50 kV tube voltage and 10 s
with 15 kV) and the investigated area is about 0.7 cm2. Acquisition and
analysis of XRF spectra were carried out using XRF Analyzer CE and XRF
Analyzed PRO. Verification of instrumental reproducibility was per­
formed with the reference silver sheets as also previously in the work
[8].
PYMCA software [23] was also used to extract the net area of Kα, Kβ
and Lα lines of X-rays fluorescence of Ag, Kα and Kβ of Fe, Kα and Kβ of Cu,
Lα and Lβ of Pb. MATLAB software with PLS toolbox pack was used for
the data treatment. The fit of the experimental data is done using an
algorithm based on routines and functions in the MATLAB toolbox curve
fitting environment.

2.2. Theoretical background Fig. 3. Layout of the measurement configuration for a double layer: b is Ag
layer covering another metal a.
2.2.1. Self-attenuation X-ray and attenuation by a second layer
To investigate homogeneity and two-layered structure of a sample, it characterization of Kα and Lα to provide further information on the na­
is essential to determine the thickness of coating layer. For this reason, ture of the surface thickness.
the detailed analysis of the fluorescence peaks and in particular the ratio In another case, when a layer of a sample a of any thickness is
values between the characteristic lines of an element present, is very covered by a second layer b (Fig. 3), the ratio between the lines of the
useful because ratios depend on the abundance of respective elements element behind the first layer is attenuated by the covering according to
deriving from a certain depth. the following theoretical equation [25,26]:
When an incident x-ray beam interacts with the atoms of the element ( ) ( )
{ }
present in a mono-elemental sample of any thickness, the excited shells Kα
=
Kα
* e− (μ1 − μ2 )d (2)
generate secondary X-rays from a point of the material at specific en­ Kβ Kβ ∞
ergies. These characteristic X-ray lines (Kα, Kβ, Lα, Lβ) are partially
where:
absorbed into the layer itself before reaching the detector. The attenu­
ation effect depends on the position of the element, that is the thickness, ( )
and the efficiency of the detector at the energies involved. The x-rays Kα
is the intensity ratio of the characteristic lines of the sample a
Kβ
emitted undergo two attenuation processes: self-attenuation of the ∞

element in its own layer and attenuation by the overlapping layer. Self- with infinite thickness;
attenuation can be expressed by the following equation [24]: μ1 is the linear attenuation coefficient (cm− 1) of the element at en­
ergy of Kα emission line of sample a
} {( ’ )} { }
μ2 is the linear attenuation coefficient (cm− 1) of the element at en­
( ) ( ) {
1 − e− (μ0 +μ1 )x
’ ’
Kα Kα ε(Kα ) μ0 + μ’2
= * * * (1)
Kβ Kβ 0 ε(Kβ ) (μ’0 + μ’1 ) 1 − e− (μ0 +μ2 )x
’ ’ ergy of Kβ emission line of sample a;
x
d is path length of the characteristic radiation (in cm) and d = cosθ2 ,
where: where x is the thickness of the layer and θ2 is the angle between the
detector and the normal to the sample.
( )
Kα
is the intensity ratio for an infinitely thin sample (that is when
Kβ
0
The Eq. (2) also applies to elements whose characteristic lines are Lα
the thickness of the sample is negligible compared to the depth of and Lβ .
penetration); From formula (2) the thickness of the coating layer d as a function of
ε(Kα), ε(Kβ) are the detector efficiency values at the energies Kα and the ratio between the Kα and Kβ lines of the substrate element is [27,28]:
Kβ; ( )
cosθ2 R1
μ0 = μ0 /cosθ1 , μ0 is the linear attenuation coefficient (cm− 1) of the
′
d = − ′′ ′′
*ln (3)
μ1 − μ2 R2
element at incident energy E0 and θ1 is the angle between the x-ray
tube and the normal to the sample surface. where:
μ1 = μ1 /cosθ2 , μ1 is the linear attenuation coefficient (cm− 1) of the
′

element at energy of Lα line and θ2 is the angle between the detector μ′′ 1 is the linear attenuation coefficient (cm− 1) of the covering layer
and the normal to the sample surface; at energy of Kα (or Lα )line;
μ2 = μ2 /cosθ2 , μ2 is the linear attenuation coefficient (cm− 1) of the
′
μ′′ 2 is the linear attenuation coefficient (cm− 1) of the covering layer
element at energy of Lβ line; at energy of Kβ (or Lβ )line;
x is the thickness of the layer (cm). R1 is the intensity ratio between characteristic lines of the element
{ } { }
′ ′ ′ ′
− μ +μ x
present in the substrate;
(μ0 +μ2 ) 1− e ( 0 0 )
The product * is self-attenuation factor. R2 is the intensity ratio between characteristic lines of the element
(μ′0 +μ′1 ) ′ ′
− μ +μ x
1− e ( 0 2 )
present in the substrate considering an infinite thickness.

If Lα and Lβ are the X-ray lines involved in the ratio, a similar The thickness of a thin layer of element b in presence of a substrate
equation is obtained. layer a (Fig. 1) can be also estimated by the ratio between the principal
This method can be further combined with the peak intensity

75
J. Brocchieri et al.
Fig. 4. 16 XRF spectra vs Ag thickness as used for the calibration curves in the four configurations: a) Ag b) Cu covered with sheets of Ag c) Pb covered with sheets of
Ag d) Fe covered with sheets of Ag.
lines of the two elements characterizing the two layers (for example, in
the case of silver-plated copper, the ratio Nb/Na = AgKα /CuKα ).
The following theoretical equation expresses its dependence on the
thickness of the layer b [25]:
( ) {( ’ )} ( ) necessarily many observations.
Nb μa0 + μ’aa
=P * 1 − e− (μb0 +μbb )ρb xb *(e(μb0 +μba )ρb xb
’ ’ ’ ’
(4)
Na (μ’b0 + μ’bb )
where:
P is the probability of detection of the line of interest. It includes the
probability of line emission, the fluorescence yield of the element
and the detector efficiency at the energy of the interest line;
μ’a0 =μa0 /cosθ1 and μ’b0 =μb0 /cosθ1 , μa0 and μb0 are the total mass
attenuation coefficients (cm2/g) of the elements a and b at incident
energy;
μ’ba = μba /cosθ2 , μba is the total mass attenuation coefficient of the
element b to the energy of the affected line of element a (cm2/g);
μ’aa = μaa /cosθ2 , μaa is the total mass attenuation coefficient of the
element a to the energy of the affected line of element a (cm2/g);
μ’bb = μbb /cosθ2 , μbb is the total mass attenuation coefficient of the
element b at the energy of the involved line of element b (cm2/g);
ρb is the density of the element b (g/cm3);
xb is the thickness of the layer b (cm).
2.2.2. The PLS regression
The Ordinary Partial Least Squares regression (PLS) is a quantitative
multivariate analysis method that has been widely used for spectra data
evaluation and it is well-known for several applications in archaeometry
[7].
PLS regression is probably the least restrictive method of the various
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Nuclear Inst. and Methods in Physics Research, B 486 (2021) 73–84
multivariate extensions of the multiple linear regression model because
it can be used also in the presence of inaccurate data. This flexibility
makes it usable in situations where other traditional multivariate
methods are limited, such as when there are many variables but not
As multivariate calibration method, PLS regression allow relating
thickness of the samples directly to measured XRF spectra (or portions of
them). The procedure comprises of two steps: calibration and validation.
Calibration step establishes the relation between the data matrices X and
Y, while validation is an essential step because it proves the ability of the
calibration model to predict the desired thickness [29].
The study of model performance consists of the evaluation of the root
mean square error of calibration (RMSEC) and the root mean square
error of validation (RMSEP) [7].
The RMSEC value represents to what extent the PLS procedure is
suited for modeling the dependent variable (i.e. coat thickness) and the
uncertainty of the reference method (spectra XRF) [30].
The RMSEP value is the mean deviation of the prediction from the
respective reference value calculated with the given model. It is an in­
dicator of the average error for coat thickness prediction on unknown
samples. Good models are characterized by low RMSEP values, close to
the error of the reference method [29].
Its value is a measure of the good fit between known thickness and
predicted thickness [31].
RMSEP is expressed in the same units as the predicted parameter.
The results of future predictions can then be presented as predicted
values ± RMSEP. This measure is valid provided that the new samples
are similar to the ones used for the calibration otherwise the prediction
error might be much higher [32].
J. Brocchieri et al. Nuclear Inst. and Methods in Physics Research, B 486 (2021) 73–84

Fig. 5. Experimental data and fit curves vs Ag layer thickness of: (a) AgKKαβ ; (b) CuKKαβ ; (c) FeKKαβ ; (d) PbLLαβ .

3. Results and discussion

Table 1
Theoretical and fit values of Ag(Kα/Kβ) vs thickness of Ag layer using Eq. (1). The
The XRF spectra acquired for the realization of calibration curves
thickness of 0.2 µm was considered infinitely thin.
with different methodologies for silver thickness estimation are shown ( )
Kα μ0 +μ1 (µm− 1) μ0 +μ2 (µm− 1)
in Fig. 4. The four configurations used are: Ag alone (Fig. 4a), Cu Ag
Kα
Kβ Kβ 0.
covered with Ag foils (Fig. 4b), Pb covered with Ag foils (Fig. 4c) and Fe
Theoretical 6.67 0.059 0.052
covered with Ag foils (Fig. 4d). Fig. 4b) c) and d) show that by increasing Fit 6.69 ± 0.03 0.61 ± 0.23 0.58 ± 0.25
the thickness of Ag attenuates the characteristic lines of the elements
behind the silver.
To determine the thickness of the silver foils in unknown samples substrate element (Eq. (2)) using the characteristic ratios versus Ag
using PXRF (Portable X-Ray Fluorescence) with the proposed theoretical thickness are shown in Fig. 5.
model a calibration method for the handheld spectrometer is required. The theoretical parameters are compared with the experimental
The calibration method proposed was made with a series of reference ones. In the case of self-attenuation, Eq. (1), the values of fit a, b and c
( )
samples with known thicknesses, where the ratio of a net area curve
represent KKαβ , μ0 +μ1 and μ0 +μ2 respectively. Theoretical and
(counts) under the peak of the element was plotted against silver 0.
thicknesses. The investigation method and the working conditions used experimental values of the Ag(Kα/Kβ) intensity ratio versus silver layer
to obtain the fit curves are the same as those obtained in a previously thickness are shown in Table 1.
work [9]. The incident radiation energy (E0 ) was set to 29.5 keV in the The unfiltered direct excitation from the source produces lower in­
theoretical curve [8]. The incident energy mean value (E0 ) was used tensity ratios that deviate from the theoretical values (Table 1).
because bremsstrahlung (and not monoenergetic) radiation was The attenuation of the x-rays by the matter is described by a
employed [25]. This energy value is not easy to determine when using
an X-ray tube, because it depends on its characteristics, on the filtering
of the X-ray beam and the hardening of the beam in the sample [33]. Table 2
Monochromatic radiation is ideally required to improve accuracy. Theoretical and fit values of Cu(Kα/Kβ), Fe(Kα/Kβ) and Pb(Lα/Lβ) vs thickness of
Despite the difficulties of using monochromatic radiation in portable Ag layer using Eq. (5). The infinitely thick thickness is obtained by measuring
instrumentation applicable in Cultural Heritage studies, unfiltered ra­ the respective metal samples without the silver coating.
diation can also be used to obtain reliable results [27]. Moreover, an (
Kα
)
(μ1 − μ2 ) a b (µm− 1)
(µm− 1)
appropriate calibration curve for PXRF system must be carried out, Kβ ∞ cosθ2
especially to decrease the uncertainties arising from the geometry used Cu
Kα 6.45 0.071 6.3 ± 0.1 0.07 ± 0.02
and minimize the background and scattered radiation. Kβ
Kα 6.58 0.123 6.46 ± 0.05 0.13 ± 0.01
The fit curves to the data that describe the self-attenuation (Ag alone, Fe
Kβ
Lα 1.65 0.056 1.62 ± 0.01 0.07 ± 0.03
Eq. (1)) and the attenuation of the surface layer of an element of a Pb
Lβ

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J. Brocchieri et al. Nuclear Inst. and Methods in Physics Research, B 486 (2021) 73–84

Fig. 6. Experimental data of Ag KLαα and fit curve vs Ag thickness layer in the four configurations analyzed using reference samples. a) Ag, b) Cu covered by Ag, c) Fe
covered by Ag and d) Pb covered by Ag.

The trends of the net area of the Kα lines as a function of the thickness
Table 3
of the Ag layer and of the element behind the silver are investigated
Fit data obtained from the linear approximation curve (ax +b) of the AgKα/Lα
(Fig. 7). The differences in trends indicate how much and how the un­
ratio and Ag thickness in the different materials used as a reference.
derlying metal affects the fluorescence of silver. Only Kα trends of the
a b (µm− 1) silver foils follow a growth curve. The curve for the Ag-only sample rises
Ag 0.30 ± 0.01 0.68 ± 0.01 faster than the other three. However, Ag on Cu and Fe approaches the
Cu 0.32 ± 0.01 0.5 ± 0.1 Ag-only curve towards the end.
Fe 0.33 ± 0.01 0.5 ± 0.1
The influence of the underlying material on the behavior of the
Pb 0.31 ± 0.01 0.6 ± 0.1
characteristic lines of Kα is shown in Fig. 7. Note that up to thicknesses of
4 µm the characteristic lines of the element behind are much less
decreasing exponential curve. Hence, ratio values of the characteristic attenuated by silver.
lines of copper, iron and lead (i.e. all the materials covered by the silver Another method to determine the thickness of a multi-layer sample is
layers) are fitted by following equation: obtained by the calibration curve of the ratio between the characteristic
( ) lines of two elements characterizing the layers. This is described by Eq.
Kα { }
= a* e− b*d (5) (4) and has been applied to (Ag-Kα /Cu-Kα ), (Ag-Kα /Fe-Kα ), (Ag-Kα /Pb-
Kβ
Lα ) ratios vs Ag thickness, assuming Cu, Fe and Pb of infinite thickness
( ) respectively.
Kα
with a = Kβ , b = (μ1 − μ2 ) and d = thickness of silver layers. Experimental data and fit curves are shown in Fig. 8.
∞.
Fit curves of the cross ratios data in presence of copper and lead are
In this case, the results of fit parameters (Eq. (5)) are in good
represented at all the Ag thicknesses analyzed (Fig. 8); for iron, it was
agreement with theoretical data (Table 2).
possible to use data of silver thicknesses up to 5.5 μm because the
Despite the fact that the ratio of AgKα/Lα vs Ag thickness is described
characteristic lines of iron after a such thickness are completely atten­
by a growth curve, its experimental and theoretical values are well
uated (as shown in Fig. 4d)).
approximated by a linear curve for sub-micrometers thicknesses (Fig. 6).
The term P, in the Eq. (4), indicates the probability of detection of the
The fit parameters derived from the linear curve (Table 3) allow tracing
line and the element of interest, which includes the probability of
the silver thickness values more easily and effectively.
emission of a given line, the fluorescence yield of the element and the

78
J. Brocchieri et al.
Fig. 7. Trend of Ag Kα peak area of silver (black) and Ag Kα peak area of copper (red), iron (magenta) and lead (green) that covered by silver foils vs thickness of
silver foils. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
energy efficiency of the detector to the energy of the line [11]. Due to the
fact that the determination of the P value is difficult, it was derived from
experimental measurements. However, it increases the uncertainty in
the theoretical trend. Table 4 shows the results obtained from the fit (Eq.
(4)) of the experimental and theoretical values.
All the described methods are based on an accurate analysis of K or L
peaks to obtain a valid calibration curve for the thickness estimation of
the surface layer in a multilayer object. A correct evaluation of the net
area and subtraction of the background of involved peaks, and an
effective separation of the peak of interest from possible contiguous,
disturbing peaks are required [6].
In the application of the PLS regression, sixteen XRF spectra were
used for calibration and seven for validation; all obtained with Ag
thickness known. The calibration spectra data were arranged in a 16 ×
1300 matrix (X) and the thickness values in a 16 × 1 matrix (Y). The
validation data were organized in a 7 × 1300 matrix (X). This method
was done for the four experimental set up. The whole spectrum, from 0
keV to 26 keV, containing all the peaks of Ag and the other elements was
used (Fig. 4).
PLS regression curves obtained for calibration of the four set up (Ag
and Cu, Fe, Pb covered by Ag) are shown in Fig. 9. The results of the
validation samples are shown in the same graphs to show their agree­
ment with the calibration curve.
79
Nuclear Inst. and Methods in Physics Research, B 486 (2021) 73–84
In the analysis of the silver thicknesses only the model with five
latent variables explained 99.67% of the variance. The determination
coefficient for the calibration curve was 0.9967 and for the prediction
data was 0.9867 (Fig. 9a). The RMSEC and RMSEP values were 0.27 and
0.33 respectively.
In the set-up of copper covered with silver the model with six latent
variables explained 99.9% of the variance. The determination coeffi­
cient for the calibration curve was 0.999 and for the prediction data was
0.9963 (Fig. 9b). The RMSEC and RMSEP values were 0.13 and 0.30
respectively.
In the case of lead covered with silver the model with six latent
variables explained 99.95% of the variance. The determination coeffi­
cient for the calibration curve was 0.9995 and for the prediction data
was 0.9989 (Fig. 9c). The RMSEC and RMSEP values were 0.10 and 0.17
respectively.
In the case of iron covered with silver the model with four latent
variables explained 99.7% of the variance. The determination coeffi­
cient for the calibration curve was 0.997 and for the prediction data was
0.998 (Fig. 9d). The RMSEC and RMSEP values were 0.25 and 0.21
respectively.
Although the prediction curves are well explained by the model.
The comparison between the various methods used for thickness
estimation is shown in Table 5.
J. Brocchieri et al. Nuclear Inst. and Methods in Physics Research, B 486 (2021) 73–84

Fig. 8. Experimental data and fit curves of Ag-Kα /Cu-Kα , Ag-Kα /Fe-Kα and (Ag-Kα /Pb-Lα ) versus Ag thickness according to Eq. (4).

to consider the irregularity and understand the composition variability

Table 4 from point to point [34,35].
Theoretical and fit values of Ag-Kα /Cu-Kα , Ag-Kα /Fe-Kα and (Ag-Kα /Pb-Lα ) Average concentration of each element is reported in Table 6. For the
versus Ag thickness layer using Eq. (4). thickness estimation the average spectra are used.
P μb0 +μbb μb0 +μba a b (µm− 1) c (µm− 1) Concentrations of the detected elements on both sides of the coin are
(µm− 1) (µm− 1) consistent considering the uncertainty. Therefore, the coin is composed
Cu 0.41 0.0596 0.075 0.11 0.098 0.32
of Cu (94.8 ± 0.4)% and Ag (3.1 ± 0.2)%. The PLS method and the
Fe 0.60 0.0596 0.067 0.43 0.025 0.67 methods of CuKKαβ and Ag-Kα /Cu-Kα ratios are used for thickness esti­
Pb 0.69 0.0596 0.130 0.75 0.0596 0.13
mation of the surface silver. Not all of them are useful and powerful for
all objects. The chosen of these methods is based on the Ag thickness. In
The thicknesses obtained with the PLS method were determined this case, in fact, the Ag thickness is very thin. The results obtained are
using the regression coefficient matrix. While the inverse formulas of the shown in Table 7.
fit equation of the characteristic line ratios were used to estimate the The estimated thickness is therefore (0.5 ± 0.2) μm in agreement
thicknesses (where possible). with the thickness estimated on some coins belonging to the same
To have a more complete view and a more immediate comparison, coinage in [15].
the same results are represented by a bar graph (Fig. 10) in which each In precious samples, especially in metal samples, a thin layer of metal
colour indicates a method used. Reference values are also reported. PLS is overlapped with a sheet of metal from another metal or alloy, e.g.
is the most accurate method by comparing the results with the reference silver plating. However, surface measurements on ancient silver samples
values. may not lead to reliable data on mass composition due to the silver
The estimate of unknown Ag thicknesses in some objects is shown enrichment of the near surface layer [36]. The composition and thick­
below through the methodologies described above. An ancient Roman ness of each layer can be determined. However, in the case of surface
coin and a modern Ag-plated object was used. enriched objects a more critical approach is needed. For Antoninianus
coin, the approach was simpler as the Ag content gradually depleted
3.1. Silver coin with the deepening while the Cu content increased. Very often the
surface enrichment thickness is thicker. The characteristic lines of silver
XRF measurements are performed on the surface of untreated coin. could be studied: the characteristic lines Kα and Lα , net areas obtained
Six XRF point measurements are performed on coin both on the observed from the spectrum, allow the evaluation of the depleted layer. While the
side and on the reverse side. This procedure is applied due to the su­ Ag Lα radiation mainly originates from the most superficial layer, from a
perficial structures and the lack of homogeneity of the samples in order depth of up to 2 μm, the information depth of the Ag Kα radiation is up to

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Fig. 9. PLS regression curves for calibration and validation samples. The error bars indicate the response residuals.

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J. Brocchieri et al. Nuclear Inst. and Methods in Physics Research, B 486 (2021) 73–84

Table 5
Thickness values for the seven silver foils determined by the different methodologies. y_m indicates the thicknesses measured with the micrometer, y_PLS indicates the
thicknesses predicted with the PLS method, y_ AgKα/Kβ, y_AgKα/Lα indicate the thicknesses obtained from the ratio curves, AgKα/Kβ , AgKα/Lα respectively.
Thickness of the surface layer of Ag (μm)

y_m y_PLS y_AgKα/Kβ y_ AgKα/Lα

0.4 ± 0.1 0.6 ± 0.3 / /

2.0 ± 0.1 1.6 ± 0.3 2.1 ± 1.0 1.6 ± 0.4
3.3 ± 0.1 2.6 ± 0.3 3.7 ± 1.0 2.9 ± 0.4
5.0 ± 0.4 5.2 ± 0.3 6.7 ± 1.0 5.5 ± 0.4
9.5 ± 0.1 9.7 ± 0.3 9.7 ± 1.0 9.8 ± 0.4
12.6 ± 0.1 12.5 ± 0.3 / 12.3 ± 0.4
14.5 ± 0.5 14.3 ± 0.3 / 14.0 ± 0.4

Thickness of the surface layer of Ag covering Cu (μm)

y_m y_PLS y_CuKα/Kβ y_Ag Kα/Lα y_ AgKα/CuKα

0.4 ± 0.1 0.5 ± 0.3 0.3 ± 0.4 0.2 ± 0.3 0.4 ± 0.3
2.0 ± 0.1 2.0 ± 0.3 1.9 ± 0.4 1.8 ± 0.3 2.1 ± 0.3
3.3 ± 0.1 2.7 ± 0.3 3.0 ± 0.4 2.9 ± 0.3 3.2 ± 0.3
5.0 ± 0.4 5.2 ± 0.3 5.1 ± 0.4 5.3 ± 0.3 5.5 ± 0.3
9.5 ± 0.1 9.9 ± 0.3 9.2 ± 0.4 9.9 ± 0.3 9.8 ± 0.3
12.6 ± 0.1 12.8 ± 0.3 11.5 ± 0.4 12.6 ± 0.3 12.8 ± 0.3
14.5 ± 0.5 14.4 ± 0.3 12.9 ± 0.4 14.1 ± 0.3 15.0 ± 0.3

Thickness of the surface layer of Ag covering Pb (μm)

y_m y_PLS y_rPbLα/Lβ y_AgKα/Lα y_ AgKα/PbLα

0.4±0.1 0.2±0.2 0.3±0.2 / 0.4±0.4

2.0±0.1 2.1±0.2 1.9±0.2 1.7±0.6 2.0±0.4
3.3±0.1 3.4±0.2 3.1±0.2 2.9±0.6 3.2±0.4
5.0±0.4 5.1±0.2 5.3±0.2 6.3±0.6 5.1±0.4
9.5±0.1 9.6±0.2 9.6±0.2 9.8±0.6 9.5±0.4
12.6±0.1 12.7±0.2 12.6±0.2 12.4±0.6 13.1±0.4
14.5±0.5 14.8±0.2 14.7±0.2 14.6±0.6 /

Thickness of the surface layer of Ag covering Fe (μm)

y_m y_PLS y_FeKα/Kβ y_Ag Kα/Lα y_ AgKα/FeKα

0.4 ± 0.1 0.4 ± 0.2 0.4 ± 0.5 / 0.6 ± 0.3

2.0 ± 0.1 1.6 ± 0.2 1.9 ± 0.5 1.7 ± 0.4 2.2 ± 0.3
3.3 ± 0.1 3.5 ± 0.2 3.1 ± 0.5 3.0 ± 0.4 3.3 ± 0.3
5.0 ± 0.4 5.3 ± 0.2 5.2 ± 0.5 5.5 ± 0.4 5.3 ± 0.3
9.5 ± 0.1 9.5 ± 0.2 9.8 ± 0.5 10.0 ± 0.4 /
12.6 ± 0.1 12.6 ± 0.2 13.0 ± 0.5 12.5 ± 0.4 /
14.5 ± 0.5 14.7 ± 0.2 15.3 ± 0.5 14.1 ± 0.4 /

100 μm in a silver-copper matrix due to its higher energy. By calculating
the Ag Kα /Ag Lα intensity ratios it is possible to obtain information on
the degree of exhaustion. The value of this ratio can be used as an
indication of whether or not silver is enriched on the surface of a coin
[16].
3.2. Silver-plated object
XRF measurements are performed on the surface of untreated sam­
ples. Two XRF point measurements are performed on both side of reli­
gious object. In particular, the head of child was analyzed.
Concentrations of the detected elements on both sides are different.
Therefore, the plated part consists of Ag (97.6 ± 0.1)% instead the back
part of the samples is composed by Al (93.8 ± 0.3)%, Fe (0.434 ±
0.003)% and Ag (5.748 ± 0.008)%. The methods used for thickness
estimation are PLS and ratio AgKKαβ and AgKα /Lα because the Ag thickness
is very thick. The results obtained are shown in Table 8. Using the self-
attenuation calibration curve, the value attenuates arriving at the
plateau after a thickness of 10 µm so after this thickness it is not possible
to define the thickness accurately.
4. Conclusions
commercial handheld instrument. It is a closed system that does not
allow particular measurement configurations that could improve its
efficiency and effectiveness, but it was adequate for this investigation. A
series of twenty-three reference silver layers with known thicknesses
was used to obtain calibration curves for the estimation of the thickness
of silver objects. A systematic determination of the intensity of Ag Kα, Kβ
and Lα and their ratios is performed for different sheet thicknesses and
for the three elements placed under the silver (copper, iron and lead).
PLS regression methodology was also used on the same spectra in order
to determinate silver thickness of the covering layers. This method uses
directly the spectrum file without any previous processing. Using the
calibration curves obtained, the thicknesses of the silver are estimated in
some objects as a result verification test. It gives consistent results within
the expected thickness range. In fact, the surface enrichment of an
ancient silver coin belonging to the Antoninianus series and the plating
layer of a religious icon were estimated.
CRediT authorship contribution statement
J. Brocchieri: Software, Formal analysis, Visualization, Investiga­
tion, Writing - original draft. E. Scialla: Software, Formal analysis, Data
curation, Investigation. C. Sabbarese: Conceptualization, Investigation,
Methodology, Validation, Supervision, Writing - review & editing.

The X-ray fluorescence technique was used to determine the thick­

ness of superficial layer, as well as providing a surface analysis of the
objects. The XRF measurements were performed using a Spectro X-SORT

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J. Brocchieri et al. Nuclear Inst. and Methods in Physics Research, B 486 (2021) 73–84

Fig. 10. Comparison of the estimated thicknesses with the different methods of the different reference samples realised.

measurements on the Antoninianus coin and for the useful information

Table 6
provided.
Average percentage concentration (%) of main and trace element of observed
(O) and reverse (R) side of the ancient Roman coin.
Appendix A. Supplementary data
Cu Ag Au Pb Fe Zn

Coins_O 94.6 ± 3.1 ± 0.10 ± 1.9 ± 0.059 ± 0.024 ± Supplementary data to this article can be found online at https://doi.
0.3 0.2 0.04 0.2 0.008 0.001
org/10.1016/j.nimb.2020.11.006.
Coins_R 95.1 ± 3.1 ± 0.07 ± 1.5 ± 0.059 ± 0.025 ±
0.6 0.3 0.04 0.2 0.006 0.001
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