Current Analytical Chemistry, 2006, 2, 271-277 271

X-Ray Fluorescence Analysis of Valuable Metals

Alicia Jurado-López and Maria D. Luque de Castro*

Analytical Chemistry Department, Marie Curie Building, Annex, Campus of Rabanales, University of Cordoba, Cor-
doba, E-14071, Spain

Abstract: This paper reviews the use of X-ray fluorescence spectrometry (XRFS) for non-destructive studies of valuable
metallic objects in the fields of jewelry, archaeology and art, as well as its application in the analysis of coatings and solu-
tions, due to the interest of these issues in jewelry manufacture. The general features of the technique as well as the most
outstanding results obtained in the commented fields are described, taking into account the most important sources of er-
ror, mainly in the case of samples that have suffered corrosion processes.
Keywords: X-rays, Noble metals, Jewelry, Cultural heritage.

1. INTRODUCTION systems and sophisticated analyzing crystals. These instru-

1.1. General Features of X-Ray Fluorescence
X-ray fluorescence (XRF) is a technique based on the
photoelectric effect. The source that provides photons of
energy sufficient to carry out it, called primary radiation, is
most often an X-ray tube in which electrons are accelerated
from the cathode to the anode by a high voltage. A high-
energy quantum radiation is generated by the interaction
with the anode material. This radiation is led to the sample,
in which the interaction generates a second X-ray beam,
called secondary radiation, that is detected and conveniently
quantified. Each element emits its unique characteristic sec-
ondary X-rays, the energy of which is related to the analyte
concentration, the sample matrix, and excitation and detec-
tion conditions [1].
There are two ways in which X-ray fluorescence emis-
sion can be collected: by measuring either the wavelength
dispersion or the energy dispersion spectra. Wavelength dis-
persive X-ray fluorescence (WDXRF) requires a crystal to
separate the wavelengths of the different sample elements,
since, for each angle of incident radiation, only the wave-
length that fulfils the Bragg’s formula is reflected to the de-
tector. The elements under analysis are selected by changing
the crystal angle. The intensity of the spectral peaks is ex-
tremely sample-dependent, being affected by interfering X-
ray lines of matrix elements and mechanical preparation of
the sample. As a consequence, quantitative analysis requires
calibration with standards as close as possible to the sample
composition and comparable surface finishing. For very ac-
curate gold analysis, mirror surface has been shown to be
necessary. Under this condition, the method allows to deter-
mining the gold fineness in a gold alloy with accuracy very
close to that obtained by cupellation, i.e. of the order of 1 wt
‰ [2-6]. WDXRF spectrometers require high voltage gen-
erators, high-energy X-ray sources, efficient water-cooling
*Address correspondence to this author at the Analytical Chemistry De-
partment, Marie Curie Building, Annex, Campus of Rabanales, University
of Cordoba, Cordoba, E-14071, Spain; Tel/Fax: +34 957218615; E-mail:
qa1lucam@uco.es
ments are expensive, with considerable installation require-
ments and elevated operational costs. Furthermore, limita-
tions in the sample chamber make WDXRF unsuitable for
assaying most finished gold jewelry articles.
Energy dispersive X-ray fluorescence (EDXRF) spec-
trometers, however, use less powerful X-ray sources than
those based on wavelength dispersion. This fact makes un-
necessary the use of water-cooling, which entails a consistent
economical saving. Thus, these instruments are cheaper and
smaller than those based on WDXRF, achieving very accu-
rate analytical results, as it will be seen further on. Moreover,
recent technological progresses have allowed the construc-
tion of completely portable small-sized EDXRF instruments
for in-situ analysis, which extends the scope of the technique
to as varied fields as archaeometry, environmental analysis
or even in vivo determinations of toxic elements [7]. The
advantages of the use of EDXRF in comparison to the use of
WDXRF have been described elsewhere, with particular
emphasis on precious metal analysis in jewels [8, 9]. In most
of the studies discussed in this review, EDXRF has been the
technique used.
Most commercial instruments are equipped either with
proportional counter or solid state detectors. The selection of
one of them must be made with a consideration on the appli-
cations to be developed. If high throughput is needed, i.e.,
priority for short measurement times, good results can be
achieved using proportional counter tube instruments [10].
However, for the simultaneous analysis of several elements
adjacent in the periodic system or for complex sample com-
position, the results are significantly better using a semicon-
ductor detector [11]. Anyway, it must be pointed out that
SiLi drift diodes are ideal devices for high-resolution X-ray
spectroscopy, since they separate the electron energies into
elemental components and collect the energy (proportional to
the impinging radiation) in the form of electrical signal,
which in turn is translated into qualitative or quantitative
elemental data in word processor format. PC menu assisted
guidance ensures easy handling and gives accurate results
even by low-experienced operators. Although these two
types of detectors are the most used, recent advances on su-

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272 Current Analytical Chemistry, 2006, Vol. 2, No. 3
perconductor and semiconductor technology have provided
new types of detectors with improved energy resolution [7].
1.2. Suitability of XRF for the Analysis of Valuable Ob-
jects
Analysis of a sample usually implies the destruction of,
at least, a part of it. However, some samples should not be
destroyed due to their value, namely unique pieces of jew-
elry or works of art, and, in these cases, the use of a non-
destructive technique is mandatory.
The information obtained in the analysis of valuable
samples can be used with different aims depending on the
kind of sample under study. Thus, in the case of jewelry
items, the main objective is the determination of the precious
metal content or fineness of the alloy with which the jewel
has been made from, in order to avoid economic, and also
sanitary frauds; the latter owing to the presence of metals,
which can cause health problems as, for example, dermatitis
[12]. In this instance, the determination of major and minor
constituents of the sample is enough for solving the problem,
unnecessary being among them, most often, the trace analy-
sis. The case of archaeological or artistic metallic objects,
however, is more complex, because the analysis must answer
questions about their provenance or the manufacturing
method used, that can help to find out historical aspects
about people from that time, such as their industrial devel-
opment or economical status. This kind of studies requires,
not only the analysis of major and minor constituents of the
object, but also the determination of trace elements that can
attribute the object to a specific place, for instance, the metal
used in the manufacture of a coin with its ore. Moreover,
scientific methods may also be used to study the state of con-
servation of a material and select the most appropriate way
for restoration [13].
According to Lahanier et al. [14], an ideal method for
analyzing objects of artistic, historic or archaeological nature
should be:
(a) Non-destructive, i.e., respecting the physical integrity of
the material/object.
(b) Fast, so large numbers of similar objects may be ana-
lyzed or a single object investigated at various positions
on its surface.
(c) Universal, so that by means of a single instrument, many
materials and objects of various shapes and dimensions
may be analyzed with minimal sample pretreatment.
(d) Versatile, allowing average compositional information
to be obtained, but also local information of small areas
from heterogeneous materials.
(e) Sensitive, so that object grouping and other types of
provenance analysis can be done, not only by means of
major elements, but also by means of trace elements,
fingerprints, etc.
(f) Multielemental, so that information on many elements
can be simultaneously obtained in a single measurement,
even on unexpected elements.
XRF meets a number of these requirements and, for this
reason, it has been widely used for performing qualitative
Jurado-López & Luque de Castro
and semiquantitative analysis of this kind of materials [15].
Nowadays, accurate quantitative analysis can also be carried
out as commented before.
XRF is, in principle, applicable to all elements, except
the first two of the periodic system (H and He), thereby cov-
ering an energy region from about 50 eV to 100 keV. How-
ever, many light elements are difficult to measure and re-
quire advanced instrumentation, which often limits practical
work to atomic numbers between 13 (Al) and 92 (U). On the
other hand, aspects related to equipment cost and increas-
ingly difficult radiation protection at high photon energies
determine that L lines (instead of K lines) are measured at
atomic numbers over 50 (Sn). Thus, the measured fluores-
cent photon energies are generally between 1 and 25 keV
and excitation (tube) voltages less than 60 kV. The energy
range is not only important as an analytical characteristic,
but also to estimate the danger of potential radiation damage
[16].
Metals are specially suited for EDXRF analysis. The high
atomic number and density of metals facilitate the obtaining
of high intensity secondary X-ray lines, even when low in-
tensity sources are used. Moreover, in the case of metal al-
loys, emission lines of the elements in the alloy can be col-
lected [17].
Quantitative XRF analysis is carried out by the funda-
mental parameters method, which is an atomic physics algo-
rithm that theoretically describes the interaction between the
X-ray spectrometer and the analytes. It basically interprets
the processed X-ray spectra into elemental composition,
taking into account the physical parameters of the spec-
trometer, namely, generation of primary X-rays from the X-
ray tube, secondary fluorescent X-ray production in the sam-
ple, inter-element matrix effects and detection of X-rays [1].
In the case of the analysis of noble metal alloys, the funda-
mental parameters method yields different accuracy, de-
pending on the alloy composition. Thus, in the determination
of gold in an alloy containing copper, an overestimation (0.5-
1%) will take place due to the overlapping of some emission
bands. On the other hand, the analysis of silver-copper alloys
is very accurate because their spectral bands are clearly sepa-
rated [18].
However, EDXRF analysis has some drawbacks, most of
them owing to the fact that the analyzed volume is very
small. The penetration of the beam in metallic samples de-
pends on the matrix, but it scarcely surpasses 100 microns.
This analysis depth is sufficient to distinguish coatings that
usually have a few microns thickness, but it is a problem
with samples affected by corrosion, because the thickness of
the patina, though dependent on the constituents of the sam-
ple, is usually bigger than the penetration depth.
The objects to be analyzed, moreover, should be homo-
geneous and have a flat surface in order to achieve a suitable
positioning for both incidence of the primary beam, and col-
lection of the secondary one by the detector. This constitutes
a drawback in the case of jewelry items, due to their wide
variety in sizes and shapes [19].
Routine methods usually require sampling, that is cutting
the object and polishing the samples in order to have the
proper surface to carry out an accurate analysis. These meth-
X-Ray Fluorescence Analysis of Valuable Metals
ods, however, cannot be used in the case of valuable objects
so the flattest surface must be selected.
1.3. Sampling and/or Sample Preparation
The energies of fluorescent lines or their intensities are
not significantly affected by the chemical state of the ana-
lyzed atoms, so destructive dissolution and/or atomization by
a flame, arc, spark or plasma, as required in techniques based
on optical emission or absorption, are not necessary. In fact,
neither sampling nor sample preparation are usually needed,
unless very accurate quantitative analyses or homogenization
are required [16]. Homogeneity becomes an important aspect
in valuable objects, such as artifacts and archaeological ones,
and also in jewelry items. This is the case, for example, of
paintings, in which a preparation layer is always required
under the pigment layers. Even in metallic objects, lack of
homogeneity occurs because, although the composing alloys
are supposed to be homogeneous, cast is not always carried
out in a proper way. Moreover, some objects could have suf-
fered from corrosion effects or be coated. Studies on these
two instances will be commented in detail later. In the par-
ticular case of jewelry items, they are generally made of sev-
eral parts that are put together by welding with an appropri-
ate alloy. This usually contains a metal of low fusion point,
which is added on purpose to facilitate the process. Thus,
depending on the part of the item on which the analysis is
carried out, the results can vary significantly, not only in the
metal content, but also in the presence or absence of a given
element.
When specimen preparation is needed, it constitutes the
largest contribution to errors in X-ray fluorescence analysis
[19]. Thus, at 2 x 10 6 counts and an insignificant background
level, the relative standard deviation (Sr) is 1/ N ≈ 7 x 10-4,
that is, 0.07%. However, when the objects to be analyzed are
homogeneous and have a regular shape, XRF can be used for
direct analysis.
2. XRF ANALYSIS OF JEWELRY ITEMS
The analysis of gold carat alloys is a central function in
manufacturing and distributing jewelry, as well as in refining
related gold carat scrap. XRF is commonly used for elemen-
tal analysis of precious metals for screening and production
control purposes, thus avoiding the processing of overcarat
and undercarat products (jewels which are over or under the
gold content expected, respectively) [1].
XRF can be used, not only in the jewelry manufacture,
but also in its trade. There have been increasing demands for
a means whereby the transactors and dealers in jewelry can
accurately and efficiently appraise the precious metal con-
tents on the premises [20]. Conventional methods such as
specific gravity measurement, the touchstone method, fire
assay method, and those based on atomic absorption spec-
trometry and similar techniques can be used to obtain the
precious metal content, but some of them are not accurate
enough, while others are destructive and require large analy-
sis times. X-ray fluorescence can be used to analyze gold
alloys in a rapid non-destructive way, with the accuracy of
the analyses depending on calibration. Thus, if the calibra-
tion set of standards covers the composition range within the
samples and mathematical correction of the matrix effects is
Current Analytical Chemistry, 2006, Vol. 2, No. 3 273
applied, the analytical results are comparable with those ob-
tained using traditional chemical methods of analysis, rang-
ing the difference between 0.01 and 0.07 % [3].
These good results can also be achieved by microbeam
X-ray fluorescence analysis, in which the sample is observed
with an optical microscope and the collimated X-ray beam
coincides with the viewing point on the surface of the sam-
ple. Measuring two sets of standards by the instrument, the
precision of gold measurement was 0.1% and 0.2% for sam-
ples with gold content over and under 90%, respectively. The
correlative coefficient between the measurement results and
the given values of the standards was better than 99.998%
[20]. Similar dependence between the determination preci-
sion and the metal content is observed in the determination
of gold, silver and platinum in gold and silver ornaments, in
which the relative standard deviation for the determination of
Au in 24-carat gold ornaments was better than the corre-
sponding to those made of 14-carat gold (0.01 and 0.82%,
respectively) [21].
XRF enables, not only the determination of major com-
ponents of gold jewelry, but also the minor ones, increasing
the standard deviation of the measurements as the metal con-
centration decreases [22].
A number of authors have also used XRF for the analysis
of platinum and platinum group metals (PGMs) with good
results. In the first instance, the determination of platinum
jewelry also containing gold, palladium, silver, copper, and
nickel was carried out in samples with Pt concentration
ranging from 85 to 99.92%, with the deviation being better
than 0.5% [23, 24]. The quantitative X-ray microfluores-
cence analysis of platinum/palladium alloys has also been
carried out, achieving better results when compared with the
conventional method because of the use of a polynomial
regression method to fit the curve [25]. This method was
applied to the determination of the homogeneity level of the
element distribution in alloys. The determination of Pt and
Pd in gold alloys was also carried out by Durand in 1969 for
samples with concentrations of these two metals between 0
and 50 parts per thousand, and an absolute precision of ± 1
part per thousand was achieved, which is more accurate than
the usual fire assay followed by acid attack [26]. In the case
of the analysis of platinum group metals, the interference
effects during their detection have been studied [27-29],
pointing out the magnitude of the effects of selective X-ray
fluorescence excitation [29].
EDXRF has been used, not only for the determination of
the components of gold jewelry, but also for testing silver in
silvery objects, with a relative standard deviation of 0.2%,
and determination range from 10 to 99% Ag [30].
3. XRF ANALYSIS OF PRECIOUS METALS IN
CULTURAL HERITAGE
X-ray based techniques in general have been used in the
field of cultural heritage nearly since its beginning. The ap-
plications have been growing and improving in parallel with
the technical and instrumental developments that X-ray pro-
duction and detection have experienced. A wide range of
techniques can be used in order to analyse either the ele-
mental composition of a material, or its mineral structure [7];
274 Current Analytical Chemistry, 2006, Vol. 2, No. 3
however, XRF stands out from other X-ray based techniques
due to its portability, which allows the in situ analysis of
large or extremely delicate objects.
3.1. Analysis of the Metal Fineness
The use of optical emission spectrography in the study of
ancient metals dates from 1931, when an extensive investi-
gation on the metallurgy of central Europe was first carried
out [31]. The analysis technique used in this field must an-
swer two questions: one concerning the evolution of the use
of metals, and the other, the authenticity of the artifacts [32].
There are some aspects that make difficult the determi-
nation of the origin of metals. The problems arise from the
rarity of the ore deposits, the high temperature required for
smelting which induces changes in trace elements, corrosion
during burial periods and the fact that metals are easily re-
melted and re-used to make new objects [32]. Other key as-
pects that make XRF analysis of archaeological metals diffi-
cult are the irregular shapes of the samples and the matrix
effects. Owing to these facts, the peak area vs concentration
–the relationship IM = f(cM), M being the metal to be deter-
mined– cannot be used and, consequently, neither the meth-
ods based on it. With the aim of minimizing this problem,
Sándor et al. have developed methods to overcome the effect
of geometrical dissimilarity [33, 34]. Other authors rotate the
objects in order to compensate for the irregularities that may
occur [35, 36]. On the other hand, Milazzo proposes the con-
dition of employing a symmetric experimental set up for
making the analysis independent of the irregularity of the
samples [37]. In this case, it is not necessary to rotate the
sample during the XRF measurement, which is an advantage
with some archaeological objects, such as statues, that can-
not be easily rotated.
Most archaeological XRF analyses have been carried out
on coins. Depending on the metal of which they were made
of and some other aspects such as burial conditions (if it is
the case) or fabrication technique, corrosion effects and their
consequent surface enrichment can take place at a variable
extent. These effects are more significant as concentration in
a non-noble metal is higher, which, therefore, can suffer
from oxidation more easily. This is the case of copper-silver
alloys, in which oxidation leads to the formation of copper
oxide that increases the volume, causing migration, i. e., dif-
fusion of the metallic components. Thus, silver atoms con-
centrate on the surface layer of the coin [16, 38, 39]. This
effect can be proved with scanning electron microscopy
(SEM), that allows taking images of the cross-sections of the
coins, in which the two phases of the alloy –the outer silver-
rich and the inner copper-rich layers– can be distinguished
[16, 35, 40]. In these cases, the dominant contribution to the
signal comes from the corroded/painated surface [41]. This
effect can be measured by determining the metal content
before and after polishing. Thus, a decrease from 93 to 82%
for Ag concentration and an increase from 6 to 17% for Cu
were obtained when the surface values were compared with
those from 100 µm deeper in the sample [42].
According to Linke et al., the ratios of AgL/AgK intensi-
ties can be used in order to obtain information on the degree
of depletion. This ratio demonstrates when the silver is en-
Jurado-López & Luque de Castro
riched at the surface of a coin and when it is not, estimating
the error of its direct analysis by EDXRF [35, 40].
Apart from the Ag-enriched layer, enrichment in copper
and other elements such as iron, sulfur and chlorine, can also
occur in some superficial areas (black stains). This can be the
result of a heat treatment, causing Cu from the bulk to rise to
the surface because of the silver oxidation by atmospheric
gases, leading to the formation of Ag2S or AgCl precipitates,
or simply as a result of mechanical wear and soiling during
coin usage [43].
In other cases, however, the differences between the
analysis before and after cleaning are not significant, so the
direct analysis of the objects can be carried out [44].
Even in gold coins with less than 94% gold, a surface
enrichment occurs, that is pointed out by the joint use of
XRF and PIXE (proton-induced X-ray emission), owing to
the fact that the proton beam used in PIXE has a shorter
penetration depth than the primary beam generated by the X-
ray tube [45].
3.2. Provenance Studies
Finding out the origin of the metals used to manufacture
artifacts is a difficult question that requires the analysis of
trace elements, either to confirm the ore from which they
originate or to identify the source of raw material. The diffi-
culties arise from the fact that chemical composition actually
changes during the melting process. In order to confirm an
already known ore, the presence of only one element can be
sufficient, but in the case when the ore is unknown, the de-
termination of a group of trace elements is needed [32].
Thus, trace analysis can be used to confirm the coin
minting places proposed by numismatists, as well as to solve
doubts about coin classification [44]. The latter can be
achieved by the ratio between the amount of one element
(bismuth, in ref. 44) with the amount of a major component.
The detection limits were of the order of 10 µg/g for the
elements with atomic number greater than 28; 50 µg/g for
chromium, manganese and iron; 250 µg/g for titanium; and
0.4% for chlorine. The lower the atomic number of the ele-
ment, the higher is its detection limit. The reason for that is
the lower excitation cross section by the silver K-line of light
elements.
Sometimes, the occurrence of a given group of metals
allows identification of the origin of the metal used. This is
the case with platinum group element inclusions in gold an-
tiquities, which indicates that gold originated from placer
deposits. This kind of gold source was extensively used in
antiquity [46]. However, in other cases, the study of the
composition of an alloy only can clarify the sources that
were not used to make the coin [47].
3.3. Authentication Studies
Information about trace elements may also be used as a
means of authentication for distinguishing false coins made
in recent times from the original ones, because the former, as
prepared by modern technology, do not contain the same
amount of trace elements. The identification of counterfeited
artifacts of artistic and archaeological interest is of out-
X-Ray Fluorescence Analysis of Valuable Metals
standing importance due to the implications from the circu-
lation and trade in the world market of this type of objects
[48]. Hence, the possibility of rapid non-destructive accurate
analysis for the authentication of metal artifacts is very use-
ful for the police, auction houses and antiquaries. Moreover,
the easy-to-operate feature of EDXRF is a clear advantage in
this field.
The XRF study of Greek silver drachmae allowed classi-
fication of coins belonging to the first century BC into sev-
eral categories, elucidating either the presence or absence of
certain elements, or the order of magnitude of a particular
element (Cu, in this case). The study pointed out the exis-
tence of original coins, Barbarian imitations, debased coins
(low silver content), official counterfeits of bronze, official
counterfeits of tin, and plated coins [49]. The analysis of the
coins, their debasing and counterfeiting, sheds light on the
difficult economical and political situation of the time (Ro-
man civil wars in ref. 49). It can also be used to evaluate the
development of the casting technology of the time [50-52].
Reiff et al. have studied gilded forgeries of ancient gold
coins, finding examples of the three gilding technologies
used in antiquity [53]. Contemporary forgeries of ancient
silver coins are much commoner than those of gold coins,
since the similarity between the specific weights of silver
and copper (in contrast to the corresponding to gold), made
the mass difference between original silver and silver-plated
forgeries not easily noticeable [54].
Classification techniques, such as principal component
analysis (PCA) and cluster analysis (CA), can help in the
interpretation of the information provided by X-ray based
techniques, allowing the distinction between a set of counter-
feit coins, considering the manufacture method used, and
differentiating between the counterfeit coins and the original
ones [55, 56].
3.4. XRF Analysis of Noble Metals in Art
The study of works of art very often requires the use of
portable equipment for the in situ non-destructive study of
the objects [13, 57-65], sometimes due to the impossibility
of transporting them (wall paintings), and sometimes be-
cause the movement of the object is not advisable due to its
delicacy or state of conservation. Furthermore, to move an
artwork is sometimes a complex process, not only for secu-
rity reasons (the artifact can be stolen), but also due to the
bureaucratic aspects involved [17].
The knowledge on the composition of artifacts is of great
importance:
a) For ensuring that the work of art really is as expected.
That is the case of the analysis of the so-called “Sceptre of
Charles the Great”, in which gold was supposed to be used,
but it was found out that it really was a silver gilded alloy
[59].
b) For conservators and curators, in order to both design
the best conservation conditions and plan possible restora-
tions. In this sense, several papers on the study of the fres-
coes of the Chapel of the Scrovegni (Padua), painted by
Giotto, and particularly, on the analysis of the composition
of the golden haloes, have recently been published [63-65].
Current Analytical Chemistry, 2006, Vol. 2, No. 3 275
These studies allow us to understand the composition of the
gold alloy used as well as the elements belonging to inner
layers. Considering to one of these elements (lead), the
thickness of the gold leaf can be calculated by means of the
ratio between its α and β lines.
XRF can also be used for the analysis of gilded metal
embroidery threads used in tapestries [66].
Finally, a 3D-micro XRF has been presented and used to
analyze the elements from different layers in ancient Mughal
miniatures [67].
4. STUDY OF PRECIOUS METAL COATINGS BY
XRF
In ancient times, gold could be hammered into a leaf with
a thickness down to approximately 0.35 µm, as it can be
concluded from the statements of Pliny the Elder (23-79
AC). Today, gold can be extended to a thickness of nearly
0.1 µm [53].
Hence, the plating of objects, either to confer beauty or
value to the object, or in order to forge an original gold item,
was a common fact in antiquity. Thus, there are objects ap-
parently made of gold, but actually made of another metal
(usually copper or copper-gold alloys), which was subse-
quently covered by gold plating. Gold leaf is very suitable
for the gilding of silver or copper blanks as it is easy to
achieve strong adhesion to the metal underneath [53]. In
Amerindian civilizations, a copper-gold alloy with a high
copper content was used to cast the bulk and then, a heating
process was carried out in order to achieve a depletion gild-
ing procedure, giving to the final product a suitable golden
aspect [68]. Nowadays, there are a number of samples that
have a noble metal coating, such as costume jewelry items
and others of technological interest, in which the accurate
measure of the coating thickness can be very useful [69].
XRF enables to recognize top coatings that can lead to
error in the determination of the bulk composition of a sam-
ple. Furthermore, both the coating thickness and the chemi-
cal composition of the base alloy can be determined. The
determination of the thickness and composition of the cov-
ering material can be carried out by measurement of the at-
tenuation of substrate line intensities and scattered photon
intensities passing through the film and using the funda-
mental parameter method [70]. Not only a thin layer can be
measured, but also the study of multilayered samples can be
carried out [71, 72]. The angular dependence of the fluores-
cence lines emitted by the substrate can be used for measur-
ing the coating thickness [73-78].
A review on the measurement of coating thickness in
vacuum processes by EDXRF, including examples of classi-
cal precious metals such as gold and silver, has been pub-
lished. The advanced design of the measuring system allows
the continuous measurement of very thin layers (up to 20
nm, approximately) [79].
5. XRF ANALYSIS OF NOBLE METAL SOLUTIONS
XRF can also be used for the analysis of solutions, thus
permitting to determine the concentration of electroplating
baths. The speed and repeatability of the system make it well
suited for in-process control [80].
276 Current Analytical Chemistry, 2006, Vol. 2, No. 3 Jurado-López & Luque de Castro

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[19] Blank, A.B.; Eksperiandova, L.P. X-Ray Spectrom., 1998, 27, 147.
Baths of different compositions were studied, and their effi- [20] Lu, R.; Le, A.; Gu, Y.; Wu, G.; Zhu, J. Nucl. Instrum. Methods B,
ciency evaluated in terms of plating rate obtained from X-ray 1995, 104, 595.
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145.
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de Ciencia y Tecnología of Spain and the EU for financial Vincze, L.; Wei, F.; Deryck, I.; Schalm, O.; Adams, F.; Rindby, A.;
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Received: 14 February, 2006 Revised: 04 April, 2006 Accepted: 09 April, 2006