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 Nuclear Instruments and Methods in Physics Research B 348 (2015) 285–290

Contents lists available at ScienceDirect

Nuclear Instruments and Methods in Physics Research B

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

Ion beam analysis of golden threads from Romanian medieval textiles

Z.I. Balta a,⇑, L. Csedreki b, E. Furu b, I. Cretu c, R. Huszánk b, M. Lupu c, Z. Török b, Z. Kertész b, Z. Szikszai b
a
National History Museum of Romania, Calea Victoriei 12, Sector 3, Bucharest, Romania
b
Institute for Nuclear Research, Hungarian Academy of Sciences, H-4001 Debrecen, P.O. Box 51, Hungary
c
National Art Museum of Romania, Calea Victoriei 49-53, Sector 1, Bucharest, Romania

a r t i c l e i n f o a b s t r a c t

Article history: In this study, metal threads from Romanian religious embroideries and precious velvet brocades dated
Received 11 July 2014 from 15th to 18th century were analyzed by using IBA methods (PIXE and RBS) which, in comparison
Received in revised form 27 December 2014 to the traditional analytical techniques (XRF, EDS), allowed the detection of their structures and accurate
Accepted 13 January 2015
identification of the trace elements (detection limits of few tens of ppm). PIXE results confirmed that both
Available online 30 January 2015
types of the metal threads studied – wires and strips – have layered structures being made of fine silver,
refined by cupellation, and gilded most probably with pure gold, and not of Au–Ag alloy, or gilded Ag–Cu
Keywords:
alloy or Au–Ag–Cu alloy, as resulted from the previously performed SEM-EDS analysis. Trace elements of
Ion beam analysis
Golden threads
historical interest like lead, mercury and bismuth have been also possible to be detected by PIXE. The
Medieval textiles resulting elemental maps allowed us to identify the areas from which the metal thread structure and
quantitative composition could be accurately determined. RBS measurements revealed that the gilding
layer is separated from the silver bulk by an interface layer resulting through atomic diffusion of silver
into the gold, which lead to the conclusion that the methods used for gilding were probably either the
diffusion bonding or the fire gilding. The gilding layers thicknesses were estimated by PIXE with the
GUPIX software and also determined from RBS measurements.
Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction
Technical studies by classical techniques routinely used for
analysis of cultural heritage materials (XRF, SEM-EDS) have been
done previously in order to determine the chemical nature and
morphology of the metal threads used in ancient textiles [1–4].
Some studies revealed that XRF and EDS could not distinguish
between alloys and layered structured materials for the small
and extremely thin gilded metal threads. Besides, EDS may some-
times give erroneous results. It was observed that the gold concen-
trations resulted for the gold coating and reported in previous
publications are often too low depending on the high accelerating
voltage used (usually 20–30 keV in practice), and thus incorrect
[5,6].
Recently, in order to overcome some of these difficulties, more
sensitive analytical techniques like AES, XPS, SIMS and laser-ICP/
MS have been used, and to our knowledge, few characterization
studies by using IBA methods have been done so far [5–8]. Elemen-
tal analysis either on surface or in a depth profile by IBA methods
are non-destructive and could provide unique information at the
⇑ Corresponding author.
E-mail address: balta_z_i@yahoo.com (Z.I. Balta).
trace level sensitivity which make them ideal for the study of the
very small and thin, possibly multilayered metal threads. Aim of
our study was to demonstrate the necessity of integrating the
advanced IBA methods with the classical analysis techniques fre-
quently used in museums, for an in-depth applied interdisciplinary
research that brought new developments and rich accurate infor-
mation on golden threads constituent materials, especially the
trace elements, elemental depth distributions and layers thick-
nesses, the ancient production technologies, metal threads struc-
ture, their provenance and origin. IBA measurements were
carried out within the EU FP7 CHARISMA FIXLAB Transnational
Access programme, in two phases: the projects IBATEX 1 and IBA-
TEX 2.
2. Selection of textiles
Metal threads selected for ion beam analysis were taken from
medieval gold brocaded velvets and religious embroideries pre-
served in the textiles collections of the Putna Monastery Museum
and the National Art Museum of Romania. For the PIXE and RBS
analysis 23 textiles were chosen, most of them with known prove-
nience (Moldavia, Italy, Near East and Greece) and consistent dat-
ing as appeared in the art historical literature [9,10]: brocades with

http://dx.doi.org/10.1016/j.nimb.2015.01.027
0168-583X/Ó 2015 Elsevier B.V. All rights reserved.
286 Z.I. Balta et al. / Nuclear Instruments and Methods in Physics Research B 348 (2015) 285–290
the inscription of donation embroidered, embroideries typological-
ly and stylistically similar and brocades with no inscription of
donation.
Embroideries were made in most cases for liturgical purposes,
worn by priests as church vestments or used during the religious
services (epitrachelion, nabedernita, altar door curtain, aer, epi-
mankia, etc.), most of them being produced locally in the Putna
Monastery’s Embroidery School. They were worked in the tradi-
tional Byzantine technique of pattern couching, using the cartoon
models painted on religious themes similar to those in the mural
paintings dating from the 15th to 17th centuries. According to
the sources, Byzantine embroidering technique consisted in laying
golden threads on the surface of the background material and
attaching them with stitches made of silk threads. The stitches
were passed over the golden thread at regular intervals, creating
different patterns [10].
Brocaded velvets were imported and produced abroad in the
Italian workshops from Venice or Florence, or in the Ottoman
Empire workshops, as mentioned in the art historical literature
[10]. Brocades were sumptuous materials of silk velvet fabrics
richly decorated with golden metal threads that were used in the
articles of clothes of Italian and Oriental influence by the Molda-
vian and Wallachian princes, princesses and boyars (ceremony cos-
tumes, court vestments, caftans, granatza, etc.). They were
sometimes donated to churches and monasteries after being worn.
With a simple cut, those clothes could be dismantled, the resulting
fabric fragments being used during the religious services as temple
veils, covers for lecterns and the Communion Table or as tomb
covers.
3. Experimental
IBA techniques were applied at the Oxford-type nuclear micro-
probe facility in the MTA Atomki, Debrecen, Hungary [11–13]. The
analyses were performed in vacuum and the size of the beam was
typically about 2 lm. The length of the threads was approximately
3–10 mm.
PIXE measurements were performed on 50 samples taken from
18 medieval textiles (IBATEX 1) and on 23 cross-sections of threads
prelevated from 8 textiles (IBATEX 2) by using a proton beam of
3 MeV energy and 100–500 pA intensity. PIXE analysis modes per-
formed were: full area elemental mapping of the sample surface,
selected raster, and point analysis. The resulting PIXE spectra were
evaluated with the GUPIX code [14]. In IBATEX 1, three different
types of metal threads were analyzed: wires wrapped around a
dyed silk yarn, strips wrapped around a dyed or undyed silk yarn
and wires with no core yarns. In order to obtain more precise
and accurate results regarding the metal threads composition
and chemical structure, our study continued with analysis on
cross-sections within the IBATEX 2 project. Cross-sections were
Fig. 1. The K3 – gilded silver wire microscopy image in reflected light and its corresponding AgL and Au PIXE maps. In the Au map, could be seen that the gold distribution is
uneven showing some parallel lines.
obtained by embedding the wires and strips in epoxy resin, the
resulted specimens being cut in transversal sections which were
then wet grounded and polished down to grit 8000.
RBS analysis were carried out on 10 samples taken from 6 tex-
tiles (IBATEX 1) and 26 samples prelevated from 12 textiles (IBA-
TEX 2) using a He+ beam of 2 MeV energy and a few hundred pA
intensity.
During the first phase (IBATEX 1), for the evaluation of the PIXE
data, it was assumed that the bulk silver includes less than 1% gold,
and the gilding layer contains only pure gold, all the trace elements
being present in the silver substrate only. The gilding layers thick-
nesses were also estimated with the GUPIX software. For the sec-
ond measurements phase (IBATEX 2), carefully cut and polished
cross-sections were prepared to assess the silver bulk composition
by PIXE without any possible contamination from the gilding layer
or the silk yarn. The thicknesses of the gilding layers were mea-
sured by dedicated RBS analysis on metal threads using an
ORTEC-type surface barrier silicon detector (‘‘ULTRA’’ Ion-
Implanted, 50 mm2 sensitive area and 25 keV system energy reso-
lution). The detector was placed at a scattering angle of 165° at
Cornell geometry [15,16]. The scan size was set to
500  500 lm2. RBS spectra were evaluated with the SimNRA com-
puter code version 6.06 [17]. With the second approach (IBATEX 2),
we also could check the validity of the assumptions made during
the first phase (IBATEX 1).
Preliminary examinations in reflected and polarized light, at
different magnifications, was performed in order to determine
the metal threads technological and morphological characteristics,
also the wires diameters (in cross-sections), with a Nikon Eclipse
LV100D microscope equipped with a D90 digital camera, a Camera
Control Pro 2.0 imaging software and a NIS Elements-BR3.0 image
analysis software.
4. Results and discussion
Preliminary optical microscopy measurements showed that the
strips had a total width of 0.2–0.6 mm and a thickness of 0.01–
0.05 mm, while the wires diameters were of approximately 0.1–
0.3 mm.
Optical microscopy and PIXE maps revealed that wires, and
some of the strips (especially strips from the brocades), present
striations on the surface caused by drawing in the manufacturing
process. In Fig. 1, the parallel longitudinal lines on the surface of
sample K3 could be visible.
Microscopy observations and PIXE lead to further information,
two different types of strips – cut and flattened – being identified.
According to written sources [5,18,19], the cut strips are early
times threads dated from the 13th century onwards, uneven in size
and quality and of variable thickness, obtained by cutting a gilt
metal sheet. The flattened strips, dated from the 14th century
 Z.I. Balta et al. / Nuclear Instruments and Methods in Physics Research B 348 (2015) 285–290
Fig. 2. Optical microscopy images in reflected light of samples J2 - gilded silver wire wrapped around a red silk yarn and K2 - gilded silver strip wrapped around a yellow silk
yarn ‘‘drappi d’oro’’ and their cross-sections PIXE maps (IBATEX 2). For wire J2, iron seems to be present in the red dyed silk yarn (Fe map), respectively, for strip K2, copper
could be seen to be present not only in silver, but also in the yellow silk yarn (Cu map).
onwards, were obtained from cast, drawn and rolled wires. They
have even width all along their length and show parallel lines on
their surface resulted from the wire drawing process.
PIXE maps obtained in IBATEX 2 on cross-sections, in comple-
tion to maps resulted in IBATEX 1, revealed the thread structure
and distribution of the elements in the layers. Fig. 2 shows the dis-
tribution maps of some of the samples’ J2 and K2 constituent
elements.
In Table 1 are presented the resulting concentrations of the ele-
ments: silver, gold, copper, lead, calcium, mercury, iron and bis-
muth, that were detected in almost all samples (wires and strips)
by PIXE bulk analysis (full selected areas). Table 1 also lists brief
descriptions and dating of the selected textiles from where sam-
ples were taken.
Silver concentration in the wires and strips measured by PIXE
(IBATEX 1) varies between 94.3% (sample B4) and 99.5% (sample
Z2), and for the wires in cross-sections (IBATEX 2) between 97.3%
(B3 cs.) and 99.4% (D3 cs.) indicating that a ‘‘pure’’ silver (Ag con-
centration > 95%), typical of a silver obtained by cupellation was
employed. According to Biringuccio [20], a cast fine cupelled silver
was used by the medieval smiths to make the so called spun silver
or gold which is actually the gilded silver strip wrapped around a
silk yarn employed in embroideries and velvet brocades. The
resulting lead concentration is in accordance with the lead content
mentioned in the literature for medieval silver [21,22]. The major-
ity of the samples, wires and strips, contain less than 0.4% Pb,
which strongly indicates cupellation. No lead, for wires A1 and
A7, or very small content of lead, for wire X2, was detected, sug-
gesting that they were obtained from native silver (argentite) or
from rich silver ores (cerussite, cerargyrite or jarosite). Ancient sil-
ver originated from native silver or from rich silver ores that could
have been smelted without recourse to lead to absorb the silver,
may contain very little or no lead at all. In the strips P3 and P4, high
amounts of lead was measured, which indicated that different sil-
ver ore sources and different technologies of production were used.
Based on the lead content results could be assumed that some
samples may belong to different periods or have a different prove-
nance. Lead can be a good indicator of the technological level of
purifying processes. Low concentrations of lead could indicate an
advanced technology for the refining process. Similar contents of
287
lead indicate similar technologies of silver extraction and refining,
while less lead suggests very advanced technologies of production.
Gold content in silver is considered a good indicator of silver
sources and one of the most important trace elements for silver
authenticity [22]. Gold concentrations as resulted in IBATEX vary
between 0.01% (Z1) and 1.8% (E4), and between 0.03% (X2 cs.)
and 1.4% (B3 cs.) in IBATEX 2, which is in accordance with the val-
ues mentioned in the literature for gold contents in the medieval
and post-medieval silver [22].
When high content of gold with low content of lead is detected
it is assumed that re-melting of ancient old silver could occur (pos-
sibly sample U2). In medieval production of precious metals
important sources were recycled silver or gold. Metal smiths used
to re-melt ancient coins, jewelry or other gold or silver objects as
their raw materials [23,24].
Another element determined by PIXE (IBATEX 1) was calcium
which according with the elemental maps seems to have a homo-
geneous distribution and to be originated from the silk yarn, being
probably present as a constituent of the silk thread, or resulting
from the silk washing waters or silk treating solutions. PIXE anal-
ysis studies on silk composition have shown that silk, besides C,
H, O and N, contains the elements Ca, Cu, P, S, Fe, and Zn [25].
No calcium was observed in the specifically prepared, presumably
contamination free cross-sections (IBATEX 2).
The presence or absence of copper (<3%) may be significant in
indicating the purity of the silver employed. Concentration of cop-
per for all samples was less than 2%, indicating that it was not
deliberately added. In some cases, copper was observed to be pres-
ent not only in silver, but also in the silk yarn as confirmed by PIXE
cross-sections maps (Fig. 2, Cu map of the sample K2).
Presence of mercury revealed by PIXE quantitative results (IBA-
TEX 1) may indicate that a gold amalgamation technique was
employed for gilding (fire gilding). Mercury may have resulted
also, from an amalgamation process used for gold extraction, or
from gold refining or parting using mercury, methods employed
long ago before the 14th century only in the Middle East, and later
on toward the end of the 15th century also in Europe. Biringuccio
[20] refers to a mercury amalgamation technique that may have
been used in silver extraction from lead ores containing large
amounts of silver, but this technique seemed to start expanding
288 Z.I. Balta et al. / Nuclear Instruments and Methods in Physics Research B 348 (2015) 285–290

Table 1
Elemental concentrations in wt% (Ag, Cu, Au, Pb, Ca) and in ppm (Fe, Hg, Bi) resulted by PIXE bulk analysis (full selected areas) within IBATEX 1and IBATEX 2 (cs = cross-section,
W = wire, S + S = strip wrapped around a silk yarn, W + S = wire wrapped around a silk yarn). The analytical uncertainty is 2–5 rel.% for the major elements and 5–20 rel.% for the
minor and trace elements.

Selected textiles Sample wt% ppm

Ag Au Cu Pb Ca Fe Hg Bi
A. Epitrachelion (Inv.70), religious embroidery with A1/W 97.5 0.30 1.54 0.55 560 200 70
inscription of donation, 15th cent. A2 cs./W 98.1 0.49 1.16 0.1
A5 cs./W + S 98.6 0.74 0.34 0.2 140 370
A5/W + S 95.8 0.83 0.36 0.21 2.68 770 390
A5b/W + S 98.6 0.55 0.21 0.15 0.42 390 70 310
A6 cs./W 98.7 0.36 0.67 170
A7 cs./W 98.6 0.23 1.12
A7/W 98.2 0.23 1.03 0.46 250 50
A12 cs./W 98.5 0.74 0.35 0.2 190
A12/W 97.9 0.83 0.38 0.21 0.56 810 420
B. Epitrachelion (Inv.36), religious embroidery with B2 cs./W + S 98.6 0.22 1.12
inscription of donation, 15th cent. (1469) B2/W + S 96.0 0.27 1.41 0.03 2.17 660 110
B3 cs./W 97.3 1.44 0.95 110
B4 cs./W + S 97.7 0.65 1.27 0.08 410
B4/W + S 94.3 0.71 1.34 0.21 3.33 640 130 330
D. Epitrachelion (Inv. 40), religious embroidery, 15th cent. D1cs./W 98.7 0.87 0.14 0.16
D1/W 98.4 0.94 0.15 0.15 0.29 170 90 90
D2 cs./W 98.7 0.87 0.14 0.15
D2/W 98.2 0.89 0.13 0.13 0.52 680 80 50
D3 cs./W 99.4 0.15 0.22 0.18
D3/W 99.3 0.24 0.24 0.18 220 120
E. Embroidery with eagles, religious embroidery with E1/S + S 98.1 0.24 0.50 0.04 0.96 440 530
inscription of donation, 16th cent. (1536) E2/S + S 97.6 1.30 0.30 0.18 0.53 300 350
E3/S + S 98.2 0.64 0.27 0.35 0.43 200 270 120
E4/S + S 96.7 1.82 0.24 0.15 1.02 520 130
F. Altar door curtain of the Assumption of Holy Virgin, F1 cs./W 98.9 0.54 0.29 0.06
religious embroidery with inscription of donation, 15th cent. (1485) F1/W 98.6 0.74 0.20 0.05 140
F2 cs./W 99.1 0.49 0.20 0.06
F2/W 99.1 0.65 0.13 0.04 140
F3 cs./W 99.0 0.24 0.17 0.47
F3/W 99.5 0.16 0.05 0.18 70 60
J. Nabedernita with pearls, religious embroidery, 15th cent. J1/W 97.2 1.24 0.50 0.26 0.60 830 290
J2 cs./W + S 98.3 0.76 0.05 0.74
J3/S + S 97.2 0.11 1.56 0.14 0.87 690 430
K. Princess Maria Voichita tomb cover, velvet brocade K3/W 98.5 0.67 0.40 0.12 0.18 420 30 30
‘‘drappi d’oro’’ (Italy) with inscription of donation, 15th–16th cent. K3 cs./W 99.2 0.24 0.40 0.12
K4/S + S 98.4 0.18 0.37 0.11 0.76 380 170 350
P. Epitrachelion (Inv. 50), religious embroidery, 15th cent. P1 cs./W 99.3 0.51 0.02
P2 cs./W 99.0 0.62 0.03 380
P3/S + S 97.2 0.62 0.31 1.08 0.62 700 40 400
P4/S + S 97.1 0.21 0.32 0.84 1.28 350 160 1660
T. Epitrachelion (Inv. 35), religious embroidery, 15th cent. T2/S + S 97.0 0.14 0.61 0.12 1.83 2150 110 200
T3/S + S 97.5 0.34 0.69 0.08 1.25 870 300 190
T4/W 98.6 0.30 0.44 0.07 0.53 290 200 230
T5/W 97.8 0.26 1.35 0.02 0.53 200 50
U. Sacos, religious embroidery, 17th cent., Near East U2/W 98.6 1.06 0.06 0.03 0.20 200
X. Altar door curtain (Zavesa) of the Annunciation, religious X1 cs./W 98.2 1.19 0.23 0.31
embroidery with inscription of donation, 15th cent. (1484) X2 cs./W 99.4 0.04 0.15 0.09
X2/W 99.5 0.38 0.04 0.004 0.04 100
Z. Nabedernita, religious embroidery, 18th cent. (1746), Greece Z1/W 99.2 0.01 0.13 0.05 0.53 320 100
Z2/W 99.5 0.04 0.08 0.052 0.26 120 250

in Europe only at the beginning of the 16th century. Low mercury
concentrations combined with high content of lead observed in
some samples (Table 1, samples P3 and P4) could exclude a silver
production by amalgamation. Compared to all the threads investi-
gated, only the samples P3 and P4 showed high concentrations of
lead and low concentrations of mercury, which could be assumed
that mercury enriched lead ores were used for producing the silver
needed for their fabrication.
Iron in the elemental maps could be seen on the metal thread
surface, and sometimes as originating from silk. In most of the
cross-sections no iron was measured, indicating that it is not a
constituent of the silver bulk. Presence of iron may also result from
an iron-gall ink used for sketching out the preparatory under-
drawings for the embroideries.
Bismuth was also among the detected elements. Usually bis-
muth accompanies silver and may give information about its prov-
enance [26,27], being determined in the medieval silver originating
from Serbia, Transylvania, Carinthia and also from the Middle East.
Absence of bismuth in some metal threads and its presence in
other samples may be an indication of different silver sources. Less
lead and no bismuth could also suggest a repeated cupellation
which could have removed the bismuth.
 Z.I. Balta et al. / Nuclear Instruments and Methods in Physics Research B 348 (2015) 285–290 289

Fig. 3. Relationship between copper and lead concentrations (in ppm) in wires ( ), wires wrapped around a dyed silk yarn ( ) and strips ( ) wrapped around a dyed or
undyed silk yarn (IBATEX 1).

Copper and lead concentration comparison was done in order to

determine if there are any qualitative differences between the
types of metal threads analyzed in the IBATEX 1 project, and if
there is any relation between the Cu/Pb ratio and the threads pro-
duction processes. In Fig. 3, the samples showed to gather depend-
ing on the lead or copper content in three groups, the majority of
them containing small lead and copper contents, suggesting that
different provenience and metal processing methods for silver
was employed. Samples P3 and P4 with high lead and small copper
content, appear to gather together in a different group, and as
revealed by optical microscopy, to be older, cut strips with no par-
allel striations on their surface. Also, the wire T5 seem to group
with B2 wire wrapped around a silk yarn (high copper and small
lead concentration), suggesting that T5 is similar with B2 and con-
firmed by optical microscopy.
Fig. 3 showed also that the majority of the wires with no core
Fig. 4. RBS spectrum resulted for sample A6.
yarn contain less than 2000 ppm copper, while the majority of
the wires and strips wrapped around a dyed or undyed silk yarn
more than 2000 ppm copper which is in accordance with the liter- leaving very small amounts of mercury in the resulting gilding
ature [18]. layer.
RBS measurements were also performed in order to determine Fig. 4 shows the diffusion zone in the RBS spectra obtained for
the metal thread structure and the gold layer thickness. Due to sample A6 – gilded silver wire.
the metal thread significant weathering, production technology PIXE measurements values of the gilding thicknesses estimated
and high surface roughness, RBS analyses were difficult to carry with the GUPIX software (IBATEX 1) were in good accordance with
out in some cases. A small area was scanned over the thread, map- the RBS results (IBATEX 2): for wires, the thickness was varying
ping the gold layer, and then point measurements were done on between 0.1 and 0.8 lm, and for strips between 0.03 and 1.3 lm.
different locations. Evaluating the RBS spectra, results revealed
that a significant atomic diffusion took place between the gilding
layer and the silver substrate, making the fitting of the spectra 5. Conclusions
challenging. The presence of this interface layer lead us to the con-
clusion that the possible methods used for gilding were either fire- Golden threads from Romanian medieval textiles have been
gilding or diffusion bonding. In the diffusion bonding, an interface analyzed for the first time by using multi-elemental non-destruc-
layer is formed between the two metal surfaces, brought in close tive IBA methods.
contact by bounding the silver and gold bars together, by heating Compared to classical XRF and EDS techniques, IBA measure-
and soldering them to unite very well. The gilded silver bar is then ments, within IBATEX 1 and IBATEX 2 projects, allowed to accu-
hammered until it could be drawn into a wire or very thin, like a rately identify the elemental composition, distribution of the
gold leaf, for being cut into strips. Biringuccio [20] described this trace elements, the layered structures and thicknesses of the gild-
method to have been used for producing both gilded silver strips ing layers. Useful information for characterization of the gilded sil-
and wires, and indicating that fine gold ducats served as raw mate- ver threads due to elemental maps concerning the constituent
rial in the gilding process. In the fire-gilding method, gold and mer- elements spatial distribution in the sample was obtained. The
cury are mixed into an amalgam paste which is evenly distributed cross-section elemental maps obtained in IBATEX 2 clearly showed
on the silver surface. By heating, mercury evaporates and acceler- the distribution of the constituent elements in the silver bulk, gild-
ates the diffusion between the silver substrate and gold coating ing layer and the silk core yarn.
290 Z.I. Balta et al. / Nuclear Instruments and Methods in Physics Research B 348 (2015) 285–290
Preliminary optical microscopy and PIXE maps revealed sub-
stantial differences in the construction of the metal threads. Paral-
lel longitudinal striations were observed on wires and some of the
strips, probably due to the drawing process, and two different
types of strips – cut and flattened - were identified.
PIXE and RBS results confirmed that both types of the metal
threads studied – wires and strips – have a layered structure being
produced from ‘‘pure’’ silver (Ag concentration > 95%) refined by
cupellation and gilded probably by fire-gilding or diffusion gilding.
In addition to silver, gold, copper, lead, calcium and traces of mer-
cury, iron and bismuth were detected by PIXE. Based on the result-
ing PIXE maps, it was assumed that copper, lead, bismuth and
probably mercury were components of the silver ores, while cal-
cium and iron appeared to be mainly contaminations from the silk
yarns.
Variation of the gold content in the silver bulk, also the variable
lead and copper contents, indicated that silver used for producing
metal threads had different provenience. The silver ore sources
used were probably native silver, rich silver ores, argentiferous
galena, copper lead ores or mercury enriched lead ores. Further-
more, metal threads from the same textile seem to have different
provenience and to be older than the period of time that the textile
was dating.
The assumed structure consisting in a layer of fine cupelled sil-
ver underneath a diffusion layer of silver into the gold and the gold
layer on top was confirmed by RBS. Thicknesses of the gilding lay-
ers were estimated by PIXE with the GUPIX software and also
determined from RBS quantitative measurements. For most of
the samples, results revealed a non-uniform and variable thickness
of the gilding layer that could be due to the non-homogeneity in
the manufacturing processes, extensive wear, defects into the gold
layer or contaminations. PIXE (IBATEX 1) and RBS measurements
(IBATEX 2) showed that the gold layers are non-uniform and extre-
mely thin: for strips, varying between 0.03 and 1.3 lm, and for
wires between 0.1 and 0.8 lm.
Data resulted on metal composition, especially the trace ele-
ments, metal thread structure, elemental depth distributions and
layers thicknesses were used to clarify and complete the existing
information concerning their techniques of production, gilding
technologies and to identify if there are any qualitative differences
between them. Considering that the selected historical textiles
were consistently dated by art historians, the results obtained
could contribute as reference and could constitute a preliminary
database on historical metal threads to further studies. Since metal
threads were easily transportable mediums of trade, it is possible
that the ratios between their constituent elements to be indicative
of the manufacturing and distribution sites. In regards with the
implications for preservation and conservation practice, results
obtained would help restorers and conservators to decide on
appropriate treatments in order to bring the object closest to its
originally intended appearance.
Acknowledgements
Financial support by the Transnational Access to Research Infra-
structures activity in the 7th Framework Programme of the EU
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(CHARISMA Grant Agreement No. 228330) is gratefully
acknowledged.
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