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Alloying Elements as Chronotechnological Marker for Second and First Century BC Fibulae from Ancient Pannonia


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Fibulae as main the metal elements of people’s costume and clothing vary significantly in form and shape through time, and therefore, they are the perfect chronological markers of periods and time horizons and help archaeologists to date associated finds and stratigraphic units precisely. Five Late La Tène fibulae (150–80 BC) typical of the Western Carpathian Basin were studied in order to achieve information of their composition and manufacture. In particular, the alloy compositions were analyzed to understand if different alloys were used for the bow and the pin of the fibulae, and to establish if Pb and Zn were present. The latter was introduced to the workshops in Gallia and Northern Italy, and reached as imports the southeast Alpine region around 50 BC, creating a chronological horizon interesting for dating. Pb with >5 wt.% also turned out to be a chronological marker of La Tène fibulae. The presence of these alloying elements thus gives an even more detailed technological and chronological picture of the metallurgical advances in the ancient region of Pannonia during the second and beginning of the first century BC.
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Alloying Elements as Chronotechnological Marker for Second
and First Century BC Fibulae from Ancient Pannonia
1.—Dipartimento di Chimica e Chimica Industriale – DCCI, Facolta
`di Scienze Matematiche,
Fisiche e Naturali, Universita
´di Genova, 16038 Genoa, Italy. 2.—Arheolos
ˇki muzej u Zagrebu, Trg
Nikole S
´a Zrinskog 19, 10000 Zagreb, Croatia. 3.—e-mail:
Fibulae as main the metal elements of people’s costume and clothing vary
significantly in form and shape through time, and therefore, they are the
perfect chronological markers of periods and time horizons and help archae-
ologists to date associated finds and stratigraphic units precisely. Five Late La
`ne fibulae (150–80 BC) typical of the Western Carpathian Basin were
studied in order to achieve information of their composition and manufacture.
In particular, the alloy compositions were analyzed to understand if different
alloys were used for the bow and the pin of the fibulae, and to establish if Pb
and Zn were present. The latter was introduced to the workshops in Gallia and
Northern Italy, and reached as imports the southeast Alpine region around 50
BC, creating a chronological horizon interesting for dating. Pb with >5 wt.%
also turned out to be a chronological marker of La Te
`ne fibulae. The presence
of these alloying elements thus gives an even more detailed technological and
chronological picture of the metallurgical advances in the ancient region of
Pannonia during the second and beginning of the first century BC.
Modern archaeology collaborates more and more
with materials science in order to study the history
of technology and its development, advances, and
changes. It has always been assumed that great
technological discoveries radically changed the life
and habits of people. On the other hand, small
deviations and little changes can be investigated
only if technological markers can be connected with
chronological developments. This article, which
focuses on metallic objects only, is meant to exem-
plify this kind of research since metals are partic-
ularly interesting due (I) to gradual and subtle
changes in their properties and characteristics by
small modifications of alloy and treatment, and (II)
to record the microstructural features and their
thermomechanical history. Copper base alloys rep-
resent the main family of metallic materials used in
prehistory until the advent of iron and its alloys
around 800/750 BC in central Europe and are
therefore of the highest interest to our study.
As the subject of research, fibulae are amongst
the most suitable metallic objects. They are an
essential part of people’s dress and costume and,
therefore, are subject to everchanging fashions,
varying strongly in form and shape through time.
Ancient fibulae not only were decorative but also
served a much more practical function as fasteners
for clothing. Usually, fibulae are found in the
shoulder area of the skeleton, indicating the fixation
of, i.e., coats or cloaks. Fibulae were usually com-
posed of three to four components: the body or bow,
the pin, the spring, or the hinge (Fig. 1). Fibulae
replaced straight pins that were used in the Neo-
lithic and Early Bronze Age and became one of the
best tools for archaeologists to date contexts pre-
cisely, since the design and shape of the fibulae
changed faster than any other kind of metal object
and enabled the establishing of a more precise
chronology. Several hundreds of different classes,
types, or varieties of fibulae are known today. Many
of the classifications are based on historical periods,
regions, and cultures, thus giving us information
about dating, trade, distribution, usage, and some-
times even status or rank of their owner. The
manufacturing techniques are strongly affected by
the base materials, and the introduction of new
alloys is therefore an important marker of techno-
logical change. This article reports on the early
JOM, Vol. 64, No. 11, 2012
DOI: 10.1007/s11837-012-0415-0
Ó2012 TMS
(Published online September 21, 2012) 1343
stage of research on five fibulae found in the south
of ancient Pannonia, a geographical area based on
the Roman province Panonnia.
The first set of analyses focused mainly on the
alloy composition of the two most important parts of
the fibula—the bow and the pin—with the aim to
reconstruct the manufacturing technique (e.g., are
they made of single parts or is there a junction?) and
its connection with the presence of Pb and Zn as
additional alloying elements in the tin-bronze alloy.
Zinc usage is in effect connected with the growing
Roman influence in the areas concerned around
50–40 BC, marking the very first intentional usage
of Zn in the region. The introduction of Zn in the
southeast Alpine region is dated to 50–40 BC and
arrived as Roman import. The introduction of Zn at
the early stage of contacts between the local popu-
lation and the expanding Roman Empire gives
important chronological information. Additionally,
from the technological point of view, it is not the use
of brass, which could be imported as a rare and
precious alloy, but the production of the alloy that
corresponds to a real revolution. Zinc as a pure
metal was totally unknown and brass was made by
cementing Cu with Zn ores. The most recent
research in this field is well summarized.
Lead in tin bronzes seems to affect the castability
and the fluidity of the alloy in a positive way,
but it
has adverse effects on the shapability by cold
deformation if used above a certain amount. The
mechanical properties of each part of the fibula as
well as manufacturing techniques are strictly
related. For instance, the elasticity and mechanical
resistance necessary for the spring and pin can only
be the consequence of a thermomechanical history
(i.e., casting followed by several steps of cold ham-
mering and recrystallization annealing) that cannot
properly work with a high amount of lead. On the
contrary, the bow can be cast, and therefore, higher
amounts of Pb as an alloying element decrease the
risk of defects. Compared to other as-cast tin bronze
objects from the Late Iron Age, >5 wt.% of Pb might
also be seen as a chronological marker for the
technological evolution for the manufacture of La
`ne fibulae, as we will point out in the following.
The five fibulae discussed hereafter (Fig. 2)
originate from Dalj and Novi Jankovci in Croatia
and Novi Banovci, Serbia. The fibulae represent a
reasonable and statistically relevant amount of the
small number of Late La Te
`ne cast fibulae from the
southeast Pannonia. They represent local copies or
were at least inspired by the Oberleiserberg type.
Since they were not part of the autochthonous
attire, their presence indicates transmission of
decorative elements between the two regions. The
Oberleiserberg type is part of a larger group of cast
fibulae characteristic for the western Carpathian
Basin and date to the early phase of the late La
`ne period—Lt D1 (c. 150–80 BC).
The La Te
period in Central Europe is divided in four phases:
A (c. 480–400 BC), B (c. 400–320 BC), C (c. 320–
150 BC), and D (c. 150–30/0 BC). Each of the four
phases is then again subdivided even more, i.e., D1,
C2, etc. This relative chronology refers to the
sequence of types and events but does not neces-
sarily determine their absolute age; the absolute
dates for the four phases are approximate dates.
Oberleiserberg fibulae and most of Late La Te
cast fibulae imitate Middle La Te
`ne features in that
their foot, which is usually decorated with two
knobs, is bent backwards and connected to the bow,
thus forming a closed frame. The bow of the fibula
was cast on the already finished wire, which forms a
spring with up to 16 coils and a pin. Their presence
in southeast Pannonia is a proof of connections and
interactions between this area and the region of
Lower Austria since it is generally thought that
they were produced in the Oberleiserberg settlement.
All fibulae mentioned in the text are noted in Table I.
Late La Te
`ne cast fibulae with ‘‘pseudo-Middle La
`ne’’ scheme as the Oberleiserberg or the Magda-
lenska gora are typical for the western part of the
Carpathian basin. Fibulae of the type Almgren 65
were one of the most numerous fibulae of the Lt D2a
(c. 80–45 BC) phase. There are around 40 known
fibulae of the Nova vas type, mostly from northern
Italy and Slovenia. Furthermore, single finds are
known also from Spain, Germany, Greece, Austria,
France, and Dalmatia. Certosa-type fibulae have 13
variants or subtypes and were the most popular
items in central Europe, Italy, and southern Pan-
nonia in the Late Hallstatt period. In the northern
Balkan area, they were part of the material culture
together with the local Balkan types.
The analyses of elements were performed on
metal chips produced by drilling microholes (with a
diameter less than 1 mm ø) in the lower, hidden
part of the bow of the fibula. The volume of matter
obtained for each sample ranges between 0.5 mm
and 0.75 mm
. Since the fibulae are covered by
corroded layers, it was necessary to carefully
Fig. 1. Construction scheme of a typical Late La Te
´ne fibula type
Oberleiserberg (find spot: Novi Jankovci, Croatia). The body bow is
cast, respectively, on the spiral/pin
¨dlinger, Drnic
´, and Piccardo1344
separate the metallic chips from the oxidized pow-
ders via stereoscope. The remaining small amount
of metal (Figs. 3,4) was then submitted to compo-
sitional characterization by energy dispersive x-ray
spectroscopy (EDXS) connected to a scanning elec-
tron microscope (SEM).
It is worth to specify that the amount of sample
collected from each fibula is not enough for other
more sensitive analytical techniques such as ion-
coupled plasma spectroscopy or x-ray fluorescence
(XRF). Moreover, the observation by SEM allows to
be aware of the area of analyses and to avoid cor-
roded or altered areas. The corrosion layers of
bronzes are in effect richer in Sn and Pb than the
metallic substrate.
Thus, nondestructive surface
analyses (e.g., XRF or proton-induced x-ray emis-
sions) are not suitable since the corrosion does not
permit the analyses of the pure metal only. The
same is true for bulk analyses (e.g., time of flight
neutron diffraction or prompt gamma activation
analyses). When corrosion layers and the metal core
are still present, the corrosion influences the mea-
surements, always leading to different amounts of
Sn and Pb and other composition elements than
expected for the real composition of the alloy. The
same should be said for minor and trace elements
important for archaeology, e.g., for studies on cop-
per ore origins. The higher sensitivity of these
methods is in our case less important than the
possibility to determine where exactly the mea-
surements were taken. The SEM-EDXS is a well-
known investigation technique matching the preci-
sion needed for a project where the elements taken
into account have to be over 1 wt.% to be considered
of some importance; it is to determine whether
metals were intentionally added or are randomly
present in the materials. Lower concentrations than
1 wt.% of alloying elements are in fact not consid-
ered intentional for such alloys and therefore cannot
be used as technological markers. The scanning
electron microscope used for this research is a Zeiss
Evo40 (Carl Zeiss, Oberkochen, Germany), working
in high vacuum and equipped with a PentaFET
EDXS detector (Oxford Instruments, Oxfordshire,
U.K.) sensitive to light elements (Z>5). The oper-
ating conditions were an accelerating voltage of
20 kV, P<10
barr and an acquisition time of 60 s
with 2000 channels of 5 eV each. For quantitative
analyses, the ZAF* 5 correction was applied
Fig. 2. The five fibulae studied. Drilling samples were taken all on the inside of the bow where the cross-section is marked. 1. Dalj (Majnaric
´, 1970); 2–4. Novi Banovci (unpublished); and 5. Novi Jankovci (Majnaric
´, 1970).
*ZAF refers to the three parts of matrix effects—atomic number
(Z), absorption (A), and fluorescence (F).
Alloying Elements as Chronotechnological Marker for Second
and First Century BC Fibulae from Ancient Pannonia
together with cobalt calibration and real standards.
Concentrations lower than 0.3 wt.% are considered
semiquantitative and taken into account only when
the identification peaks are clearly visible in the
acquired spectrum. The compositions reported in
this article are in weight percent and normalized.
They correspond to the mathematical average of
9–16 spectra with suitable fit index per each sample.
The elemental analyses of the five fibulae are
reported in Table II. It is clearly visible that the
alloy of the bow of each fibula is a copper base
material particularly rich in lead (ranging from 8 to
19 wt.%). Despite the important differences in the
amount of tin (from 2 up to 10 wt.%), all alloys can
be classified as leaded tin bronzes. Zinc is only
present as a minor element in one fibula (invno.
P-6261) and, if ever present, under the limit of
detection in all other samples. Other elements have
been considered as well that might be connected
with the alloy production or origin and could be of
some help for further analyses performed on similar
objects (Ag, S, Fe, Ni, As, and Co).
None of the fibulae, therefore, contained alloying
levels of Zn. This is consistent with the current
dating of the introduction of Zn only as import
of brass objects in the southeast Alpine region to
50–40 BC. The traces of Zn in the fibula P-6261
are most likely residues of the copper ore. The
same explanation can be suggested also for the
small amounts of Co, Ni, and Ag found in fibulae
P-20945, P-20839, and P-6261. The traces of Fe, in
contrast, might be part of copper sulfide inclusions
as in the case of fibula P-20945 (Table II). As and
Ag are important elements that should always be
considered since they might be used for the iden-
tification of copper ore sources along other ele-
ments such as Co, Sb, or Ni. Only arsenic was
found in all five samples as a minor element,
confirming that these fibulae have originated from
arsenic ores. Arsenic was the earliest element
used to produce copper base alloys and it is still
debated whether this is due to the specific selec-
tion of As-rich copper ores or due to adding As in
a voluntary alloying process; this may also differ
from region to region. Silver can be also associated
with Pb due to the high frequency of Ag-rich
Pb-ores. In copper base alloys with more than
1 wt.% Pb, it is highly possible that Pb was added
intentionally. It might be, therefore, interesting to
track and quantify the introduction of Ag as minor
element once high amounts of lead are found in
the bronze artifacts.
Only a small number of previous studies could be
used as comparative data, which mainly focused on
Table I. Type, date, distribution and design characteristics of the fibulae noted in the text
Type and Date
Distribution Design Characteristics
150–80 BC
Lower Austria,
western Hungary
Pseudo-Middle La Te
`ne construction—the
bow and
the foot form a closed frame
False clasp on the connection of the
foot and the bow (smooth or notched)
Two knobs on the foot (smooth or notched)
Wide spring with an external cord
gora 150–80 BC
Southeast Alpine
Pseudo-Middle La Te
`ne construction— the bow
and the foot form a closed frame
False clasp on the connection of the foot and the bow
Two knobs on the foot of different shapes
Wide spring with an external cord
80–45 BC
Italy, central Europe Late La Te
`ne construction—the bow and the foot
form a closed frame of triangular, rectangular, or
trapezoidal shape
Boss in the form of the disc on the bow
The spring which usually comprises of six
coils with an external cord
Nova Vas
120–80 BC
Northern Italy,
southeast Alpine region
Late La Te
`ne construction
The bow with three transverse ribs
Triangular or rectangular open foot
The spring with four coils and an internal cord
6th–4th c. BC
Italy, central Europe,
southeast Europe
The bow usually of semicircular or biconvex cross-section
The foot with the pin holder and the
button at the ending
The spring with two coils that exceeds to a needle
¨dlinger, Drnic
´, and Piccardo1346
slightly older La Te
`ne fibulae,
namely the fibulae
from Pottenbrunn and Mannersdorf, Austria, dat-
ing to the Lt A2-C1 period (400–220/200 BC) as well
as fibulae from Switzerland and Bohemia. Previous
investigations performed on these fibulae show
much smaller amounts of Pb than those from Pan-
nonia described in this article. The alloys of the
Swiss and Bohemian fibulae contain no lead at all,
while the fibulae from Pottenbrunn contain
2–3 wt.% of Pb and those from Mannersdorf only
1–2 wt.% of Pb.
Contemporary fibulae of the Mag-
dalenska gora type from Croatia also have a bow
cast of leaded tin bronze while the pin and the spiral
were made of CuSn only.
The same is the case for
the slightly younger fibulae of the type Almgren_65
from Germany dated to La Te
`ne D2a (80–45 BC)
and the Nova Vas type, Slovenia, dated to La Te
D1b (120–80 BC).
The bows of the two fibulae of
the Almgren_65 type from the Kleinen Gleichberg,
Germany, contain 6–8 wt.% Pb in the tin bronze;
strangely, the results of this analysis were not fully
published. The springs of the same fibulae are made
of tin bronze without lead, containing 6 wt.% tin in
one object and 12 wt.% in the other; this difference
is macroscopically visible in a clear color difference
of both spirals. Further details of the EDXS analy-
ses are not published yet.
This indicates that the
usage and the amount of Pb in La Te
`ne fibulae is a
technological and chronological marker just as we
know it from Zn and its introduction to the West by
the Romans from Asia Minor around 50 BC.
The differing composition between the bow and
the spring/pin is an important and clearly visible
factor to distinguish different manufacturing pro-
cesses. Unfortunately, only one of the fibulae stud-
ied (no. P-4471) had a fragment of the spring/pin
still in place and suitable for surface analyses.
Sampling this part was not possible due to the high
risk of breaking the pin and damaging the fibula.
The surface of the spring/pin was then analyzed by
a portable XRF on the linear part of the pin without
abrasion of the corroded layers. The results are
qualitative only but clearly indicate that the
metallic substrate covered by the patina is a CuSn
alloy without any Pb.
A highly leaded CuSn alloy can be shaped only
slightly manually, while it is more suitable for
machining, a manufacturing technique that was
developed by the Romans later. The prehistoric
shaping process applicable to all monophasic a-Sn
bronzes consists of casting, cold hammering, recrys-
tallization annealing between 550°C and 630°C, and
sometimes water quenching (a sort of solubility
quenching ‘‘ante-litteram’’). For the cold deformation,
the recrystallization steps were repeated as many
times as need to achieve the desired size (e.g., thick-
ness of plates) and shape of the object. The resulting
microstructural features were a nearly homogeneous
Fig. 3. Metal chips achieved by drilling of the bow of fibula P-4471-
74 for the analyses of the alloy composition.
Fig. 4. Metal chips from the fibula P-6261. Note the distribution of Pb
(white globular inclusions).
Table II. Average composition of the drilling samples from the Fibula bows in wt.% (gained by SEM analysis)
Invno. Cu Sn Pb Zn As Ag S Fe Co Ni
Fibula P-20945 86.6 2.8 10.3 n.d. 0.1 <0.1 <0.1 0.3 n.d. n.d.
Fibula P-4471 81.9 9.9 7.8 n.d. 0.5 n.d. n.d. 0.1 n.d. n.d.
Fibula P-20839 72.6 7.4 19.2 n.d. 0.3 0.2 n.d. 0.2 0.1 0.1
Fibula P-20846 85.9 5.1 8.5 n.d. 0.5 n.d. n.d. 0.1 n.d. n.d.
Fibula P-6261 81.2 8.4 9.5 0.1 0.4 0.3 n.d. 0.2 n.d. 0.1
Alloying Elements as Chronotechnological Marker for Second
and First Century BC Fibulae from Ancient Pannonia
solid solution (increasing with the number of per-
formed annealing) and well-recrystallized small
grains with numerous thermal twins. The mechanical
properties of such alloys made them suitable for all
uses, from small objects to weapons, and could be
improved by a last step of cold hardening as it was the
case of the spring of the fibulae. The pin and the spring
are in effect the parts with the highest strain during
the daily usage. The demands on the materials were
primarily the toughness ofthe pin and the elasticity of
the spring. The manufacturing of the pin leads to a
microstructure responding well to these needs. The tip
of the pin is usually cold hardened by hammering and
sharpening, while the spring is cold hardened by the
twisting process applied to shape the spirals. If Pb was
present in this alloy, then the manufacturing process
would be really difficult if not impossible and the
chances of failure would dramatically increase.
contrast, the Pb in the bow of the fibulae does not
represent a problem since the bow was a separate,
cast-on part.
Previous studies have in fact shown that once the
spiral and the pin were finished, the bow of the
fibula was usually cast on, using the lost wax tech-
nique. This has been, for example, describe for the
fibulae of the Magdalenska gora type
or for the
much older Certosa type.
After casting, the sur-
faces of the fibulae were smoothened and additional
decoration could be applied by using punches and
chisels. The presence of Pb in the bow is therefore a
clear hint on the nature of the fibula composed by
almost two well-distinguishable parts: the wrought
tin bronze spring/pin and the cast leaded tin bronze
bow. This represents a well-defined technological
decision regarding the design by the craftsman, a
professional who knew precisely, if only empirically,
the properties and behavior of materials.
It should be pointed out that there are numerous
instances of the conscious use of Pb in prehistoric
bronze objects corresponding to the manufacturing
technique. The main conclusion is that the presence
or absence of Pb is never random but always
intentional, as has been proven for several other
objects contemporary to the fibulae discussed. The
helmet type Novo Mesto from the river Sava near
Nova Gradis
ˇka, Croatia
is a very good example.
Here, Pb was only used for the solder and enamel
but not for the bronze sheets. This is also consistent
with Late Bronze Age tin-bronze objects, were Pb
was only added to objects that did not have to go
through intense deformation such as bronze sheets,
thus indicating a high level of knowledge about the
metals in use several thousand years ago. However,
leaded bronze was used more widely in Central and
Eastern Europe from the Late La Te
`ne period on.
The composition of the fibulae can be placed
within general regional trends in the circulation of
bronze before the introduction of Zn around 50–40
BC as a consequence of Romanization. Further-
more, we know that leaded Sn-bronze as used for
the bow of the fibulae was not used for the only
preserved spiral and needle (fibula no. P-4471). This
makes perfect sense from the point of material
characteristics since the spring and the pin needs to
be flexible and elastic and had to be hammered to its
final shape. We can also assume a cast-on of the bow
to the spring for the analyzed fibulae like it was
documented for the fibulae type Magdalenska gora.
The Pb in the bow of all fibulae can be considered
as a well-defined chronotechnological marker, thus
being the main evidence of a specific manufacturing
technique where the spring/pin and the bow are
made with different alloys and treated with differ-
ent manufacturing techniques. The spring and pin
are produced first, and then the bow is cast over the
shorter extremity of the spring, most likely using
the lost wax technique. The skills and knowledge of
the craftspeople as well as the time of adapting new
alloying elements are highlighted by the simple
presence of Pb in the copper base alloy.
The authors would like to thank the Austrian
Science Fund (FWF) and the FP7/Marie Curie
actions who supported the research of Marianne
¨dlinger with the Schro
¨dinger-fellowship no. J
3109-G21. Special thanks to Barry Molloy, Univer-
sity of Sheffield, United Kingdom, for the analyses
with the portable XRF as well as Miljenka Galic
Igor Krajcar from the Archaeological Museum in
Zagreb for drawings and photos of the fibulae.
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Alloying Elements as Chronotechnological Marker for Second
and First Century BC Fibulae from Ancient Pannonia
... A similar choice of alloy with a high lead content has been noted for cast fibulae of the same, i.e. Late La Tène, period (Mödlinger et al. 2012;Drni} 2012). 83 Dizdar, in print. ...
... A similar choice of alloy with a high lead content has been noted for cast fibulae of the same, i.e. Late La Tène, period (Mödlinger et al. 2012;Drni} 2012). 83 Dizdar, in print. ...
... 1: type VII. 36 Rustoiu 2011a2012, 366, Pl. 15. 37 Spasi} 1992 Jacanovi}, }or}evi} 1989-90, 30, Pl. LXXXVII: 4-6; Jovanovi} 1998, Pl. ...
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The focus of the paper is on bronze astragal belts in the south-eastern part of the Carpathian Basin, interpreted as part of the female costume. In particular, their production seems to have two peaks, one at the end of the Early Iron Age (6th-4th cent. BC) and another during the Late La Tène period. However, there is a continuity of the form throughout the Late Iron Age. Requiring a significant amount of material and craftsmanship, these belts imply the presence of skilled artisans, as well as a supply network that enabled the production. A new typological and chronological assessment of the known examples allows not only a better understanding of the possible production areas of astragal belts, but also the social implications behind the organisation of production, offering also the possibility to better evaluate the role of this particular item as a part of the autochthonous female costume and identity.
... Bei Legierungen aus der Hallstattzeit liegt der Mittelwert bei 4,6 % Blei und steigt bei Legierungen aus der Latènezeit auf 6,5 % an. Dieser Anstieg der Bleigehalte lässt sich auch in anderen Regionen Mitteleuropas beobachten (Frana et al. 1997;Mödlinger et al. 2012;Pollard et al. 2015 ...
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The excavations at the settlement in Virovitica revealed fibulae which, along with many ceramic forms, allow us to place the settlement in the Late La Tène period. Similarities with the ceramic finds from contemporaneous settlements in the Slovenian part of Podravina and Prekmurje are particularly numerous. Fibula cast in lead bronze belongs to the female attire of the Late La Tène period, and different variants of similarly cast fibulae have been found at the sites of the La Tène Culture in Central Europe. The bronze fibulae of the Beletov vrt type, found in the fillings of pit-dwellings in the north-eastern part of the settlement, are considered to be one of the characteristic Late La Tène forms of the Mokronog Group. In view of the typological characteristics and distribution, it can be presumed that the fibulae originated from workshops located in the area of Podravina.
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Prior to the mastering of metallic zinc production in the mid-19th century, brass making in Europe was based on the so-called cementation process: within a more or less closed vessel, gaseous zinc is produced by the carbothermic reduction of zinc ore at around 1,000°C (±100°C), and simultaneously diffuses into metallic copper. Few ancient brass objects dated before the Industrial Revolution analyzed so far bear more than 30 wt.% zinc, so that this zinc content value has become a dating criterion for these artifacts. The systematic laboratory-scale experimental simulations of the ancient process presented here permit the multiple influences of temperature, isothermal treatment duration, and initial Zn/Cu ratio on the zinc content of the final products, and on the zinc recovery rates as well, to be investigated for the first time.
This chapter presents that tin bronzes have been materials in common use since archaeological times. Many factors, such as the composition and microstructure of bronzes and the corrosive environment features of the burial context, can influence the chemical and structural nature of patinas. In general, the corrosion compounds have been roughly identified by X-ray diffraction (performed on the surface directly or on powder produced from the patina). Bronze corrosion exhibits complex and heterogeneous structures. However, it is established that patinas of ancient bronze objects reveal numerous common morphological features, such as the presence of tin-enriched corrosion layers. Furthermore, the formation process of bronze patinas in natural environments is mainly related to a selective dissolution of copper. The understanding of bronze patinas is most often based on two types of corrosion structures, according to the presence or absence of an original surface preserving the original shape of the artefact. It is introduced and detailed in the chapter. One of the main goals of the study presented in the chapter is to obtain a structural characterization of the nature of the corrosion compounds of internal tin-enriched corrosion layers in the case of “type 2” patinas. In addition to the classical approaches (optical and electron microscopy, elemental analysis), the Raman microspectroscopy and the X-ray microdiffraction are used in the study to get a structural analysis of the compounds with a lateral resolution at the microscopic level. The chapter discusses the results achieved in the frame of a better understanding of bronze corrosion mechanisms.
Air pollution in museum showcases is one main problem within preventive conservation. Applied materials for construction and decoration of showcases are potential emission sources for a broad variety of volatile organics. These might accumulate under those almost static conditions that are set within showcases due to conservation requirements. In particular, the knowledge of the potential hazardous impact of airborne pollutants on cultural assets caused a fundamental shift in material selection for showcase production during the last decades. However, systematic indoor air analyses within those modern-type showcases are missing so far. Hence, there is no knowledge if there has been achieved any improvement of air quality compared to traditional enclosures. In order to make the first move for evaluating the current situation in museum showcases, air analyses within passive-type enclosures of different construction types and ages have been performed. The focus was on concentrations of volatile and semi-volatile organic compounds (VOCs/SVOCs). Formaldehyde and organic acids have also been considered due to their known corrosive impact. All these target compounds have been determined by active and passive sampling and subsequent chemical analysis. It was found that in contrast to old-type showcases main emission sources have shifted from wood-based products and acid curing silicone rubbers to solvent-borne lacquers and neutral curing sealants. Due to secondary reactions, levels of acetic acid are still elevated. Thus, damage on artefact materials can still be suspected. The results reveal that a careful selection of construction materials is often not sufficient to lower air pollution levels. The development of risk assessment strategies and new technologies is therefore recommended.
Stability relations of malachite and azurite are calculated and shown in Eh-pH diagrams, using ΔF (Gibbs free energy) values listed in Garrels and Christ (1965). The malachite/azurite transition is very sensitive to small chemical changes in the environment: equilibrium is reached at P CO 2 = 10 −3.45 atm., i.e. close to normal values, whereas the precipitation of both minerals from cupric-ion-bearing solutions takes place at pH values between 6 and 8, depending CO 2 partial pressures. It is shown that stability relations of these minerals can be better explained in terms of activities of the carbonate and bicarbonate ion. Azurite can be formed only under relatively acid conditions at relatively high carbonate activities. Since the latter imply mostly basic conditions, this explains why malachite is the more common form of copper carbonate and that azurite can be formed only under rather unusual conditions. It also explains the frequent alteration of azurite into malachite, due to small changes in carbonate/bicarbonate activities. These alterations include pseudomorphs of malachite after azurite.
d’Enza (Reggio Emilia, Italy), was discovered during the second half of the 19th century on the right side of the Enza River at the entrance of the valley, in a key position for controlling some of the most important communications routes in the area. During the sixth century B.C., the village of Servirola extended about six hectares and sustained many production areas, including a metallurgical quarter equipped with a foundry. At the beginning of the fifth century B.C., the village, consisting of simple huts, was transformed into an urban settlement crossed by two orthogonal road axes oriented south-north and east-west, as in the urban center of Marzabotto (Bologna, Italy). A variety of objects, such as vessels, instruments, and ornaments, from this urban period have been unearthed at the site. Because of the number of these objects, some of the items were analyzed to establish if they were produced locally. Through this research (subsidized by the Special Project for the Safeguard of Cultural Heritage of the Italian CNR), some Certosa-type brooches (also called fibulae) were examined. This type of fibula is well documented in the Apennine area of Western Emilia, between the provinces of Reggio Emilia, Parma, and Piacenza.
The objectives of the project were to assess the critical relationships between environmental factors and damage of the artifacts and other cultural property exposed inside museums, by studying: (a) the outdoor/indoor pollutant concentration and their transfer inside the museum; (b) the distribution and circulation of pollutants inside the museum influenced by various factors; (c) chemical interactions between pollutants in the gas phase leading to removal and/or formation of secondary pollutants; (d) the final deposition of the indoor pollutants on surfaces of artistic interest and the damage on them, governed by strictly defined physicochemical parameters. All the above information, together with the main factors influencing each stage, were obtained by applying the methodology developed and described in detail here. Measurements of rate constants of reactions in the gas phase, of physicochemical deposition parameters on artefacts, and the synergistic effects of pollutants on the deposition parameters, were conducted. Seven PC programmes for analysing the experimental data were written and used. The pollutants, the solid materials and the museums chosen in this programme are only examples needed to develop the necessary methodology. The numerical results obtained serve the purpose of exemplifying the procedures and not enriching the world's bibliography with useless empirical information. Two commercially available protectives for marble were investigated from the point of view of their reactivity towards SO2 by using a diffusional technique. From measurements of SO2 concentration carried out on three types of marble, the deposition velocities have been calculated. Indoor monitoring of the church of San Luigi dei Francesi and of the Museo della Civiltá Romana in Rome has shown that indoor production of nitrous acid most likely results from heterogeneous reactions indoors, on the walls and the exposed surfaces.
Metallic objects are considered among the most significant findings in Cultural Heritage and represent the 'culture of Materials' and the habits of an historical period and of a population. They also preserve traces of time: from the transformation of the ores in metal (by smelting) to the degradation from metal to oxidised compounds (by corrosion processes). Metallography, historically devoted to connect the microstructural features to production processes and to chemical-physical-mechanical properties is a powerful and relatively easy approach to characterise metallic findings. All analytical tools and methods in the hands of a metallographer are improved through experience and practice and provide a large number of information (elemental composition, primary and secondary microstructures, surface treatments, corrosion rate, original ores traces) by the preparation of a fairly small microdestructive sample. A wise and careful use of the metallography allows the balance "object sacrifice/knowledge improvement" to lean on the right side contributing to the hard work of rebuilding humankind history. Beside a description of a research protocol some practical examples concerning archaeological findings are presented in this paper.
Late LaTène-Roman cemetery in Novo Mesto, Ljubljanska cesta and Okrajno Glavarstvo
  • D Bož
D. Bož, Late LaTène-Roman cemetery in Novo Mesto, Ljubljanska cesta and Okrajno Glavarstvo (Ljubljana, Slovenia: Narodni Muzej Slovenije, 2008), pp. 74–77.