Investigations of Gold Tissues Surface from the Сathedral of Assumption (Kyiv) Sarcophagus
The objects of the cultural heritage discovered by archaeologists on the area of ancient Kyiv (Old Russia) were examined by non-destructive techniques such as SEM with EDXRS, XPS and AFM. The topographical examination shows that the fragments of gold tissues (XI–XVI AD) content two kinds of material...
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Інститут хімії поверхні ім. О.О. Чуйка НАН України
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irk-123456789-289802011-11-27T12:28:34Z Investigations of Gold Tissues Surface from the Сathedral of Assumption (Kyiv) Sarcophagus Zazhigalov, A.V. Balakin, S.A. Bacherikova, I.V. Zazhigalov, V.A. The objects of the cultural heritage discovered by archaeologists on the area of ancient Kyiv (Old Russia) were examined by non-destructive techniques such as SEM with EDXRS, XPS and AFM. The topographical examination shows that the fragments of gold tissues (XI–XVI AD) content two kinds of materials: golden spiral threads and light colour flakes. In the composition of the threads, Au is the basic element but the flakes contain C, O, Mg, Al, Si, P, S, Ag, Ca, and Fe. The origin of these flakes today is unknown (the traces of cloth or varnishes possible). The presence of Rb in golden artefacts testifies the existence of own gold output and technology on the area of ancient Kyiv. The absence of Cu, which presents in oldest gold tissue, in the samples manufactured in XV–XVI AD can be connected with an improvement of melting technology. The difference in the composition in the golden threads for all samples examined shows them to be manufactured in various regions of Old Russia. Об'єкти культурної спадщини, знайдені археологами на території старовинного Києва (Київська Русь), було досліджено за допомогою неруйнівних методів СЕМ разом з ЕДРС, РЕС і АСМ. Топологічне дослідження показало, що фрагменти золотих тканин (ХI–XVI ст. н.е.) містять два типи об'єктів: золотисті спіральні нитки і пластівці ясного кольору. В складі ниток основним елементом є золото, в той час як пластівці містять С, О, Mg, Al, Si, P, S, Ag, Ca та Fe. Природа цих пластівців на цей час не з’ясована (можливо це залишки одягу чи лаку). Наявність Rb в золотих нитках свідчить про існування власного видобутку золота і технології його обробки на території стародавнього Києва. Відсутність Cu, яка є в складі виробленої в ХІ ст. тканини, в об'єктах, що походять з XV–XVI ст. н.е., може бути пов'язано з покращенням технології виділення золота. Відмінності у вмісті елементів в усіх досліджених нитках свідчать, що вони були вироблені в різних регіонах стародавньої Русі. Объекты культурного наследия, найденные археологами на территории древнего Киева (Киевская Русь) были исследованы неразрушающими методами СЭМ совместно с ЭДРС, РЭС и АСМ. Топологическое исследование показало, что фрагменты золотых тканей (ХI–XVI в. н.э.) содержат два типа объектов: золотистые спиральные нити и хлопья светлого цвета. В составе нитей основным элементом является золото, в то время как хлопья содержат С, О, Mg, Al, Si, P, S, Ag, Ca и Fe. Природа этих хлопьев в настоящее время не выяснена (возможно, остатки одежды или лака). Наличие Rb в золотых нитях свидетельствует о существование собственной добычи золота и технологии его обработки на территории древнего Киева. Отсутствие Cu, которая присутствует в наиболее старой ткани, в объектах, произведенных в XV–XVI веках н.э., может быть связано с улучшением технологии выделения золота. Различие в содержании элементов во всех исследованных нитях показывает, что они были произведены в различных регионах древней Руси. 2010 Article Investigations of Gold Tissues Surface from the Сathedral of Assumption (Kyiv) Sarcophagus / A.V. Zazhigalov, S.A. Balakin, I.V. Bacherikova, V.A. Zazhigalov // Хімія, фізика та технологія поверхні. — 2010. — Т. 1, № 2. — С. 209-218. — Бібліогр.: 24 назв. — англ. 2079-1704 http://dspace.nbuv.gov.ua/handle/123456789/28980 544.72 en Хімія, фізика та технологія поверхні Інститут хімії поверхні ім. О.О. Чуйка НАН України |
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The objects of the cultural heritage discovered by archaeologists on the area of ancient Kyiv (Old Russia) were examined by non-destructive techniques such as SEM with EDXRS, XPS and AFM. The topographical examination shows that the fragments of gold tissues (XI–XVI AD) content two kinds of materials: golden spiral threads and light colour flakes. In the composition of the threads, Au is the basic element but the flakes contain C, O, Mg, Al, Si, P, S, Ag, Ca, and Fe. The origin of these flakes today is unknown (the traces of cloth or varnishes possible). The presence of Rb in golden artefacts testifies the existence of own gold output and technology on the area of ancient Kyiv. The absence of Cu, which presents in oldest gold tissue, in the samples manufactured in XV–XVI AD can be connected with an improvement of melting technology. The difference in the composition in the golden threads for all samples examined shows them to be manufactured in various regions of Old Russia. |
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Zazhigalov, A.V. Balakin, S.A. Bacherikova, I.V. Zazhigalov, V.A. |
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Zazhigalov, A.V. Balakin, S.A. Bacherikova, I.V. Zazhigalov, V.A. Investigations of Gold Tissues Surface from the Сathedral of Assumption (Kyiv) Sarcophagus Хімія, фізика та технологія поверхні |
| author_facet |
Zazhigalov, A.V. Balakin, S.A. Bacherikova, I.V. Zazhigalov, V.A. |
| author_sort |
Zazhigalov, A.V. |
| title |
Investigations of Gold Tissues Surface from the Сathedral of Assumption (Kyiv) Sarcophagus |
| title_short |
Investigations of Gold Tissues Surface from the Сathedral of Assumption (Kyiv) Sarcophagus |
| title_full |
Investigations of Gold Tissues Surface from the Сathedral of Assumption (Kyiv) Sarcophagus |
| title_fullStr |
Investigations of Gold Tissues Surface from the Сathedral of Assumption (Kyiv) Sarcophagus |
| title_full_unstemmed |
Investigations of Gold Tissues Surface from the Сathedral of Assumption (Kyiv) Sarcophagus |
| title_sort |
investigations of gold tissues surface from the сathedral of assumption (kyiv) sarcophagus |
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Інститут хімії поверхні ім. О.О. Чуйка НАН України |
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2010 |
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http://dspace.nbuv.gov.ua/handle/123456789/28980 |
| citation_txt |
Investigations of Gold Tissues Surface from the Сathedral of Assumption (Kyiv) Sarcophagus / A.V. Zazhigalov, S.A. Balakin, I.V. Bacherikova, V.A. Zazhigalov // Хімія, фізика та технологія поверхні. — 2010. — Т. 1, № 2. — С. 209-218. — Бібліогр.: 24 назв. — англ. |
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Хімія, фізика та технологія поверхні |
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Хімія, фізика та технологія поверхні. 2010. Т. 1. № 2. С. 209–218
_____________________________________________________________________________________________
* Corresponding author zazhigal@ispe.kiev.ua
ХФТП 2010. Т. 1. № 2 209
УДК 544.72
INVESTIGATION OF GOLD TISSUES SURFACE FROM THE
CATHEDRAL OF ASSUMPTION (KYIV) SARCOPHAGUS
A.V. Zazhigalov1, S.A. Balakin1, I.V. Bacherikova2, V.A. Zazhigalov2*
1National Kyiv-Pechersk Historico-Cultural Preserve, Department of Archaeology
21 Ivan Mazepa Street, Kyiv 01015, Ukraine
2Institute of Sorption and Problems of Endoecology of National Academy of Sciences of Ukraine
13 General Naumov Street, Kyiv 03164, Ukraine
The objects of the cultural heritage discovered by archaeologists on the area of ancient Kyiv
(Old Russia) were examined by non-destructive techniques such as SEM with EDXRS, XPS and
AFM. The topographical examination shows that the fragments of gold tissues (XI–XVI AD) con-
tent two kinds of materials: golden spiral threads and light colour flakes. In the composition of
the threads, Au is the basic element but the flakes contain C, O, Mg, Al, Si, P, S, Ag, Ca, and Fe.
The origin of these flakes today is unknown (the traces of cloth or varnishes possible). The pres-
ence of Rb in golden artefacts testifies the existence of own gold output and technology on the
area of ancient Kyiv. The absence of Cu, which presents in oldest gold tissue, in the samples
manufactured in XV–XVI AD can be connected with an improvement of melting technology. The
difference in the composition in the golden threads for all samples examined shows them to be
manufactured in various regions of Old Russia.
INTRODUCTION
Archaeology tries to reconstruct the culture
and history of past societies, especially of those
on which no or poor written sources exist and for
which information on every day life is in scare.
Archaeology today uses a variety of methods and
tools: survey and excavation, environmental
analysis or glacial records, scientific and histori-
cal dating methods, historic and iconographic
sources, archaeological experiments and, last but
not least, material analysis of found artefacts. The
material analysis has two main topics: the charac-
terization of the material of which objects consist
and the characterization of technical treatment or
manufacturing of the objects. The first can, for
instance, give information about the provenance
of the material while the latter helps us to recon-
struct ancient techniques.
The excavations and investigations of archae-
ologists often lead to discovery of golden arte-
facts. Among the metals used by man in past,
gold has a privileged place. Mainly obtained by
the exploitation of quartz veins (primary deposits)
and placers (second deposits), found free in na-
ture, gold was one of the first metals used in fab-
rication of objects [1]. The analysis of gold ob-
jects contributes to the knowledge of many as-
pects of their fabrication [2]. Various information
can be obtained on the manufacturing technolo-
gies of the objects and on the provenance of the
metal as a result of the analytical methods use.
The aim of the first studies is an accurate descrip-
tion of the objects using information given by
their analysis. The aim of the second point is the
identification of the extraction, refining and alloy-
ing techniques.
A variety of instrumental analytical technique
can be applied to the physical and chemical ex-
amination of the works of art and archaeology but
mainly without any sampling. The most examined
from the gold finds are different jewellery, coins,
metal alloy and shards discovered in America and
Europe [2–16]. The use of modern methods of
non-destructive analysis permits us to determine
the provenance of gold or its origin difference [2,
9–13, 17, 18] and to propose a technique of the
objects manufacture or treatment [2, 8, 13–15, 17,
18]. In the same time, it is necessary to note that
the objects of the cultural heritage found in the
East Europe, on the area of Old Russia particu-
larly, belong to the number of less studied.
The fragments of gold tissues, somewhat ex-
otic materials, found by archaeologists in differ-
ent tombs of the Cathedral of Assumption (Kyiv)
were the objects of this investigation. SEM with
A.V. Zazhigalov, S.A. Balakin, I.V. Bacherikova, V.A. Zazhigalov
_____________________________________________________________________________________________
210 ХФТП 2010. Т. 1. № 2
EDXRS (Scanning Electron Microscopy with
Energy Dispersion X-ray Spectrometry), XPS
(X-ray photoelectron spectroscopy) and AFM
(atomic force microscopy) methods were used for
non-destructive chemical composition and topog-
raphical analysis of these archaeological finds. It
is necessary to note that two last methods were
not used for the study of gold artefacts in contrast
to the first technique [17, 18].
EXPERIMENTAL
The samples of the gold tissues studied in this
work were found in different sarcophagi of the
Cathedral of Assumption (Kyiv). The characteris-
tics of the objects studied are shown in Table 1.
Table 1. Description of tissue samples
Sample Characteristic of sample
T1
Fragment of gold tissue 2.4x1.5 m from
sarcophagus N 2; the tomb a man (proba-
bly the member of family of Knight
S.Olel’kovich); XV–XVI AD
T2
Fragment of gold tissue of a head-rest cov-
erlet from sarcophagus N 4; the tomb a
woman (probable the wife of Knight
M.Olel’kovich); XV–XVI AD
T3
Fragment of gold tissue from sarcophagus
N 3; the tomb of unknown man (probably
the church man); XI–XIII AD
The images of the gold tissues fragments and
their element composition on the subsurface re-
gion (probing depth up to 2 µm) for all samples,
without their cover by carbon, were obtained by
the method SEM with Jeol JSM 5400 and
EDXRS LINK ISIS Seria 300 instruments. The
composition analysis was realized by an elec-
tron microbeam in several places of each sam-
ple (see Figs).
The surface composition up to 2 nm was ob-
tained from XPS spectra recorded by a VG Sci-
entific ESCA-3 photoelectron spectrometer us-
ing AlKa radiation (1486.6 eV). Binding ener-
gies of electrons of analyzed elements were ref-
erenced to the C 1s peak at 284.8 eV. The spec-
trometer was interfaced with IBM PC AT micro-
computer for acquisition and processing. The
relative content of elements in the samples was
determined by a method analogous to that de-
scribed in [19].
The surface morphology of the samples and
its roughness in nanometric region was studied
by atomic force microscopy (AFM) using a
Nanoscope E, Digital Instruments Scanning
Probe Microscope Controller.
RESULTS AND DISCUSSION
The microphotographs of two fragments of
T1 sample presented in Fig. 1 show that the to-
pography of this object is complicated. The
amorphous compounds of light colour, looking
like flakes (points B1 and B2), present in the
surface of golden colour spiral threads (point A,
A1, and A2). It can be seen that these golden
threads represent the twisted foil with the
width equal to 150–200 µm and the thickness
near 2–5 µm. The flakes have the greater thick-
ness but the lesser other dimensions. The habitus
of these objects permit the use of microbeam
technique for the reliable quantitative analysis of
their chemical composition.
A
B
A1
A2
B1
Fig. 1. The microphotographs of gold tissue T1
Investigations of Gold Tissues Surface
_____________________________________________________________________________________________
ХФТП 2010. Т. 1. № 2 211
a
b
c
Fig. 2. EDXR analysis of the gold tissue T1 chemical
composition in points A (a), A1(b) and A2 (c)
a
b
Fig. 3. EDXR analysis of the gold tissue T1 chemical
composition in points B (a) and B1 (b)
The chemical analysis of the T1 sample by an
electron microbeam was realized in five points of
golden spiral threads (three points shown in
Fig. 1) and in four points of light flakes (two
points shown in Fig. 1). The analysis data pre-
sented in Fig. 2 show that the basic element in the
composition of spiral threads (points A) is Au.
Simultaneously they content a small quantity of
Ag and Rb. The composition of the threads de-
termined in other points is practically equal to the
data presented in Fig. 2. The analysis of light
flakes is presented in Fig. 3. The data of the
analysis demonstrate that these objects content
the following elements: C, O, Mg, Al, Si, P, S,
Ag, Ca, and Fe. The traces of Au were also ob-
A.V. Zazhigalov, S.A. Balakin, I.V. Bacherikova, V.A. Zazhigalov
_____________________________________________________________________________________________
212 ХФТП 2010. Т. 1. № 2
served. Analogous results were obtained for other
points B of T1 sample fragments.
The calculation results of the objects compo-
sition found in golden tissue T1 are presented in
Table 2 and Table 3.
Table 2. Composition of gold threads in tissues deter-
mined by EDXRS
Component, wt. %
Tissue Point
Au Ag Rb Cu
A 96.2 2.7 1.1 -
A1 95.8 3.0 1.2 -
A2 96.4 2.6 1.0 -
A3 96.8 2.3 0.9 -
T1
A4 97.1 2.2 0.7 -
A 96.6 1.9 1.5 -
A1 96.6 2.0 1.4 -
A2 96.5 2.1 1.4 -
A3 96.4 2.3 1.3 -
T2
A4 97.1 1.8 1.1 -
A 94.5 2.0 2.4 1.1
A1 94.3 1.9 2.6 1.2
A2 95.0 1.5 2.7 0.8
A3 95.4 1.4 2.5 0.7
A4 94.7 1.9 2.5 0.9
T3
Sum 94.9 1.8 2.3 1.0
Table 3. Composition of light flakes in tissue T1 de-
termined by EDXRS
Component, wt. %
Point
C O Ca Si Al P S Mg K Fe
B 25 16 17 14 9 6 8 1 1 3
B1 27 18 14 12 8 5 7 2 2 5
B2 20 16 19 17 11 4 5 1 3 4
B3 32 21 11 6 7 8 3 3 2 7
The fragments of golden tissues T2 and T3
are presented in Fig. 4. A small number of light
flakes is present on surface of golden spiral
threads in sample T2 but the surface of tissue T3
is practically free from these objects. The results
of chemical analysis by an electron microbeam of
these flakes (points B and B1) presented in Fig. 5
show that their composition differs from that de-
termined on tissue T1 (Fig. 3). The presence of
Ca and Si lines (the most intensive in Fig. 3) and
a high intensity of C and O lines against back-
ground of elements spectrum characteristic of
golden threads can be only observed. The absence
of other elements characteristic of the flakes
(Fig. 3) can be connected with small dimensions
and friable structure of these objects on sample
T2. As a result, the microbeam analysis shows the
base composition of gold threads disposed under
or near the flakes. The chemical analysis of gold
threads (points A and A1 on sample T2) demon-
strates the presence of Au (basic elements) and
little quantity of Rb and Ag (Fig. 6). These data
have no qualitative difference with the results
presented in Fig. 2 for tissue T1. The quantitative
data of the analysis of gold threads composition
are present in Table 2. The absence of all compo-
nents of light flakes (the major elements, Ca and
Si are only present in the spectrum,) did not per-
mit us to realize their composition quantitative
determination.
The microbeam analysis of golden threads
(points A and A1) in T3 sample permits the pres-
ence of Cu additive side by side with basic ele-
ments Au, Ag, and Rb found (Fig. 7). Since of
absence of the flakes on tissue T3, an EDXR
spectrum of the whole fragment presented in
Fig. 4 was obtained. The results show (Fig. 7,
spectrum Sum) the presence of Ca traces and in-
creased content of C and O in comparison with
the data for points A and A1 which are character-
istic for the composition of the flakes.
The composition of the flakes presented in
Table 3 shows that they content a large quantity
of carbon and oxygen and this fact permits us to
assume the organic origin of these objects. From
the one point of view, these flakes could present
the traces of cloth but, from the other hand, these
objects content enough number of inorganic ele-
ments. The analysis of published data shows that
these objects can belong to remains of the var-
nishes. It is known that varnishes are mixtures of
natural products in which the main components
are organic substances but, beside these major
components, some inorganic substances (as pig-
ments, siccatives, etc) were added to control the
properties of the historical varnishes [6].
The analysis of small flakes of varnishes de-
tected more than 20 elements in their composition
[6] among which silicon, phosphorus, sulphur,
potassium, aluminium, calcium, and iron, also
determined by us in this study. The published
data shown the impossibility to calculate the mass
fractions of the detected elements in relation to
the total sample mass and the relative content of
element with respect to the sum of all detected
elements was only determined.
Investigations of Gold Tissues Surface
_____________________________________________________________________________________________
ХФТП 2010. Т. 1. № 2 213
a
b
Fig. 5. EDXR analysis of the gold tissue T2 chemical
composition in points B (a) and B1 (b)
a
b
Fig. 6. EDXR analysis of the gold tissue T2 chemical
composition in points A (a) and A1 (b)
T2 T3
A
A1
B
B1
A
A1
Fig. 4. The microphotographs of gold tissue T2 and T3
A.V. Zazhigalov, S.A. Balakin, I.V. Bacherikova, V.A. Zazhigalov
_____________________________________________________________________________________________
214 ХФТП 2010. Т. 1. № 2
Presented in literature data demonstrate a
large change of the component ratio in different
samples of these artefacts. This operation was
also realized in our case and obtained data are
presented in Table 3. It is necessary to note that
quantity of the light flakes decreases for the sam-
ple T3 which is older for 2–3 centuries than T1
and T2.This fact can be connected with destruc-
tion of these objects (cloth or varnishes) and dis-
solution of inorganic elements or with the ab-
sence of this technique early and lower social
situation of the burial place object. Thus, the ori-
gin of the flakes detected by us today is unknown
and only further investigations would provide a
definitive answer about the nature of light flakes.
In order to determine the origin of gold artefact
not only the concentration of the base component
(gold) but the fingerprinting of gold or the con-
tent of specific trace and ultra-trace other ele-
ments has a big importance. The results of the
EDXR analysis of golden threads of the tissues
T1-T3 presented in Figs. 2, 6 and 7 are summa-
rized in Table 2 for all places of the composition
determination.
These data show a high content of gold in
all studied artefacts. The other elements de-
termined in these objects were Rb, Ag, and Cu
in the sample T3.Comparison with published
data of the gold artefacts analysis show that
two last elements present practically in all
goods but Rb was determined by different
methods in any ancient objects found in Bel-
gium [13], Macedonia [14], Spain [8, 10, 21],
Siberia and Mongolia [2, 11,16], South Amer-
ica and Mexico [17], Portugal [11, 18], France
[18], Italy [4, 9, 20], Greece [9] and other
places. The presence of this element in gold
objects from sarcophagus of the Cathedral of
Assumption can testify about the availability
of own gold output on Old Russia. On the
other hand, the oldest tissue T3 contents a Cu
additive in the composition which is absent in
another samples. This fact can be connected
with the difference in gold sources or in places
of these tissues manufacture in ancient Kyiv
(Old Russia). The change of gold production
technology which could take place at 2–3 cen-
turies can be taking in consideration also. It is
necessary to note that the concentration of
base element gold in threads of T3 (mean
value is equal to 94.8% wt.) is lower than in
T1 and T2 (96.5 and 96.6% wt., respectively).
The content of copper in artefact T3 is also
low (mean quantity is equal to 1.0% wt., Ta-
ble 2) and expected for native gold.
a
b
c
Fig. 7. EDXR analysis of the gold tissue T3 chemical
composition in points A (a), A1(b) and over
fragment presented in Fig. 4 (Sum) (c)
Investigations of Gold Tissues Surface
_____________________________________________________________________________________________
ХФТП 2010. Т. 1. № 2 215
The samples T1 and T2 have the same con-
tent of gold (see above) but the concentration of
additives (Ag and Rb) differs. If the amount of
silver and rubidium in threads of T1 is equal to
2.5 and 1.0% wt., their content in T2 is of a 2.0
and 1.4% wt., respectively. The observed differ-
ence between T1 and T2 in amount of impurities
can be connected in our opinion with the modifi-
cation of purification method of the same prove-
nance gold.
It is known that for the gold rich objects prob-
lems of patina or corrosion are absent. In connec-
tion with this the data of surface analysis by XPS
method and their comparison with the results ob-
tained by EDXRS permit us to determine the ho-
mogeneity of the samples or shed light on the
method of their manufacture. The determined
values of the electron binding energies (BE) of
the base elements of golden threads are presented
in Table 4. These data show that in samples T1
and T2 gold has one peak with BE value near
84.0 eV which is characteristic of metallic Au (0).
In the case of sample T3, two components in
spectrum of Au 4 f7/2-electrons are observed: the
first has BE = 83.9 eV (Au0) and the second with
BE = 85.6 eV which characterize the presence of
oxidized gold Au3+. The quantity of this last gold
form is equal to 10%. It is necessary to note that
practically the same BE of gold (84.0 and
85.5 eV) and amount of Au3+ (14%) values were
determined for a gold artefact in [21]. Analogous
results were observed for BE of Ag 3d5/2-
electrons: in the case of T1 and T2 samples the
spectrum was well fitted by one peak with value
of BE characteristic of Ag0 but two peaks with
BE of 367.8 and 368.6 eV were obtained for T3
sample which characterize the presence of Ag0
and Ag+ simultaneously with amount of Ag+ near
12%. All three samples demonstrate one peak of
Rb 3d5/2-electrons with value of BE near
110.0 eV. The low number of publications con-
nected with the XPS spectra of Rb did not permit
us to determine the valence state of this element.
In accordance with published data, this value of
BE was observed for metallic rubidium and its
compounds [22–24]. Copper was observed in the
XPS spectrum of T3 sample only and this spec-
trum of Cu 2p3/2-electrons had one peak with BE
= 932.3 eV corresponded to metallic element, and
the second peak with BE = 933.6 eV which could
be connected with oxidized copper. The presence
of the satellite peaks permits us to indicate the
existence of Cu2+ in the sample (Cu+ does not a
satellite). The ratio of these copper forms
Cu0/Cu2+ can be estimated as 70/30. The results
obtained permit us to suppose that presence of
copper in gold alloy initiates and catalyses the
surface oxidation of other elements or the forma-
tion of their carbonate surface layer.
Table 4. Electron binding energies of the elements of
golden threads
Binding energy of electrons, eV
Sample
Au 4f7/2 Ag 3d5/2 Rb 3d5/2 Cu 2p3/2
T1 83.9 367.8 109.8 -
T2 84.0 367.9 109.7 -
T3
83.9;
85.6
367.8;
368.6
110.0 932.3;
933.6
It is known that the determination of absolute
concentration of the elements by XPS method is a
very difficult problem but the atomic ratio of the
elements within surface layer can be determined
sufficiently exactly. These data are presented in
Table 5 as compared with the atomic ratio of the
elements calculated from the results obtained by
EDXRS. From Table 5 it is possible to see that
the atomic ratio of the components in samples T1
and T2 within surface and sub-surface layers is
practically the same. But an excess of copper
within surface layer of the sample T3 and a si-
multaneous decrease in silver content is observed.
This fact can be a reason of some corrosion of the
sample T3 surface layer. The increased content of
copper on surface in comparison to bulk of the
gold threads can be connected with diffusion of
this element in the times. On the other hand, these
results confirm the opinion connected with differ-
ence of technology of the manufacture of tissues
T1, T2, and T3.
Table 5. The atomic ratio of the elements of golden
threads
Atomic ratio of the elements
XPS analysis EDXRS analysis
Sam-
ple Au/Ag Au/Rb Au/Cu Au/Ag Au/Rb Au/Cu
T1 22.6 42.3 - 21.3 41.9 -
T2 25.7 30.1 - 26.2 29.6 -
T3 26.8 15.3 41.2 30.0 16.6 30.6
The results of study of golden threads of sam-
ple T1–T3 surface by AFM method are presented
in Fig. 8. The measurement of roughness of the
threads showed that its value for the T3 sample
A.V. Zazhigalov, S.A. Balakin, I.V. Bacherikova, V.A. Zazhigalov
_____________________________________________________________________________________________
216 ХФТП 2010. Т. 1. № 2
a b
c
Fig. 8. Surface morphology of the golden threads samples T1 (a), T2 (b), T3 (c) (AFM)
(1.70 nm) is practically two times more than
that the in samples T1 (0.81 nm) and T2
(0.97 nm). This fact can be connected with
partial surface oxidation of gold threads T3 or
with the difference in manufacture technique
of artefacts studied. The difference in rough-
ness of the golden threads of samples T1 and
T2 is less significant.
Thus, the investigation of the surface of
gold tissues found in sarcophagus of the Ca-
thedral of Assumption on the area of ancient
Kyiv permits us to determine the presence of
own original gold output on the territory of
Old Russia. The composition of the theses
gold artefacts differs from that of golden ob-
jects found in other countries of Europe and
America by the presence of Rb. It was found
that oldest tissue (XI–XIII AD) contents along
with base elements (Au, Ag, Rb) the addition
of copper which is absent in tissues manufac-
tured in XV–XVI AD. The low amount of
copper in tissue is a characteristic of native
gold. The presence of this addition leads to
light corrosion of surface layer of golden
threads of the oldest tissue which is absent in
other artefacts. The process of surface oxida-
tion leads to formation of Au3+, Ag+, and Cu2+
ions and increases the roughness of golden
threads. It can suppose the improvement of
smelting technology during 2–3 centuries
which led to a decrease of impurities in gold.
A definite difference in the composition of
golden threads for all three tissues can testify
that these goods were manufactured in differ-
ent regions of ancient Kyiv or Old Russia. On
the surface of gold threads of tissues produced
in XV–XVI AD the traces of cloth or var-
nishes were found. Their absence in tissue
manufactured early can testify the difference
of tissues technique preparation or the destruc-
tion of these objects in time.
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Received 12.05.2010, accepted 20.05.2010
A.V. Zazhigalov, S.A. Balakin, I.V. Bacherikova, V.A. Zazhigalov
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218 ХФТП 2010. Т. 1. № 2
Дослідження поверхні золотих тканин зі саркофагів
Успенського собору (Київ)
О.В. Зажигалов, С.А. Балакін, І.В. Бачерикова, В.О. Зажигалов
Національний Києво-Печерський історико-культурний заповідник, Відділ археології
вул. Івана. Мазепи 21, Київ 01015, Україна
Інститут сорбції і проблем ендоекології Національної академії наук України
вул. Генерала Наумова 13, Київ 03164, Україна, , zazhigal@ispe.kiev.ua
Об'єкти культурної спадщини, знайдені археологами на території старовинного Києва (Київська Русь),
було досліджено за допомогою неруйнівних методів СЕМ разом з ЕДРС, РЕС і АСМ. Топологічне дослі-
дження показало, що фрагменти золотих тканин (ХI–XVI ст. н.е.) містять два типи об'єктів: золотисті
спіральні нитки і пластівці ясного кольору. В складі ниток основним елементом є золото, в той час як пла-
стівці містять С, О, Mg, Al, Si, P, S, Ag, Ca та Fe. Природа цих пластівців на цей час не з’ясована (можли-
во це залишки одягу чи лаку). Наявність Rb в золотих нитках свідчить про існування власного видобутку
золота і технології його обробки на території стародавнього Києва. Відсутність Cu, яка є в складі вироб-
леної в ХІ ст. тканини, в об'єктах, що походять з XV–XVI ст. н.е., може бути пов'язано з покращенням
технології виділення золота. Відмінності у вмісті елементів в усіх досліджених нитках свідчать, що вони
були вироблені в різних регіонах стародавньої Русі.
Исследование поверхности золотых тканей из саркофагов
Успенского собора (Киев)
А.В.Зажигалов, С.А.Балакин, И.В.Бачерикова, В.А.Зажигалов
Национальный Киево-Печерский историко-культурный заповедник, Отдел археологии
ул. Ивана Мазепы 21, Киев 01015, Украина
Институт сорбции и проблем эндоэкологии Национальной академии наук Украины
ул. Генерала Наумова 13, Киев 03164, Украина, zazhigal@ispe.kiev.ua
Объекты культурного наследия, найденные археологами на территории древнего Киева (Киевская
Русь) были исследованы неразрушающими методами СЭМ совместно с ЭДРС, РЭС и АСМ. Топологи-
ческое исследование показало, что фрагменты золотых тканей (ХI–XVI в. н.э.) содержат два типа
объектов: золотистые спиральные нити и хлопья светлого цвета. В составе нитей основным эле-
ментом является золото, в то время как хлопья содержат С, О, Mg, Al, Si, P, S, Ag, Ca и Fe. Природа
этих хлопьев в настоящее время не выяснена (возможно, остатки одежды или лака). Наличие Rb в
золотых нитях свидетельствует о существование собственной добычи золота и технологии его об-
работки на территории древнего Киева. Отсутствие Cu, которая присутствует в наиболее старой
ткани, в объектах, произведенных в XV–XVI веках н.э., может быть связано с улучшением техноло-
гии выделения золота. Различие в содержании элементов во всех исследованных нитях показывает,
что они были произведены в различных регионах древней Руси.
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