Presently, deterioration of glass beads is a significant problem in conservation and restoration of beaded exhibits in museums. Glass corrosion affects nearly all kinds of beads but cloudy blue-green ones are more than others subjected to disastrous destruction. However, physical and chemical mechanisms of this phenomenon have not been understood thus far. This article presents results of a study of elemental and phase composition of glass of the blue-green beads of the 19th century obtained from exhibits kept in Russian museums. Using scanning electron microscopy, X-ray microanalysis, and X-ray powder analysis, we have detected and investigated Sb-rich microinclusions in the glass matrix of these beads and found them to be micro crystallites of KSbSiO5. These crystallites were not detected in other kinds of beads which are much less subjected to corrosion than the blue-green ones and deteriorate in a different way. We believe that individual precipitates of KSbSiO5 and especially their clusters play a major role in the blue-green bead deterioration giving rise to slow internal corrosion of the bead glass.

1.

It is known from archeology and history of arts, however, that beads have been used for adornment, especially for ornamentation of clothes or decorative weaving, during the whole human history since the very ancient time.2 

2.
L. S.
Dubin
,
The History of Beads: From 100,000 B.C. to the Present
, Revised ed. (
Harry N. Abrams
,
New York, USA
,
2009
).
3.
M.-J.
Opper
and
H.
Opper
,
BEADS
3
,
44
(
1991
);
I.
Ninni
,
BEADS
3
,
73
(
1991
).
4.
E. S.
Yurova
,
Old Russian Works of Beads
(
Istoky
,
Moscow, Russia
,
1995
) (in Russian).
5.
E. K.
Stolyarova
, “
Glass beads from the kurgan near Kholmy village
,” in
The Archaeology of the Moscow Region
, Proceedings of Scientific Seminar 7, edited by
A. V.
Engovatova
,
V. Yu.
Koval
, and
I. N.
Kuzina
(
Institute of Archaeology of the Russian Academy of Sciences
,
Moscow, Russia
,
2011
), pp.
422
428
.
6.
T. V.
Yuryeva
and
V. A.
Yuryev
,
J. Opt.
16
,
055704
(
2014
).
7.
S.
Lougheed
, “
Deteriorating glass beads on ethnographic objectsobjects: symptoms and conservation
,” in
Symposium 86: The Care and Preservation of Ethnographic Materials
, edited by
R.
Barclay
,
M.
Gilberg
,
J. C.
McCawley
, and
T.
Stone
(
Canadian Conservation Institute
,
Ottawa, Canada
,
1988
), pp.
109
113
.
8.
D. A.
Rumrill
,
BEADS
3
,
5
(
1991
);
K.
Karklins
and
C.
Schrire
,
BEADS
3
,
61
(
1991
).
9.
R. G. V.
Hancock
,
S.
Aufreiter
, and
I.
Kenyon
,
MRS Proc.
462
,
181
(
1996
).
10.
P. J.
Sirois
, “
The deterioration of glass trade beads from Canadian ethnographic and textile collections
,” in
Conservation of Glass and Ceramics: Research, Practice and Training
(
James & James
,
London, UK
,
1999
), pp.
84
95
.
11.
A.
Lovell
,
Glass Bead Deterioration of Ethnographic Objects: Identification, Prevention, and Treatment
(
John F. Kennedy University
,
CA, USA
,
2006
).
12.
R.
Ohern
,
Ethnographic Conserv. Newsl.
35
,
14
(
2013
);
R.
O'Hern
and
K.
McHugh
,
Bead Forum
63
,
1
(
2013
);
R.
O'Hern
and
K.
McHugh
,
AIC Objects Spec. Group Postpr.
21
,
205
(
2014
).
13.
A.
Bonneau
,
J.-F.
Moreau
,
R. G. V.
Hancock
, and
K.
Karklins
,
BEADS
26
,
35
(
2014
)
14.
M.
Wood
,
J. Afr. Archaeology
9
,
67
(
2011
);
P.
Robertshaw
,
M.
Wood
,
A.
Haour
,
K.
Karklins
, and
H.
Neff
,
J. Archaeol. Sci.
41
,
591
(
2014
).
15.
L. C.
Prinsloo
,
A.
Tournié
, and
P.
Colomban
,
J. Archaeol. Sci.
38
,
3264
(
2011
);
F.
Koleini
,
L. C.
Prinsloo
,
W. M.
Biemond
,
P.
Colomban
,
A.-T.
Ngo
,
J. C.
Boeyens
, and
M. M.
van der Ryst
,
J. Cult. Heritage
19
,
435
(
2016
).
16.
It should be noted that beads for embroidery and beads for manufacture of necklaces, rosaries, chaplets, bangles, etc., often are not distinguished between in the literature despite the difference in their sizes as well as manufacturing processes.
17.
R. H.
Brill
, “
Crizzling—A problem in glass conservation
,” in
Conservation in Archaeology and the Applied Arts, Stockholm Congress
, edited by
N. S.
Brommelle
and
P.
Smith
(
International Institute for Conservation of Historic and Artistic Works (IIC)
,
London, UK
,
1975
), pp.
121
134
.
18.
Etymology of the term “crizzling” is connected with the appearance of the rough and cracked glass surface resembling sunburnt skin on face or hands.17 
19.

See also Ref. 20 for effect of atmospheric water on corrosion of potassium glass and a series of articles presented in Ref. 21 for effect of organic polutants including acid from wooden cabinets or showcases on glassware corrosion.

20.
A.
Tournié
,
P.
Ricciardi
, and
P.
Colomban
,
Solid State Ionics
179
,
2142
(
2008
);
P.
Colomban
,
A.
Tournié
, and
P.
Ricciardi
,
J. Raman Spectrosc.
40
,
1949
(
2009
).
21.
L.
Robinet
,
C.
Coupry
,
K.
Eremin
, and
C.
Hall
,
J. Raman Spectrosc.
37
,
1278
(
2006
);
L.
Robinet
,
C.
Coupry
,
K.
Eremin
, and
C.
Hall
,
J. Raman Spectrosc.
37
,
789
(
2006
);
L.
Robinetand
,
K.
Eremin
,
C.
Coupry
,
C.
Hall
, and
N.
Lacome
,
J. Non-Cryst. Solids
353
,
1546
(
2007
);
L.
Robinet
,
C.
Hall
,
K. A.
Eremin
,
S.
Fearn
, and
J.
Tate
,
J. Non-Cryst. Solids
355
,
1479
(
2009
).
22.
T. V.
Yuryeva
,
I. B.
Afanasyev
, and
V. A.
Yuryev
, “
Investigation of deterioration and destruction of historical glass beads by means of scanning electron microscopy and x-ray microanalysis
,” in
XIX Russian Symposium on Electron Microscopy (SEM'15), 1–4 June, 2015
, edited by
E. B.
Yakimov
(
Institute of Microelectronics Technology and High Purity Materials RAS
,
Chernogolovka, Russia
,
2015
), pp.
418
419
.
23.
P.
Debye
,
Ann. Phys.
351
,
809
(
1915
).
24.
B. E.
Warren
,
X-ray Diffraction
(
Addison-Wesley
,
Reading, MA/Dover, Mineola, NY, USA
,
1969
).
25.
R. T.
Downs
and
M.
Hall-Wallace
,
Am. Mineral.
88
,
247
(
2003
);
S.
Gražulis
,
D.
Chateigner
,
R. T.
Downs
,
A. T.
Yokochi
,
M.
Quirós
,
L.
Lutterotti
,
E.
Manakova
,
J.
Butkus
,
P.
Moeck
, and
A.
Le Bail
,
J. Appl. Crystallogr.
42
,
726
(
2009
);
S.
Gražulis
,
A.
Daškevič
,
A.
Merkys
,
D.
Chateigner
,
L.
Lutterotti
,
M.
Quirós
,
N. R.
Serebryanaya
,
P.
Moeck
,
R. T.
Downs
, and
A.
Le Bail
,
Nucleic Acids Res.
40
,
D420
(
2012
);
A.
Merkys
,
A.
Vaitkus
,
J.
Butkus
,
M.
Okulič-Kazarinas
,
V.
Kairys
, and
S.
Gražulis
,
J. Appl. Crystallogr.
49
,
292
(
2016
).
26.

Note that the only exception was detected at point 23; in this sample striation was observed with the stria containing some amount of Sb (Fig. 3, panel l; Table I).

27.

A wider data array than that presented in Table I was employed in the correlation analysis.

28.
T. V.
Yuryeva
,
I. B.
Afanasyev
, and
V. A.
Yuryev
, “
Scanning electron microscopy and x-ray microanalysis of glass beads of the 19th century
,” in
XXVI Russian Conference on Electron Microscopy (SEM'16), 30 May– 3 June, 2016
, edited by
E. B.
Yakimov
(
Technounity, Zelenograd
,
Moscow, Russia
,
2016
), pp.
582
583
.
29.
M. P.
Crosnier
,
D.
Guyomard
,
A.
Verbaere
, and
Y.
Piffard
,
Eur. J. Solid State Inorg. Chem.
27
,
845
(
1990
).
30.

A higher temperature of the phase transition between tetragonal and orthorhombic phases of KSbOSiO4 (1200 °C) is given in Ref. 31.

31.
Y.
Kanno
,
J. Mater. Res.
9
,
2323
(
1994
).
32.
J. E.
Shelby
,
Introduction to Glass Science and Technology
(
The Royal Society of Chemistry
,
Cambridge, UK
,
1997
).

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