033001-1 CHINESE OPTICS LETTERS / Vol. 9, No. 3 / March 10, 2011
Nondestru ctive identification of ancient Chinese glasse s by
Raman and proton-induced X-ray emission spectrosco py
Hongxia Zhao (
ëëë
___
)
1∗
, Huansheng Cheng (
«««
)))
)
2
, Qinghui Li (
ooo
¬¬¬
)
1
, and Fuxi Gan (
ZZZ444
)
1,2
1
Center of Sci-Tech Archaeology, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences,
Shanghai 201800, China
2
Institute of Modern Physics, Fudan University, Shanghai 200433, China
∗
Corresponding author: tulipzhao@163.com
Received August 5, 2010; accepted O ctober 14, 2010; posted online February 21, 2011
Nondestructive Raman spectroscopy and external-beam proton-induced X-ray emission (PIXE) technique
to analyze eight ancient glasses unearthed from the provinces of Henan, Hubei, and Jiangsu, which allowes
for a good characterization of the glass matrix and chemical compositions, is carried out. The results
indicate that all the eight glass samples could be typically divided into three systems: faience (sample
No. SZWG-4), PbO-BaO-SiO
2
(sample Nos. NYWK I-5-1, HNWK II-88, and HNWK II-84), and Na
2
O-
CaO-SiO
2
(sample Nos. HBWKI-16, HBWKI-17, HBWKI-18, and SZWG-1). Ad ditional relationships
between the Raman spectra and parameters, such as residues of raw materials and opacifying agent, are
also discussed by respectively comparing them with similar glass samples excavated from other historical
sites.
OCIS codes: 300.6450, 160.2750.
doi: 10.3788/COL201109.033001.
Glass, as an important artificial material and key evi-
dence for East-West cultural and technical exchange, has
played a great role in the course of human civilization
[1]
.
The chemical compositio ns of ancient glas ses are very
impo rtant for the determination of their types. The
analyses currently being used in ancient glasses usually
include inductively coupled plasma atomic emission s pec-
trometry (ICP-AES) and sc anning electron microscopy
(SEM), which are considered as destructive methods.
The us e of nondestructive techniques, such as Raman
sp e ctroscopy and external-beam proto n-induced X-ray
emission (PIXE), for the characterization of archaeo-
logical and historical artifacts has been demonstrated.
In the past 20 years, through the close cooperation
between archeologists and scientists, some new results
about the composition o f ancie nt Chinese glasses have
been obtained
[2]
, but very few Raman data have been
published. Faience, glas s, ceramics, and enamel around
the world have b e e n widely studied and compared by Ra-
man spectroscopy in the last decades. In addition, the
representative production technologies of the selected
artifacts in different areas such as Asian (Vietnamese
porcelains and celadon glazes), Islamic, European, and
African were also studied in many re search
[3−13]
. Hence,
the two techniques should also be applied in the analysis
of ancient Chinese glasses with very varied and complex
nature.
This study aims to provide some preliminary Ra-
man data on ancient Chinese glasses unearthed in the
provinces of Hubei, Henan, and J iangsu from the late
spring and autumn period to the Han dynasty. We
confirm the usefulness of these two techniques for a com-
pletely nondestructive study of a ncient Chinese glas ses
and clarify the correspondence between the Raman spec-
tra and the results of chemical compositions. Particular
attention is also given to the relationship between the
Raman spectra and the glass parameters such as residues
of raw materials and opacifying agent.
In this letter, eight ancient glasses were provided by
Suzhou Administration Committee of Cultural Relics,
Nanyang Institute of Cultura l Relics and Archaeology,
Henan Institute of Cultural Relics and Archaeology,
and Hubei Institute of Cultural Relics and Archaeology.
Fig. 1. Photos of the selected ancient Chinese glasses.
1671-7694/2011/033001(4)
c
2011 Chinese Optics Letters