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Co speciation in blue decorations of blue-and-white porcelains from
Jingdezhen kiln by using XAFS spectroscopy†‡
Lihua Wangab and Changsui Wang*b
Published on 23 May 2011. Downloaded by Temple University on 22/10/2014 14:16:32.

Received 14th December 2010, Accepted 15th April 2011

DOI: 10.1039/c0ja00240b

Co K-edge XAFS measurements were carried out to characterize the oxidation state and chemical
environment of cobalt element in the blue decorations of blue-and-white porcelains manufactured by
Jingdezhen official kiln during Yuan and Ming dynasties with the aim to investigate its coloring
mechanism. XANES spectra showed that cobalt was present as both divalent and trivalent ions and the
ratios of Co2+/Co3+ were almost similar for all samples with different historical periods. EXAFS
analysis indicated that cobalt atom was situated in both octahedral and tetrahedral sites. Considering
the empirical optical absorption in visible region, it was assumed that divalent ions located at
tetrahedral sites made the main contribution to the blue color.

Introduction
In China, blue-and-white porcelain usually designates white
porcelain decorated with blue pigment, which usually is cobalt
oxide under the glaze. As archaeologists discovered, blue-and-
white porcelain originated in Gongxian kiln, Henan province in
Tang dynasty.1 However, such a technique did not spread
extensively in Song dynasty. Till Yuan and Ming dynasties, blue-
and-white porcelain was developed and achieved its maturity in
Jingdezhen, Jiangxi province. Since then, blue-and-white porce-
lain has been well-known all around the world for its skilful
techniques and great artistic merit. A large quantity of blue-and-
white porcelains was manufactured in Jingdezhen city, especially
in the official kiln managed by the government named Guan kiln.
At that time, blue-and-white porcelains from Guan kiln were
considered as the highest quality of ancient Chinese ceramics and
exported to the whole world. However, previous research
pointed out that the cobalt pigment ore used for making blue-
and-white porcelain was from West Asia.2 Thus, to some extent,
blue-and-white porcelain played an important role in the cultural
exchange between the east and the west as the carrier of culture.
To date, issues about blue-and-white porcelain, such as
manufacturing technique, provenance of cobalt blue pigment
ore, dating, authentication, cultural exchange and trade contact
a
Shanghai Institute of Applied Physics, Chinese Academy of Sciences,
Shanghai, 201800, China
b
Department of Scientific History and Archaeometry, Graduate University
of the Chinese Academy of Sciences, Beijing, 100049, China. E-mail:
cswang@gucas.ac.cn
† This article is part of a themed issue highlighting the latest research in
the area of synchrotron radiation in art and archaeometry.
‡ Electronic supplementary information (ESI) available. See DOI:
10.1039/c0ja00240b
over the whole world, etc, have attracted large attention from
archaeologists, scientists, collectors and even artists.
Through the observation, it was found that tones of blue
decorations were different from one sample to another, in
particular samples with different historical periods. For example,
there were light blue, dark blue, blue with greenish hue, blue with
black hue, and so on. Previous studies of blue-and-white porce-
lains have demonstrated that transition metal elements including
cobalt, iron and manganese take part in the coloring effects
based on the chemical composition characteristics of blue deco-
rations.3–14 Cobalt was considered as the main element which was
responsible for blue color. However, most previous studies only
focused on the chemical composition of blue decorations with
the aim to investigate subjects about where the cobalt pigment
ore were from, where and when the blue-and-white porcelains
manufactured, where these porcelains were from and would go,
and so on. The contribution of cobalt, iron and manganese to the
color of blue decorations is not clear enough to date.
Generally speaking, transition metal elements can provide
a characteristic range of color tones which mainly depends on the
oxidation state and chemical environment of this element.15
Thus, for better understanding of the coloring mechanism of blue
decorations, some researches on the speciation of transition
metals, especially cobalt element, contained in blue decorations
have been carried out in recent years and several possibilities
could be found in literatures. One was cobalt aluminate
(CoAl2O4) which was obtained by Kock and de Waal16 through
performing Raman analysis on a blue decoration of underglaze
blue ceramic shards manufactured in Ming dynasty and late 19th
century. However, cobalt oxide (CoO) was another possibility
reported by J. Zuo et al.17 also through micro-Raman spectro-
scopic analysis of blue-and-white porcelain produced at Yongle
period, Ming dynasty. D. de Wall18 also investigated a blue
pigment of 17th century Delft dish by means of micro-Raman

1796 | J. Anal. At. Spectrom., 2011, 26, 1796–1801 This journal is ª The Royal Society of Chemistry 2011

spectroscopy and proposed that the main constituent was close
to the alpha-cobalt silicate with olivine structure (a-Co2SiO4).
Clearly, there were contradictions among results of the above
researches. This was partly due to the complexity of blue deco-
rations. On the other hand, the glaze layer on the surface of blue
decorations would induce strong fluorescence during analysis of
Raman spectroscopy. So by means of Raman spectroscopy, only
phase with high crystalline degree in blue decorations could be
detected and the Co speciation dissolved in glass matrix was
difficult to obtain.
Fortunately the value of X-ray absorption fine structure
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(XAFS) as a useful technique for getting information of oxida-
tion state and chemical environment of transition metals con-
tained in ancient materials has been demonstrated.19–30 It is
because XAFS is a nondestructive, element-selective and is
sensitive to trace elements. In addition to that, XAFS is an
atomic probe, which makes XAFS suitable for the analysis of
materials with unknown structure or amorphous phase.31
Based on the above situations, in this study, we focused on
a series of blue-and-white porcelains produced by Jingdezhen
official kiln in Yuan and Ming dynasties. The chemical compo-
sition of blue decorations was determined firstly using energy-
dispersive X-ray fluorescence spectroscopy. Then XAFS analysis
was carried out to identify cobalt speciation, including the
oxidation state of cobalt and the chemical environment
surrounding cobalt atoms. The primary purpose of this study
was to investigate the relationship between blue color and the
oxidation state and chemical environment of cobalt contained in
blue decorations.
Samples and methodologies
Samples
Five blue-and-white porcelain shards examined in this work were
provided by the Institute of Archaeology on Ceramics of Jing-
dezhen (Fig. S1‡). Among these shards (Table 1), Y10 was
produced in Yuan dynasty (AD1271–1368). YL14, XD3, CH9
and WL6 were from Ming dynasty, which was Yongle period
(AD1403–1424), Xuande period (AD1426–1435), Chenghua
period (AD1465–1487) and Wanli period (AD1573–1620),
respectively. The areas examined here were categorized as
a normal blue area where the pigment was dissolved in the glaze.13
Energy-dispersive X-ray fluorescence
Prior to XAFS analysis, chemical composition of blue decora-
tions and transparent glazes for all blue-and-white porcelains
were determined non-destructively by energy-dispersive XRF
Table 1 Detailed information of blue-and-white porcelains analyzed in
this study
Sample Period Date
Y10 Yuan Dynasty with unknown AD1271–1368
period
YL14 Yongle Period, Ming Dynasty AD1403–1424
XD3 Xuande Period, Ming Dynasty AD1426–1435
CH9 Chenghua Period, Ming Dynasty AD1465–1487
WL6 Wanli Period, Ming Dynasty AD1573–1620
This journal is ª The Royal Society of Chemistry 2011
View Article Online
analysis (type EAGLE-IIIm, made by EDAX International Inc.).
This instrument was run at the voltage of 35 kV and the current
of 400 mA. The elements analyzed here were: Na, Mg, Al, Si, K,
Ca, Mn, Fe, Co.
XAFS measurements
Co K-edge XAFS measurements were performed on beamline
1W1B at Beijing Synchrotron Radiation Facility (BSRF). The
storage ring energy was operated at 2.5 GeV with a ring current
of 100 mA to 250 mA. The source of 1W1B was derived from
a 7-pole wiggler device with magnetic field of 1.28 T and magnet
period was of 23 cm. A Si (111) double-crystal monochromator
was used to monochromatize the white beam. And higher
harmonics were rejected by detuning the Bragg angle of the
second crystal. At the site of sample, the flux was about 1011
photo/s and the beam size was ca. 0.9 (H)
0.3 (V) cm2.
All Co K-edge XAFS spectra of blue-and-white porcelains
were collected in fluorescence yield mode with Lytle detector at
room temperature. For comparison, compounds (CoO, Co3O4
and Co2O3) with analytical grade were used as reference mate-
rials and detected in transmission mode with ion chambers. In
different energy region, the absorption scan was recorded with
different energy steps and integral times (energy region, energy
step, integral time), that is in the pre-edge region (7589–7689 eV,
4 eV, 1s), in the absorption region (7689–7759 eV, 0.7 eV, 1s),
and in the EXAFS region (7759–7909 eV, 1 eV, 2 s; 7909–
8109 eV, 2 eV, 3 s; 8109–8509 eV, 4 eV, 3 s). Energy calibration
was carried out by measuring the XAFS spectrum of Co foil and
the first inflection was assumed to be 7709 eV.
XAFS data analysis
XANES spectra were analyzed using the ATHENA program in
IFEFFIT package.32 Background was subtracted by a linear
equation that was fitted to the region below the absorption edge
and a polynomial function of degree 2 that was fitted to the
EXAFS region. Then the spectra were normalized by cubic spline
method.
After that, EXAFS spectra were analyzed in the conventional
procedure with the aid of ATHENA and ARTEMIS program in
IFEFFIT package. EXAFS oscillations, c(k), was first extracted
from the spectra and transformed from k-space (k3, kmin ¼ 2.5 A 1,
kmax ¼ 8.8 A 1) using a Hanning window to R-space to obtain the
radial structure function (RSF). The EXAFS spectrum for the
first shell was isolated by inverse Fourier Transform of the RSF
over the appropriate region and fitted using the single scattering
EXAFS equation in both k- and R- space. The amplitude and
phase functions used for fitting the first shell were generated from
Co3O4 using program FEFF8.2. The residue used to evaluate the
quality of fits was the square root of the average square difference
between simulation and experimental data.
Results
Chemical composition
The chemical analysis of major elements (Table 2) revealed that
the colorless transparent glaze of all blue-and-white porcelain
shards were silica-aluminum system with calcium and sodium as
J. Anal. At. Spectrom., 2011, 26, 1796–1801 | 1797
 View Article Online

flux agent. Chemical composition of blue decorations showed

that cobalt, manganese and iron were responsible for the color of
blue decorations. Just as previous studies identified,13 cobalt was
the main color agent responsible for the blue color.

XAFS results
Fig. 1 shows the normalized XANES spectra collected at Co
K-edge for Co2O3, CoO and all blue-and-white porcelain shards.
Here, energy of the absorption edge was defined as the energy at
half maximum of the edge crest. The characteristic energy for
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XANES spectra of each sample and related reference materials

were summarized in Table 3. As shown in Fig. 2, there was a shift
of 1.9 eV towards a high energy side in the spectrum of Co2O3
compared with that of CoO. This positive shift can be under-
stood due to the valence increase. Because cobalt is a trivalent ion
form in Co2O3 whereas cobalt is a divalent ion form in CoO. For
all blue-and-white porcelain shards, energies of absorption edge
shifted toward high energy side compared with that of CoO and
shifted toward low energy side compared with that of Co2O3.
This result indicated that cobalt in blue decorations of blue-and-
white porcelain shards was present as both divalent and trivalent
ions. In addition to that, the XANES spectra of blue-and-white
porcelains were almost identical, which indicated that the ratios
of Co2+/Co3+ were similar in all blue-and-white porcelains
analyzed here.
After that, the result of c(k) with no k weight for all blue-and-
white porcelains and reference materials CoO and Co3O4 are
reported in Fig. 2.
Fig. 3 shows the radial structure function (RSF) with phase
uncorrected for CoO, Co3O4 and all blue-and-white porcelain
shards. Theoretically, CoO has a simple cubic structure, in which
cobalt is coordinated by 6 oxygen atoms with the Co–O distance
 While Co3O4 has a spinel structure with 1/3 cobalt
of 2.133 A.
atom located at tetrahedral site and the others situated in octa-
hedral site. The nearest neighboring atoms were 4 oxygen atoms
with the Co–O distance of 1.92 A.  33,34 Accordingly, the first

major peak at 1.626 A in Fig. 3 for CoO was due to the first
neighboring 6 oxygen atoms. And the first peak for Co3O4 in
 should be attributed to the first 4 oxygen
Fig. 3 located at 1.435 A
atoms. By contrast, all the blue-and-white porcelains mainly
 to 1.59 A.
 Discussion
showed one major peak at the distance from 1.47 A
According to the inter-atomic distance, this peak could be
attributed to Co–O bonds. Here, the lack of a more neighboring
Fig. 1 Normalized Co K-edge XANES spectra for blue-and-white
porcelain shards as compared with reference materials.
peak could be due to the amorphous phase where the cobalt atom
is situated.
The best fitting results are reported in Fig. 4 where the
experimental values were illustrated by solid line and the calcu-
lated values were illustrated by open circles. As shown in Fig. 4,
there is fairly good agreement between the experimental and
calculated data for all samples in both R- and k-space. This
agreement was also identified by the fitting parameter R-factor
which demonstrated the fit quality as shown in Table 4.
Table 4 reports the structural parameters calculated by the
least-squares fit of inverse Fourier transformed EXAFS oscilla-
tions with k3 weight. The inter-atomic distances were at 1.98 A, 
   
1.96 A, 1.96 A, 1.98 A and 1.97 A for sample Y10, YL14, XD3,
CH9 and WL6 respectively. The relatively short Co–O bond
lengths (1.97 A) suggest that the cobalt atom in blue decora-
tions preferred the tetrahedral site since the tetrahedral distance
was shorter than that of the octahedral site.35 However, cobalt
atoms located at octahedral sites could not be excluded
completely. Here, the coordination number was not taken into
account for our discussion. This was because these data involve
an intrinsic ambiguity due to the disorder effect typical for
amorphous phase.
In most ancient Chinese ceramics, color originated from the
absorption of transition metal ions contained in glaze or

Table 2 Chemical composition of blue decorations and transparent colorless glaze of blue-and-white porcelains analyzed in this study (wt%)

Sample Detective site Na2O MgO Al2O3 SiO2 K2O CaO MnO Fe2O3 CoO

Y10 Blue decoration 2.16 0.35 14.19 69.04 3.84 8.56 0.11 1.51 0.21
Glaze 2.05 0.18 13.90 70.73 3.72 8.24 0.10 1.06 0.01
YL14 Blue decoration 1.46 1.00 12.39 65.78 4.77 8.15 0.48 4.79 1.20
Glaze 1.42 0.77 12.59 71.48 5.05 7.63 0.12 0.95 nda
XD3 Blue decoration 1.50 0.49 12.51 70.73 4.18 5.77 2.42 1.89 0.47
Glaze 1.35 0.56 12.44 72.09 3.75 8.63 0.12 1.05 nd
CH9 Blue decoration 1.04 0.32 16.11 69.21 6.49 3.82 1.16 1.51 0.30
Glaze 1.22 0.24 14.64 71.90 7.25 3.40 0.12 1.15 nd
WL6 Blue decoration 2.02 0.56 15.50 62.98 4.89 7.46 2.25 3.07 1.22
Glaze 1.32 0.21 15.40 67.22 5.19 8.54 0.13 1.92 nd
a
nd, not detected.

1798 | J. Anal. At. Spectrom., 2011, 26, 1796–1801 This journal is ª The Royal Society of Chemistry 2011
 View Article Online

Table 3 Characteristic energies of Co K-edge XANES spectra for all

blue-and-white porcelains and reference materials

Energy (eV)

Sample Edge Edge crest

Co2O3 7719.7 7731.4

CoO 7717.8 7727.3
Y10 7718.6 7727.2
YL14 7718.7 7727.1
XD3 7718.7 7727.1
CH9 7719.0 7727.0
WL6 7718.8 7727.1
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Fig. 3 k3-weighted, phase uncorrected FT of all blue-and-white porce-

lains and reference materials CoO and Co3O4. The capital letter stood for
CoO (A), Co3O4 (B), Y10 (C), YL14 (D), XD3 (E), CH9 (F), WL6 (G)
respectively from top to bottom. Spectra were stacked vertically for
clarity.

Fig. 2 EXAFS oscillations, c(k), with no k weight for reference mate-

rials CoO, Co3O4 and all blue-and-white porcelain shards: CoO (A),
Co3O4 (B), Y10 (C), YL14 (D), XD3 (E), CH9 (F), WL6 (G) respectively
from top to bottom.

decorations in the visible region. As one of the transition metal

elements regularly used, cobalt in divalent ion form with four
oxygen atoms coordinated will give rise to blue color whereas six
oxygen atoms coordinated will obtain a mauve color. The
changes from mauve to blue are associated with the change of
cobalt coordination with the oxygen atoms from six-fold to four-
fold.36 For cobalt in trivalent ions form, it has found that the
trivalent cobalt optical absorption had no defined maxima in the
visible spectra. But its characteristic absorption increased
progressively in value toward shorter wavelengths to give
a yellow color. Among the above absorptions, the absorption of
Co2+ ions located in the tetrahedral site is apparently stronger
than the others.37
On the basis of XANES analysis, cobalt in blue decorations of
all blue-and-white porcelains was present as both divalent and
trivalent ion form and the ratios of Co2+/Co3+ were similar for all
Fig. 4 The best fitting results both in R- and k-space for blue and white
porcelains. Experimental and calculated values were illustrated by solid
line and open circles, respectively. Spectra were stacked vertically for
clarity. The capital letter stood for samples Y10 (A), YL14 (B), XD3 (C),
CH9 (D), WL6 (E), respectively from top to bottom.
samples. Such result excluded the possibility that the different
tones of the blue color in decorations of the samples analyzed
here came from the different oxidation of Co just as assumed by
Barlaro et al.38 who also performed XAFS analysis on blue
decorated Renaissance pottery fragments from Caltagirone
(Sicily, Italy).

This journal is ª The Royal Society of Chemistry 2011 J. Anal. At. Spectrom., 2011, 26, 1796–1801 | 1799

Table 4 Structural parameters calculated by the least-squares fit of the inverse Fourier transformed EXAFS oscillations with k3 weight. So2, R, CN, s2
referred to the scattering amplitude, inter-atomic distance, coordination number and Debye-Waller factor, respectively
Sample So2 
R (A)
Y10 0.71  0.18 1.98  0.02
YL14 0.62  0.05 1.96  0.01
XD3 0.71  0.06 1.96  0.01
CH9 0.71  0.12 1.98  0.01
WL6 0.67  0.07 1.97  0.01
EXAFS analysis indicated that cobalt atoms preferred to
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locate at tetrahedral sites, although that located at octahedral site
could not be excluded completely. Considering the empirical
absorption data of cobalt ions with different ligand field, it could
be assumed that divalent cobalt ions located at tetrahedral sites
made the main contribution to the color of blue decorations. As
for the color difference between different blue-and-white porce-
lains, it could be ascribed to the different proportion of cobalt
atoms situated in tetrahedral or octahedral sites. Besides, we plan
to investigate the other transition metals contained in blue
decorations, such as manganese and iron, later, which also had
influence on the coloring effect of blue decorations.
Generally, cobalt aluminate (CoAl2O4) and alpha-cobalt sili-
cate (a-Co2SiO4) with olivine structure are the phases relative to
blue pigment with cobalt as the main colorants. Theoretically,
the nearest Co–O distance of CoAl2O4 is 1.95 A  with the coor-
dination number of 4.39 In a-Co2SiO4, cobalt atoms are situated
in distorted octahedral sites and the nearest Co–O distance is
from 2.07 A  to 2.23 A.
 40 Based on the fitting result, the average
first Co–O distance for blue-and-white porcelains (1.97 A)  was

close to that of CoAl2O4 (1.95 A). Whether this result means that
cobalt was in the phase of cobalt aluminate as identified by Kock
and de Waal,16 we could not give the conclusive identification for
the lack of more convincing evidence. Besides, XANES spectra
gave the average information of cobalt element contained in blue
decorations which indicated the amorphous phase where cobalt
atoms are also situated.
Consequently, although the result present here was not
a perfect one, XAFS analysis provided a possible way to inves-
tigate the coloring mechanism of blue decorations of blue-and-
white porcelains. Further research using more reference mate-
rials, as well as iron and manganese elements which are also
contained in blue decorations, were planned during the next
experiment campaign.
Conclusions
Blue-and-white porcelains from Jingdezhen official kiln
produced in Yuan and Ming dynasties were investigated in this
study with the purpose of understanding the relationship
between the tones of blue decoration and the oxidation state and
chemical environment of cobalt. The oxidation state of cobalt in
blue decorations was demonstrated by XANES spectra as being
in both divalent and trivalent ion forms. The ratios of Co2+/Co3+
were similar in samples with different historical periods. Struc-
tural analysis of the EXAFS spectra revealed that cobalt atoms
preferred to situate in tetrahedral sites although there were a few
cobalt atoms still located at octahedral sites. In combination with
1800 | J. Anal. At. Spectrom., 2011, 26, 1796–1801
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CN  2)
s2 (A R-factor
2.8  1 0.005  0.003 0.002
2.5  1 0.002  0.001 0.005
2.8  1 0.004  0.001 0.001
2.9  1 0.005  0.002 0.001
2.7  1 0.004  0.001 0.009
the empirical optical absorption in the visible region, it could be
assumed that divalent cobalt ions located at tetrahedral sites
could be responsible for the color of blue decorations.
Acknowledgements
This work was supported by the project of National Nature
Science Foundation of China (Grant No.10979075). Authors
also thank Nan Qiu from the Institute of High Energy Physics of
the Chinese Academy of Sciences for the help of XAFS
measurements, and Shuo Zhang from Shanghai Institute of
Applied Physics of the Chinese Academy of Sciences is appre-
ciated for help with the EXAFS data analysis.
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