Journal of Alloys and Compounds 479 (2009) 579–582

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jallcom

XRD and FTIR structural investigations of erbium-doped bismuth–lead–silver

glasses and glass ceramics
Maria Bosca a , Lidia Pop a,∗ , Gheorghe Borodi b , Petru Pascuta a , Eugen Culea a
a
Department of Physics, Technical University of Cluj-Napoca, Romania
b
National Institute for Research and Development of Isotopic and Molecular Technology, Cluj-Napoca, Romania

a r t i c l e i n f o a b s t r a c t

Article history: Glasses with the xEr2 O3 (100 − x)[72Bi2 O3 ·25PbO·3Ag2 O] composition where x = 0–20 mol% were pre-
Received 29 June 2008 pared and later thermally treated. The local environments characteristic of this system were investigated
Received in revised form 24 December 2008 using X-ray diffraction and FTIR spectroscopy. The results show that the glass or glass ceramic network
Accepted 6 January 2009
structure resembles to that of the host matrix, being composed of [BiO3 ], [BiO6 ], [PbO3 ] and [PbO4 ] struc-
Available online 20 January 2009
tural units. The addition of Er2 O3 stabilizes the host glass or glass ceramic structure. The erbium ions play
the role of a network modifier in the studied glasses. It was shown that the heat treatment at 650 ◦ C leads
Keywords:
to the crystallization of the Bi2 O3 and PbO1.44 phases.
Bismuth–lead–silver glasses and glass
ceramics © 2009 Elsevier B.V. All rights reserved.
Er2 O3
X-ray diffraction
FTIR spectroscopy

1. Introduction
The local environment of the rare earth ions obviously plays an
important role in determining the chemical and physical proper-
ties of the host glass systems [1]. It has been commonly accepted
that rare earth ions from glasses tend to cluster together at higher
concentrations. Since these processes modify the local environment
and the properties of the host glass, the study of the clustering of the
rare earth ions from glass matrices is also of great importance [2].
The erbium containing glasses have attracted a great interest
due to the intense use of such materials in the field of optical com-
munications and laser technology [3,4].
On the other hand, the heavy metal oxide glasses, such as the
bismuthate glasses, have attracted an important interest for opto-
electronic and photonic applications because of their important
properties such as the high refractive indices (>2.0), the optical non-
linearities and transmission at longer wavelengths in the infrared
region. Due to these properties, the use of the mentioned glasses
provides the possibility of developing more efficient lasers and fiber
optic amplifiers [3–6]. Despite the fact that Bi2 O3 is not a classical
glass former, due to the high polarizability of the Bi3+ ions, in the
presence of other glass formers such as B2 O3 [7], PbO [8–10], V2 O5
[11] or of some alkali oxides (i.e., lithium oxide) [12], it may build
up a glass network.
∗ Corresponding author. Tel.: +40 264 401 262; fax: +40 264 595 355.
E-mail address: Lidia.Pop@phys.utcluj.ro (L. Pop).
Finally, glasses with silver ions are at the focus of current inter-
est because of their high stability against humidity and their high
electrical conductivity in the range of 100 to 10−2 S m−1 at room
temperature [10,13]. It is known that the solubility of Ag2 O in glass
melts is limited by thermodynamic factors, the partial pressure
of oxygen, the temperature and the glass composition. However,
glasses of the Bi2 O3 –PbO–Ag2 O system based on two heavy metal
glass formers (Bi2 O3 and PbO) and containing a high amount of
Ag2 O (up to 30 mol%) were reported to be obtained by using the
quenching of the melts in a twin-roller. These glasses show a
fast ion conduction being important for applications as solid state
electrochemical devices [10]. The glasses containing silver have
attracted attention due to their antibacterial activity. Thus, it is
known that the Ag ion prevents the increase of bacterial population
[14,15].
In the present work, a new glass system with the
Er2 O3 –Bi2 O3 –PbO–Ag2 O composition was investigated by XRD
and FTIR spectroscopy. To our knowledge, no similar work has been
published concerning this newly developed vitreous system so far.
2. Experimental
Glasses of the nominal composition described by the general formula
xEr2 O3 (100 − x)[72Bi2 O3 ·25PbO·3Ag2 O] with x = 0, 1, 3, 5, 7, 10, 12, 15 and 20 mol%
were prepared by the melt quenching technique from reagent grade Bi2 O3 , PbO, Ag2 O
and Er2 O3 . First, the base 72Bi2 O3 ·25PbO·3Ag2 O glass was prepared by mixing suit-
able amounts of Bi2 O3 , PbO and Ag2 O and melting the mixture at 1100 ◦ C for 30 min.
The melt was quenched on a refractory steel block. The obtained base glass was
crushed and powdered. Appropriate amounts of Er2 O3 and 72Bi2 O3 ·25PbO·3Ag2 O
glass powder were mixed and milled in an agate ball mill. Then, the mixtures were

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doi:10.1016/j.jallcom.2009.01.001
580 M. Bosca et al. / Journal of Alloys and Compounds 479 (2009) 579–582

Fig. 1. X-ray diffraction patterns for the xEr2 O3 (100 − x)[72Bi2 O3 ·25PbO·3Ag2 O] sys- Fig. 2. X-ray diffraction patterns for the xEr2 O3 (100 − x)[72Bi2 O3 ·25PbO·3Ag2 O]
tem before heat treatment. system after heat treatment.

remelted at 1100 ◦ C for 15 min. The glass samples were obtained by pouring the
melts on stainless steel. Some of the glass samples were heat treated at 650 ◦ C for
20 h.
The X ray diffraction analysis was performed by a XRD-6000 SHIMADZU difrac-
tometer using the Cu K␣ radiation ( = 1.54056 Å), at 45 kV and 35 mA. The 2 scan
range was 10–80◦ , with a step size of 2◦ /min. To identify the crystalline phases in
the analysed samples the powder diffraction file (PDF) was used.
FTIR measurements were performed with a JASCO FTIR 6200 spectrometer on
the 400–1170 cm−1 range using the KBr pellet technique. The samples were crushed
in an agate mortar in order to obtain a fine powder. This procedure permitted to
obtain good quality FTIR spectra.
All measurements were carried out at room temperature.
FC cubic phase type with lattice parameters very close each to the
other. Thus, the Bi2 O3 phase has the a = 5.45 Å lattice parameter [17],
while the PbO1.44 phase has the a = 5.469 Å lattice [18].
Fig. 4 shows the simulated diffraction patterns for the Bi2 O3 or
PbO1.44 crystalline phases, as well as the experimental diffraction
pattern for the sample with x = 0. A simple comparison of these
spectra, namely the coincidence of their peak positions and inten-
sities, suggests that the examined x = 0 sample contains both the
Bi2 O3 or PbO1.44 crystalline phases.

3.2. FTIR data

3. Results and discussion
FTIR spectroscopy was used to obtain essential information con-
3.1. XRD data cerning the arrangement of the structural units from the studied
glasses and glass ceramics. The experimental FTIR spectra of the
The X-ray diffraction patterns for the samples with Er2 O3 con- xEr2 O3 (100 − x)[72Bi2 O3 ·25PbO·3Ag2 O] glass system with various
centrations from 1 to 20 mol% are shown in Fig. 1. One can see that contents of erbium oxide are presented in Fig. 5. The bands observed
for Er2 O3 concentrations up to x = 10 mol%, the X-ray diffraction pat- in these FTIR spectra and their assignments are summarized in
tern shows a broad halo characteristic of amorphous samples. For Table 1. The assignments were made comparing the experimen-
the samples with x ≥ 12 mol%, beside the amorphous halo, diffrac-
tion peaks corresponding to some crystalline phases occur. These
peaks increase in intensity with increasing the Er2 O3 content of the
samples. The position and intensity of the diffraction peaks were
analysed using the powder diffraction file (PDF) and were found to
be characteristic of the ␦Bi2 O3 crystalline phases.
The heat treatment performed at 650 ◦ C for 20 h exerted an
important effect on the studied samples. After the heat treatment all
the samples were found to contain the important Bi2 O3 or PbO1.44
crystalline phases, the amorphous phase becoming minor, as one
can see on Fig. 2.
Thus, for the samples with x ≤ 3 mol% the diffraction patterns
shows the presence of a single FC cubic phase with the lattice
constant a = 5.5 Å. With increasing the Er2 O3 concentration of the
samples, the peaks corresponding to this phase gradually disap-
pears and a large number of other reflections appear. Most of these
new reflections can be assigned to the ␦Bi2 O3 body centered cubic
phase with the a = 10.25 Å lattice constant [16].
Fig. 3 presents the X-ray diffraction patterns for the two sam-
ples without Er2 O3 , namely those with the 72Bi2 O3 ·25PbO·3Ag2 O
and 75Bi2 O3 ·25PbO compositions. As can be seen from this figure,
their X-ray diffraction patterns are almost identical. The crystalline
phase observed for the 72Bi2 O3 ·25PbO·3Ag2 O and 75Bi2 O3 ·25PbO Fig. 3. X-ray diffraction patterns for the 72Bi2 O3 ·25PbO·3Ag2 O and 75Bi2 O3 ·25PbO
samples may be the Bi2 O3 or PbO1.44 because both phases are of samples after heat treatment.
 M. Bosca et al. / Journal of Alloys and Compounds 479 (2009) 579–582 581

Fig. 4. Simulated X-ray diffraction patterns for the PbO1.44 and Bi2 O3 crystalline
phases and experimental diffraction pattern for the 72Bi2 O3 ·25PbO·3Ag2 O sample
after heat treatment.

tal data obtained in the present study with those of some related
crystalline and vitreous compounds [19–28].
The FTIR spectrum of the glass matrix, 72Bi2 O3 ·25PbO·3Ag2 O,
consists of three wide and intense absorption bands positioned
at 480 cm−1 , 722 cm−1 and 890 cm−1 . Furthermore, some shoul-
ders located at 510 cm−1 , 560 cm−1 , 669 cm−1 , 850 cm−1 , 960 cm−1
and 1090 cm−1 were detected in the glass matrix spectrum. The
band at 480 cm−1 is characteristic both of the Bi–O bending vibra-
tion from BiO6 and/or BiO3 structural units [19] and of the Pb–O
stretching vibration in PbO4 structural units [20,21]. The absorption
band from 510 cm−1 is assigned both to the Bi–O stretching vibra-
tion from BiO6 units [22] and to the Pb–O symmetrical bending
vibration [23].
The absorption band from 560 cm−1 corresponds to the Ag–O
and Bi–O bonds (from the BiO6 units) vibrations [26,27].
The absorption bands located at 669 cm−1 and 722 cm−1 are
due to the Pb–O bonds vibrations of PbOn units with n = 3 and/or 4
[24,27].
The bands situated at 850 cm−1 and 890 cm−1 corresponds to the
Bi–O symmetrical stretching vibration from BiO3 and BiO6 struc- Fig. 5. FTIR spectra of xEr2 O3 (100 − x)[72Bi2 O3 ·25PbO·3Ag2 O] glasses with
0 ≤ x ≤ 10 mol% (a) and 12 ≤ x ≤ 20 mol% (b).
tural units [28]. The absorption band from 960 cm−1 is assigned
to the Pb–O symmetrical stretching vibrations from different
structural units. The Pb–O asymmetrical bending vibration was
Table 1 identified at 1090 cm−1 [23].
FTIR absorption features and their assignments for the xEr2 O3 (100 − x)[72Bi2 O3 ·25 The addition of the erbium oxide in the host glass matrix and
PbO·3Ag2 O] system. then the increasing of its content involves an increase in the inten-
Wavenumber [cm−1 ] Assignment sity for the IR features from 510 cm−1 , 560 cm−1 and 960 cm−1 .
Moreover, for higher contents of erbium ions (x ≥ 7 mol%), a new
480 Bi–O bending vibrations in BiO6 and/or BiO3 units
Pb–O bonds vibrations in PbO4 units
band appears at 922 cm−1 attributed to the Pb–O–Bi, Pb–O–Ag,
Er–O bonds vibrations Bi–O–Ag, Pb–O–Er, Bi–O–Er or Bi(3)–O–Bi(6) bonds specific vibra-
510 Bi–O stretching vibrations in BiO6 units tions [25].
Pb–O symmetrical bending vibration The shoulder from about 850 cm−1 increases for higher erbium
560 Bi–O bonds vibrations in BiO6 units
oxide content (x = 20 mol%). Simultaneously, the shoulder from
Ag–O bonds vibrations
Er–O bonds vibrations ∼890 cm−1 becomes less intense with the increase of the erbium
669, 722 Pb–O vibrations from PbOn pyramidal units (n = 3 oxide content.
and/or 4) The compositional evolution of the FTIR features for the
850 Bi–O stretching vibrations in BiO3 units xEr2 O3 (100 − x)[72Bi2 O3 ·25PbO·3Ag2 O] system suggests that the
890 Bi–O stretching vibrations in BiO6 units
922 Pb–O–Bi, Pb–O–Ag, Bi–O–Ag, Pb–O–Er, Bi–O–Er or
presence of erbium ions influences the surrounding of the Bi3+ ions,
Bi(3)–O–Bi(6) specific vibrations favouring the formation of BiO3 units.
960 Pb–O symmetrical stretching vibration from The FTIR spectrum of the crystalline (cubic) Er2 O3 shows char-
different structural units acteristic absorption bands located at 563 cm−1 (s) and 465 cm−1
1090 Pb–O asymmetrical bending vibration
(b, sh) assigned to the Er–O bonds vibrations [26]. Therefore, the
582 M. Bosca et al. / Journal of Alloys and Compounds 479 (2009) 579–582

The structural changes observed by varying the Er2 O3 con-

centration of xEr2 O3 (100 − x)[72Bi2 O3 ·25PbO·3Ag2 O] systems, as
suggested by the FTIR investigation, shows that the erbium ions play
a network modifier role in these glass and glass ceramic systems.

4. Conclusion

The structural changes induced by heat treatment in the

bismuth–lead–silver glasses doped with erbium ions are well
reflected in their X-ray diffraction patterns and FTIR spectra. The
heat treatment of the samples produces their crystallization, the
presence of the Bi2 O3 and PbO1.44 crystalline phases being evi-
denced by X-ray diffraction analysis.
The FTIR data suggest the presence of both the BiO6 and BiO3
structural units, as well as of the PbO4 and PbO3 structural units
in the studied bismuth–lead–silver glasses. The amount of the
BiO3 and PbO4 structural units is higher in the heat treated sam-
ples. In both the as cast and heat treated glasses, the number
of BiO6 and PbO3 structural units decreases in the favour of the
BiO3 and PbO4 units with increasing the erbium ion content of the
samples.
Fig. 6. FTIR spectra of the xEr2 O3 (100 − x)[72Bi2 O3 ·25PbO·3Ag2 O] system after heat
treatment.
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