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Journal of Alloys and Compounds 398 (2005) 249–255

New oxysulphide glasses in Sb2S3–MmOn and


Sb2S3–Sb2O3–MmOn systems
Rachid Makhloufi a , Ahmed Boutarfaia a,∗ , Marcel Poulain b
aLaboratoire de Chimie Appliquée, Université de Biskra, BP145, RP-Biskra, 07000 Algérie, France
b Laboratoire des Matériaux Photoniques, UMR6512, Université de Rennes I, F-35042 Rennes, France

Received 20 December 2004; received in revised form 11 February 2005; accepted 14 February 2005
Available online 23 March 2005

Abstract

New oxysulphide glasses involving antimony sulphide (Sb2 S3 ), antimony oxide (Sb2 O3 ) and Mm On (M = Cu+1 , Pb+2 , Sn+2 , Zn+2 , Ba+2 , In+3 ,
+3
Bi and V+5 ) have been investigated and characterized. They exhibit physical properties, different from those of classical oxide glasses and
chalcogenide glasses. Glass-forming regions have been found in the Sb2 S3 –Mm On binary systems based on antimony sulphide as the main
glass former and Sb2 S3 –Sb2 O3 –Mm On ternary systems derived from the Sb2 S3 –Sb2 O3 binary glass. Most glasses are easy to prepare and
quite stable in air. Depending on the composition and the nature of the M cation, glass transition temperature, Tg , is between 190 and 290 ◦ C,
crystallization temperature, Tc , is between 243 and 442 ◦ C and the stability factor Tc −Tg is between 23 and 170 ◦ C. Optical properties of these
glasses have been measured. They generally appear black with no transparency in the visible range. For some thin glass samples, the infrared
absorption edge extends up to about 12 ␮m.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Oxysulphide glasses; Binary glass; Ternary glass

1. Introduction ternary glasses could be obtained by adding a metal oxide as


a modifier to this Sb2 O3 –Sb2 S3 system.
There are several reports of oxysulphide glasses based on The purpose of the present study is to investigate new
antimony [1–3]. Their glass forming ability, chemical dura- oxysulphide glass compositions in Sb2 S3 –Mm On binary and
bility and some properties are often better than those of pure Sb2 S3 –Sb2 O3 –Mm On ternary systems. Their preparation,
oxide and chalcogenide glasses [2]. Sb2 S3 is considered as a glass forming ability and characterization are reported.
glass progenitor but a pure vitreous Sb2 S3 is very difficult to
prepare. This can be explained by the fact that the respective
values of glass transition temperature Tg and crystallization 2. Experimental
temperature Tc of the Sb2 S3 glass are extremely close, around
174 ◦ C [4]. Antimony oxide (Sb2 O3 ) is also considered as a 2.1. Glass preparation
glass progenitor, and requires fast quenching to be obtained in
the vitreous form [5–10], with Tg = 245 ◦ C and Tc = 296 ◦ C For glass preparation, starting materials are Sb2 O3 (Acros
[5]. Ling et al. have investigated (100 − x)Sb2 O3 − xSb2 S3 +99%), Sb2 S3 (Aldrich +99%), ZnCO3 and BaCO3 (Pro-
oxysulphide glasses that may be formed in a large composi- labo pur), Cu2 O (Avocado 98%), In2 O3 (Metaleurop ppm
tion range (20 < x < 80) [3]. According to the usual behavior pure metals), V2 O5 (Aldrich +98%), Bi2 O3 (Aldrich 99.9%),
of the glass forming melts, it was expected that more stable PbCO3 (Merck +99%) and SnO (Alfa 99%).
After careful weighing and mixing, the appropriate raw
∗ Corresponding author. materials were rapidly flame heated in a silica glass crucible
E-mail address: aboutarfaia@yahoo.fr (A. Boutarfaia). at 900–1100 ◦ C at room atmosphere. The batch is completely

0925-8388/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2005.02.013
250 R. Makhloufi et al. / Journal of Alloys and Compounds 398 (2005) 249–255

melted after 3 min. Then, the melt is homogenized for 2 min. phases, a diffuse pattern is observed with a halo centered
This time has to be short because of the tendency of Sb2 S3 at 2θ = 30◦ as shown in Fig. 1.
and Sb2 O3 to volatilization, as their melting temperatures are The density of the samples was determined using a helium
550 and 656 ◦ C, respectively. Two quenching processes have picnometer (Micromeritics, AccuPyc 1330). The chemical
been used, corresponding to decreasing quenching rates: composition of glasses has been checked by element analy-
sis using energy dispersion spectrometry (Oxford Link ISIS)
- For investigating glass forming range, the melt is poured set-up incorporated into a JSM 6400 Jeol scanning electron
onto a brass plate at 25 ◦ C, and immediately flattened with microscope.
a brass hammer (“quenched glasses”).
- For compositions less prone to devitrification, the melt is
poured into a brass mould, preheated around (Tg − 10)◦ C, 3. Results
Tg being the glass transition temperature, which allows
samples of a few millimeters in thickness to be obtained. 3.1. Glass formation
An annealing cycle is then carried out to reduce thermal
stresses: the glass piece is heated at a temperature around 3.1.1. Binary glasses
(Tg − 10)◦ C for 12 h and then slowly cooled down to 25 ◦ C. Systematic experiments were carried out in the
Sb2 S3 –Mm On (M = Cu+1 , Pb+2 , Sn+2 , Zn+2 , Ba+2 , In+3 , Bi+3
2.2. Physical measurements and V+5 ) binary systems in order to assess stabilizing ef-
fect of metal oxide. The glass-forming ranges in the differ-
Thermal characteristics include temperatures for glass ent binary systems are displayed in Fig. 2. Quenching is re-
transition, Tg , onset of crystallization, Tc , maximum of
exothermic crystallization peak, Tp , and melting, Tm . They
are determined by differential scanning calorimeter (DSC)
using a SEIKO S 220 Instruments. Samples were set in alu-
minum pans under Ar atmosphere and heated at 10 K min−1 .
The estimated error on the temperature is ∼2 ◦ C. Assessment
of glass stability is made from semi-empirical parameters: the
value of the stability range T = Tc − Tg [11] and the S factor
[12] defined as S = (Tc − Tg )(Tp − Tc )/Tg with temperatures
expressed in Kelvin.
Infrared transmission spectra were recorded with a
spectrophotometer (BOMEM Michelson 100) in the
400–4000 cm−1 range. UV–vis transmission spectra between
800 and 200 nm were obtained using a double beam spec-
trophotometer (Varian, Cary 5).
The amorphous character of the samples is checked
by powder X-ray diffraction (XRD) using a diffractometer
(Philips PW3020) with Cu K␣ radiation. For amorphous Fig. 2. Glass-forming ranges in the binary systems Sb2 S3 –Mm On .

Fig. 1. Cu K␣ X-ray diffraction pattern for: (a) 80Sb2 S3 –10Sb2 O3 –0.5ZnO–0.5BaO and (b) 20Sb2 S3 –70Sb2 O3 –0.5ZnO–0.5BaO glasses.
R. Makhloufi et al. / Journal of Alloys and Compounds 398 (2005) 249–255 251

Table 1
Basic composition, characteristic temperatures and density of Sb2 S3 –Mm On binary glasses
Binary system Composition (mol%) Tg (◦ C) Tc (◦ C) Tp (◦ C) Tm (◦ C) Tc −Tg (◦ C) S (K) Density (g/cm3 )
Sb2 S3 –Cu2 O 90:10 212 286 303 460 74 2.52
85:15 210 295.5 314 460 85.5 3.31 4.446
80:20 208 297 321 457.5 89 4.48 4.510
75:25 206 294 317.5 456 88 4.32 4.629
70:30 203 268 277.5 451 64.5 1.28
Sb2 S3 –PbO 90:10 230 285 299.5 472 55 1.56 4.511
85:15 229.5 265.5 282.5 461 36 1.21 4.549
Sb2 S3 –SnO 90:10 223 295.5 308 483 72.5 1.79
80:20 222 280 291 471 58 1.26
70:30 223 258 262 454 35 0.28
60:40 220 243.5 250 455 23.5 0.31
Sb2 S3 –ZnO 80:20 221.5 289 303 466 67.5 1.87
Sb2 S3 –(0.5ZnO–0.5BaO) 90:05:05 236 306.5 322 455 70.5 2.16
80:10:10 248 343 363 458 95 3.65
Sb2 S3 –In2 O3 95:05 236.5 303 318.2 475 66.5 1.98 4.281
90:10 244 291 312 485 47 1.81 4.328
Sb2 S3 –Bi2 O3 90:10 244 271 282 492 47 1.05
80:20 190 259 264.5 500 69 0.80
Sb2 S3 –V2 O5 95:05 227 285 297 490 58 1.36
90:10 222.5 281.5 293.5 488 59 1.42
Sb2 S3 [4] 100 174 174 – – 0 0

quired to prepare: Sb2 S3 –ZnO, Sb2 S3 –SnO, Sb2 S3 –Bi2 O3 glass samples are given in Table 1. Under the above con-
and Sb2 S3 –V2 O5 glasses while a slower cooling rate may be ditions, Sb2 S3 alone cannot be vitrified. Nevertheless, such
used for the other binary glasses: Sb2 S3 –Cu2 O, Sb2 S3 –PbO, glasses may be considered as stabilized vitreous Sb2 S3
Sb2 S3 –(0.5ZnO–0.5BaO) and Sb2 S3 –In2 O3 . Compositions, because in all cases antimony sulphide content is very
characteristic temperatures, stability factors and density for large.

Fig. 3. Glass forming areas in the ternary systems: (a) Sb2 S3 –Sb2 O3 –ZnO; (b) Sb2 S3 –Sb2 O3 –(0.5ZnO–0.5BaO) and (c) Sb2 S3 –Sb2 O3 –V2 O5 .
252 R. Makhloufi et al. / Journal of Alloys and Compounds 398 (2005) 249–255

Table 2
Basic compositions, characteristic temperatures and density of Sb2 S3 –Sb2 O3 –Mm On ternary glasses
Ternary system Composition (mol%) Tg (◦ C) Tc (◦ C) Tp (◦ C) Tm (◦ C) Tc −Tg (◦ C) S (K) Density
(g/cm3 )
Sb2 S3 –Sb2 O3 –ZnO 10:80:10 258.5 394.5 436 – 136 10.71
30:60:10 250.5 366 390 473.5 116 5.35 5.237
40:50:10 240.5 336 353 488 95.5 3.16 5.073
70:20:10 229 306.5 314 491 77.5 1.13 4.173
10:70:20 250 333 368.5 – 83 5.62
20:60:20 246 368 402 466.5 122 8
50:30:20 235 319.5 332 497 84.5 2.04
70:10:20 223 305 316 492 82 1.72
Sb2 S3 –Sb2 O3 –(0.5ZnO–0.5BaO) 70:25:2.5:2.5 244 350 368 470 106 3.64 4.484
85:10:2.5:2.5 233 330 354 483 97 4.62 4.332
10:80:05:05 277 436 471.5 >550 159 10.26 5.030
20:70:05:05 275 443 474 550 168 9.52 4.895
40:50:05:05 266 420 471 502 154 14.63 4.704
60:30:05:05 255 374.5 389 431 119.5 3.35 4.518
80:10:05:05 238 319 330.5 472.5 81 1.84 4.365
70:10:10:10 249 347 368 465 98 3.92
Sb2 S3 –Sb2 O3 –V2 O5 10:80:10 268.5 363 381 481 94.5 3.19
20:70:10 264 350 374.5 485 86 3.92
40:50:10 255 332 360 473 767 4.07
50:40:10 250 316 352 487 66 4.51
60:30:10 238 310 330 496 72 2.85
70:20:10 231 321 329 491 90 1.43
80:10:10 232 293 313 484 61 2.43
Tg corresponds to glass transition, Tc to onset of crystallization, Tp to the top of the crystallization peak and Tm to melting.

3.1.2. Ternary glasses does not exceed 2 mol% with the exception of sulphur (S)
Glass formation was investigated in three ternary sys- whose loss reaches 4 mol%.
tems derived from the Sb2 S3 –Sb2 O3 binary association: Optical properties of the glasses have been measured. In
Sb2 S3 –Sb2 O3 –ZnO, Sb2 S3 –Sb2 O3 –(0.5ZnO, 0.5BaO) and the Sb2 S3 –Sb2 O3 –ZnO ternary system, the UV–vis cut-off is
Sb2 S3 –Sb2 O3 –V2 O5 . The limits of the vitreous areas are dis- shifted toward 0.8 ␮m. The infrared transmission, as shown
played in Fig. 3. Table 2 reports the chemical compositions, in Figs. 5 and 6 for samples of 3–5 mm in thickness, is lim-
the characteristic temperatures, the stability criteria and the ited by a strong absorption band at 1800 cm−1 occurring be-
density for some glass samples synthesized in these ternary fore the multiphonon absorption edge and the characteristic
systems. OH absorption band around 3300 cm−1 . For some thin glass
samples, e.g. in binary systems, the infrared absorption edge
extends up to about 12 ␮m. In all cases, density is larger than
3.2. Characterization
4.25 g cm−1 and it can reach 5.23 g cm−1 in ternary systems.
Thermal properties of all sample glasses are measured by
differential scanning calorimetry and a typical DSC scan is
shown in Fig. 4. These glasses are not transparent in the visi-
ble range and consequently are black in color, with the excep-
tion of the samples containing more than 70 mol% Sb2 O3 ,
which are red. The synthesis of these glasses by melting and
cooling appears easy and rapid, and the resulting samples are
generally stable at room atmosphere. Depending on the com-
position and the nature of M cation, the glass transition tem-
perature, Tg , is between 190 and 290 ◦ C, the crystallization
temperature, Tc , is between 243 and 442 ◦ C and the stability
factor Tc − Tg is between 23 and 170 ◦ C.
To compare the compositions of the batch and those of
the glass sample, some glasses were analysed by energy dis-
persion spectroscopy in a scanning electron microscope. The
atomic compositions of some of the glasses analysed are pre-
sented in Table 3. The deviation from nominal composition Fig. 4. Typical DSC curve.
R. Makhloufi et al. / Journal of Alloys and Compounds 398 (2005) 249–255 253

Table 3
Chemical analysis of some glasses by energy dispersion spectrometry
Glass compositions (mol%) Atom (%) O S Sb Cu Zn Ba
Sb2 S3 –Cu2 O, 80:20 Nominal 4.35 52.17 34.78 8.69 – –
Analysed 4.97 49.3 36.9 8.89 – –
Sb2 S3 –Sb2 O3 –ZnO–BaO, 75:20:2.5:2.5 Nominal 13.4 46.39 39.17 – 0.52 0.52
Analysed 13.0 43.9 41.9 – 0.56 0.67

volatilization during melting and fining have a limited influ-


ence on the final composition.
From Table 1, we can see that binary oxysulphide glasses
may be formed in combining Sb2 S3 and Mm On metal ox-
ide (M = Cu+1 , Pb+2 , Sn+2 , Zn+2 , Ba+2 , In+3 , Bi+3 and V+5 ).
Table 1 shows that the Tg values of the new oxysulphide are
higher than those of single component Sb2 S3 glass; for PbO or
SnO addition the value of Tg is not very sensitive to the metal
oxide content. It is equal to 230 and ∼222 ◦ C, respectively,
for (0.5ZnO–0.5BaO) or In2 O3 addition. For Cu2 O, Bi2 O3
or V2 O5 , in addition, the value of Tg is decreased when the
metal oxide content increases. The stability range Tc − Tg is
influenced by both metal oxide composition and content. It
Fig. 5. IR transmission spectrum for the (75Sb2 S3 –25Cu2 O) glass. Sample is maximum in the case of Cu2 O addition for which Tc − Tg
thickness is 3 mm. value can reach 89 ◦ C.
From Table 2, we can also see that ternary oxysulphide
4. Discussion glasses may be formed by incorporation of a third metal
oxide in the Sb2 S3 –Sb2 O3 binary system. Because the
As it might be expected, these results demonstrate that concentration of the third component is limited (<20 mol%),
oxide additives may stabilize antimony sulphide glass under and in order to locate the more stable compositions in
the condition that the nature and the content of metal oxide ternary systems, we have plotted in Fig. 7 the evolu-
are correct. The chemical analysis of the glass samples is in tion of Tg and Tc − Tg versus the Sb2 O3 content (x) in
good agreement with the nominal composition as determined glasses defined by the three following composition rules:
from weighed starting materials; losses that could arise from (90 − x)Sb2 S3 –xSb2 O3 –10ZnO, (90 − x)Sb2 S3 –xSb2 O3 –

Fig. 6. IR transmission spectra of some (90 − x)Sb2 S3 –xSb2 O3 –0.5ZnO–0.5BaO glasses: (a) 20Sb2 S3 –70Sb2 O3 –0.5ZnO–0.5BaO, (b) 30Sb2 S3 –
60Sb2 O3 –0.5ZnO–0.5BaO, (c) 40Sb2 S3 –50Sb2 O3 –0.5ZnO–0.5BaO and (d) 60Sb2 S3 –30Sb2 O3 –0.5ZnO–0.5BaO.
254 R. Makhloufi et al. / Journal of Alloys and Compounds 398 (2005) 249–255

Fig. 8. Evolution of density vs. Sb2 O3 concentration for glasses defined by


the following composition rule: (a) (90 − x)Sb2 S3 –xSb2 O3 –10ZnO and (b)
(90 − x)Sb2 S3 –xSb2 O3 –(0.5ZnO, 0.5BaO).

ular volume increases. In practical substitutions, both factors


act in opposite ways.
The absorption band at 3300 cm−1 results from the hy-
droxyl groups (OH) that originate from water contamination.
They can be eliminated if starting materials and processing
are strictly controlled. The other extrinsic absorption band
corresponds to the first overtone of the Si–O vibration aris-
ing from the contamination of the melt by the silica work-
Fig. 7. Evolution of glass transition temperature and stability range vs. ing tubes. The optical transmission of our prepared glasses
Sb2 O3 concentration for glasses defined by the following composition rule: is close to 50%, which is much lower than expected from
(a) (90 − x)Sb2 S3 –xSb2 O3 –10ZnO, (b) (90 − x)Sb2 S3 –xSb2 O3 –(0.5ZnO, the value of the Fresnel losses (<20%). These large opti-
0.5BaO) and (c) (90 − x)Sb2 S3 –xSb2 O3 –10V2 O5 .
cal losses are consistent with the observation of the vitre-
ous samples under optical microscope, showing numerous
(0.5ZnO, 0.5BaO) and (90 − x)Sb2 S3 –xSb2 O3 –10V2 O5 . defects: bubbles, inhomogeneities and inclusions. These de-
In a general way, the Tg values increase when Sb2 O3 fects should be drastically reduced for potential applications
content increases and they are influenced by the nature of by the selection of high purity starting materials and by pro-
the third component; Tg values increase according to the cessing optimisation. In oxide glasses, there is a strong corre-
sequence ZnO, V2 O5 and (0.5ZnO, 0.5BaO). The stability lation between the infrared absorption edge and the network-
range Tc − Tg is smaller with V2 O5 , larger for ZnO and forming cations. This correlation may be scaled using the
maximum for (0.5ZnO, 0.5BaO), which is consistent with field strength, Z/r2 , where Z is ionic charge and r is crystal
the confusion principle that expresses that glass stability ionic radius [13]. The field strengths of cations that can par-
increases as the number of glass components increases. ticipate in a glassy network are given in Table 4 and these val-
The stability range Tc − Tg is 135 ◦ C for the composition ues indicate that the absorption arises mainly from antimony,
10Sb2 S3 –80Sb2 O3 –10ZnO while it can reach 170 ◦ C for the vanadium and zinc, and the cut-off wavelength depends on
20Sb2 S3 –70Sb2 O3 –(0.5ZnO, 0.5BaO) composition. the concentration of the most absorbing specie, usually the
The evolution of density versus the Sb2 O3 content (x)
is shown in Fig. 8 for glasses defined by the follow- Table 4
ing composition rule: (90 − x)Sb2 S3 –xSb2 O3 –10ZnO and Mass and field strength of glass-forming cations
(90 − x)Sb2 S3 –xSb2 O3 –(0.5ZnO, 0.5BaO). In a general way, Cation Charge (Z) Mass Radius Field strength
the density increases when the content of Sb2 O3 increases at (g mol−1 ) (r, Å) (Z/r2 )
the expense of Sb2 S3 , which is in agreement with the great Cu +1 63.54 0.96 1.085
difference of ionic radii of O2− (1.32 Å) and S2− (1.84 Å). Zn +2 65.39 0.74 3.65
The partial substitution of Zn2+ (0.74 Å, 65.4 g mol−1 ) by
Ba +2 137.33 1.34 1.114
Sn +2 119.71 0.93 2.312
Ba2+ (1.34 Å, 137.33 g mol−1 ) provokes a decrease of den- Pb +2 207.2 1.20 1.3
sity values in the range 30 < x (mol%) < 70 of Sb2 O3 con- In +3 114.92 0.81 4.572
centration. Otherwise, it leads to larger density values. All Bi +3 209.9 0.96 3.3
these observations can be explained by the fact that density Sb +3 122 0.76 5.2
V +5 50.94 0.59 14.36
increases if molecular weight is larger and decreases if molec-
R. Makhloufi et al. / Journal of Alloys and Compounds 398 (2005) 249–255 255

Sb O bond. This is consistent with Fig. 6 that shows the composition. Changes of specific temperatures, density and
evolution of the IR absorption edge with Sb2 S3 content: in- infrared absorption edge versus composition have been stud-
frared absorption decreases as the number of Sb O bonds ied in some oxysulphide glasses. These glasses are potential
decreases. candidates for photonic applications.
Chemical analysis of glass samples is in good agreement
with the composition that may be determined from weighed
batch starting materials: volatilization during melting and fin- References
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