Elaboration and Structural Investigation of Iron (III) Phosphate Glasses
Elaboration and Structural Investigation of Iron (III) Phosphate Glasses
Elaboration and Structural Investigation of Iron (III) Phosphate Glasses
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Said Aqdim
Université Hassan II de Casablanca
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Received November 14, 2013; revised December 8, 2013; accepted December 21, 2013
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ABSTRACT
The regular melting-quenching method allowed isolating very large vitreous domains within the ternary system Li2O-
P2O5-Fe2O3 at 1100˚C. The vitrification and crystallization effects are discussed in terms of phosphorus pentaoxide
concentration (mol%). In the course of the present study, we analyzed chemical durability along the glass domain and
many sample glasses were isolated. We noticed that our compounds demonstrated very high chemical resistance to at-
tack, even with very highly concentrated mineral acid solutions. This behavior can be assigned to the presence of poorly
crystalline phases in these glasses, which tended to increase as the Fe2O3 content increased. This property is a prerequi-
site for many interesting industrial applications. XRD, IR spectroscopy and SEM micrographs allowed an efficient in-
vestigation of the structural changes versus composition within ternary diagrams. The results were found to be consis-
tent with the regular structural changes of phosphate glasses.
Keywords: Phosphate Glasses; Glass Formation; Chemical Resistance; IR Spectroscopy; XRD; SEM
(NH4)2HPO4, was initially tempered at various tempera- [13]. In the binary system Fe2O3-P2O5, the substitution of
tures between 100˚C - 600˚C to achieve a preparation P2O5with Fe2O3 led to black glasses that were not hygro-
before glass preparation. The melts were achieved in scopic for ironoxide contents between 0 and 30 mol%
alumina crucibles for about 15 min at 1080˚C ± 10˚C. (Figure 1). Ternary glasses rich in Fe2O3 content had a
The isolated glasses had regular shapes and an approxi- dark brown color which became more and more brown
mate size of 10 mm in diameter and 2 mm in thickness. clear as the lithium oxide content increased and the
The vitreous state was first evidenced from the shiny Fe2O3 content decreased. The demarcation of the glassy
aspect and then confirmed from XRD patterns. Anneal- zone within the ternary diagram Li2O-Fe2O3-P2O5 is
ing of these glasses was performed at increasing tem- given by the following limits: 0 ≤ x ≤ 62; 0 ≤ y ≤ 30; 36
peratures in intervals of 100˚C. The first structural ap- ≤ χ ≤ 1; (mol%) (Figure 1).
proach was made using X-ray diffraction which allowed
us to follow the crystallization of the vitreous domain of 3.1. Annealing Temperature
Li2O-Fe2O3-P2O5. The microstructure of sample glasses
was characterized by scanning electron microy (SEM), The annealing of the ternary glasses was performed by
equipped with a microanalyzer full system (EDX- increasing the temperature in intervals of 100˚C. An in-
EDAX). The chemical durability of the glasses with the crease in the lithium oxide modifier led to a slight in-
composition x Li2O-y Fe2O3-χP2O5; (χ- = (100 − (x + y)) crease in the crystallization temperature. For the glasses
were subjected to acid solutions using weak and strong with the composition xLi2O-5Fe2O3-χP2O5, the crystal-
concentrations of HCl and H2SO4 (0.1 N, 1 N and 10 N). lization temperature increased from 390˚C to 480˚C for x
The duration of attack for some glasses and solution = 30 to x = 50, respectively (Figure 2 [14]. On the other
concentration continued for up to 30 days. The infrared hand, Figure 3 shows that an increase in the Fe2O3 con-
(IR) spectra for each glass were measured between 400 tent in the glasses xLi2O-yFe2O3-χP2O5(with x/χ = 0.54)
and 1400 cm−1 using mX-1 and NIC-3600 FTIR spec- caused a quick increase in the value of the crystallization
trometers. Samples were prepared by pressing a mixture temperature from 120˚C for a binary glass Li2O-P2O5 (y
of about 2 mg of glass powder with 100 mg of anhydrous = 0) to 540˚C for y = 18 [6,15]. Figure 4 shows for the
KBr powder. binary glasses Fe2O3-P2O5 that the variation in the an-
nealing temperature (Tc) according to the Fe2O3 conten-
3. Results thad a maximum at 700˚C for the glass composition 16
Fe2O3-84P2O5 and was constant when the Fe2O3 content
In the system Li2O-P2O5, transparent glasses were pre- was more than y = 25 [16,17].
pared for 0 ≤ x ≤ 62 (Figure 1). These values are in
agreement with published results [9,10], but they are
3.2. X-Ray Diffraction
superior to those given by other authors [11,12]. This
was probably caused by the different experimental con- The X-ray diffraction spectra show that the crystallized
ditions (temperature of melting, speed of tempering, etc.) glasses seemed to be similar to the closest crystalline
Figure 1. Extended from the vitreous field within the ternary diagram of Li2O-P2O5-Fe2O3 to 1080˚C - 1100˚C.
xLi2O-yFe2O3-χP2O5
x/χ = 0.54 LiFeP2O7
y = 18 mol%
y = 15 mol%
Intensity (arbry)
y = 10 mol%
y = 5 mol%
y = 2.5 mol%
y = 0 mol%
(a)
10 20 30
xLi2O-5 Fe2O3-χP2O5 2 (Degree)
yFe2O3-(100-y) P2O5
y = 28 mol%
Χ = 40 mol%
Fe(PO3)3 y = 25 mol%
y = 20 mol%
10 20 30
Intensity (arbry)
2θ (Degree) y = 16 mol%
(b)
1225-1250
yFe2O3-(100-y)P2O5 1075-1100 460-540
940-905
1290
1085
940
480
735-758
Absorbance relative
5 mol%
y = 10 mol%
785
1080
1260
935
480
10 mol%
Absorbance relative
1065
785
1246
930
y = 16 mol%
495
1075
1200
925
Li4P2O7
780
490 y = 20 mol%
1070
925
18 mol%
760
y = 25 mol%
530
775
Wavenumber (cm−1)
xLi2O-5Fe2O3-χP2O5
y = 10 mol%
900
510
1120
1255
X = 40 mol%
Absorbance relative
y = 15 mol%
X = 45 mol%
y = 20 mol%
740
Absorbance relative
X = 50 mol%
y = 25 mol%
X = 55 mol%
y = 30 mol%
1100
1280
Wavenumber (cm−1)
475
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