January 2014 Highly Transparent Tellurite Glasses and Glass-Ceramics Prepared by Spark Plasma Sintering 165

geometry. The intensity of the SHG signal collected in trans-
mission geometry is indeed strictly equal to zero due to either
some signal already weak in reflection geometry or to the
opacity of the sample resulting from its partial/total devitrifi-
cation. In our SHG measurements, we estimate the error
bars to be around 10%.
III. Results and Discussion
(1) 85TeO2–15WO3 Amorphous Powder
Figure 2(a) shows the particle size distribution of both fine
and coarse 85TeO2–15WO3 amorphous particles. The mean
particle diameter (D50) is, respectively, 6 and 167 lm for the
fine and coarse particles. A broadening of the size distribu-
tion is observed in the case of fine particles indicating the
presence of different modes. At the opposite, the size distri-
bution of coarse particles is almost single mode.
The sintering of glassy particles is generally assumed to
occur through a viscous flow mechanism just above the glass
transition temperature, Tg.21 Therefore, it is believed that the
initial size of the amorphous powder does not influence the
final properties of the samples. In contrary, the initial grain
size of crystallized particles is of great importance for the
targeted applications in the process of ceramics sintering
(alumina, spinel, etc.) where the sintering mechanisms (solid–
solid, solid–liquid, etc.) are different from the ones using
amorphous powders.
For the synthesis of glass-ceramics, two mechanisms have
been assumed depending on the glass composition. The first
one associates the densification of the glassy powder through
viscous sintering to a subsequent devitrification of the
matrix.21 The second possible mechanism implies the densifi-
cation of the matrix through the growth of neck between
glassy particles and concomitantly a gradual crystallization
of the latter. For one given glass composition, the amor-
phous phase has a considerably lower viscosity than the cor-
responding crystalline phase, so that the sintering of
polycrystalline material is inevitably more difficult than its
amorphous counterpart. This suggests that the first mecha-
nism described above, that is, achieving full density prior to
any significant crystallization, is likely at play. However, the
glass-ceramics obtained in the TeO2–WO3 system from the
conventional MQ technique and subsequent heat treatment
between Tg and Tc (crystallization temperature) of the amor-
phous bulks leads to surface instead of bulk crystallization.20
Therefore, the resulting sintering mechanisms might be more
complex.
The morphology of both fine and coarse particles is repre-
sented in Figs. 2(b) and (c). In the latter case, the particles
display sharp angular edges as shown by the SEM photo-
graphs.
Figure 3 shows the DSC thermograms recorded for the
85TeO2–15WO3 fine and coarse particles, as well as that cor-
responding to the glass bulk of the same composition. The

(a) 9

8 85TeO2-15WO3 fine particle

7 85TeO2-15WO3 coarse particle

5
% volume

–1
1 10 100 1000
Size (μm)

(b) (c)

Fig. 2. (a) Particle size distribution of the initial fine and coarse 85TeO2–15WO3 glass particles. SEM photographs of initial 85TeO2–15WO3
glass particles, (b) fine, (c) coarse.