164 Journal of the American Ceramic Society—Bertrand et al.
current and is also enhanced by plasma-assisted deposition
within the sample undergoing consolidation.14
The influence of pressure, heating rate, particle size of ini-
tial powder, chemical composition of the die seems to play an
important role on the carbon contamination.17 Nevertheless,
to obtain high light transmission, all the sources of light scat-
tering have to be avoided (carbon, inclusions, porosity, etc.).
It is well-known that the addition of WO3 to tellurite glass
provides numerous advantages such as the enhancement of
chemical durability and resistance against devitrifica-
tion.2,18,19 This last point is of particular interest since only
surface crystallization of high nonlinear c-TeO2 phase is
reported in this binary composition when using the conven-
tional melt-quenching (MQ) technique and subsequent heat
treatment in a furnace.20 Surface crystallization, while
providing enhancement of the mechanical properties, limits
drastically the optical potential of this particular glass.
This study, focused on the 85TeO2–15WO3 glass composi-
tion, aims at studying the influence of the initial glass particle
size, the use of carbon diffusion barrier (alumina, tantalum
foil, platinum environment), and the effect of an additional
pressureless sintering step prior to SPS experiments on the
optical properties of the samples (glass and glass-ceramics)
obtained through the SPS technique.
II. Experimental Procedure
The glassy samples with composition 85TeO2–15WO3 (mol%)
were synthesized in platinum crucible in air. Raw materials,
TeO2 (Alfa Aesar, London, UK, 99.99%) and WO3 (Sigma-
Aldrich, St. Louis, MO, 99.9%), were first weighed in pre
determined quantities (to obtain a total batch of 30 g) and
heated in a furnace up to 850°C for 2 h. The samples were
quenched between two stainless plates. Two populations of
particles were then selected: the first one named coarse parti-
cles in the following was obtained by grinding and sieving the
particles, keeping those ranging from 80 to 250 lm. The sec-
ond population named fine particles was obtained by ball-
milling (Fritsch, Idar Oberstein, Germany, pulverisette 6).
The particle size distribution was checked by a laser scattering
analyzer (Malvern, Worcestershire, UK, Mastersizer 2000).
Differential scanning calorimetry (DSC) experiments were
performed using TA instruments (New Castle, DE) Q100
equipment (with a heating rate of 10°C/min). To investigate
the phase crystallization sequence during the glass powder
(fine and coarse particles) heat-treatment, temperature Raman
spectroscopy was performed from room temperature up to
580°C. All data were recorded using a T64000 Jobin-Yvon
spectrophotometer at the 514 nm wavelength (Edison, NJ).
Heating of the samples from room temperature to 580°C
was achieved using a TS1500 Linkam device (Surrey, UK)
with the same heating rate as the DSC measurements, that is,
10°C/min. Raman spectra were recorded in backscattering
mode using a long working distance objective (950), and
acquisition time was 10 s with a step of 100°C between room
temperature and 300°C and each 10°C between 300°C and
580°C.
The image (400 lm 9 400 lm, 5 lm step) is reconstructed
from the integrated intensity of main c-TeO2 band (between
658 and 695 cm
1) obtained from the 6400 spectra. The col-
ors contrast represents the variation in the intensity fluctua-
tion associated with the stretching Te–O vibration band.
Spark plasma sintering performed with the Dr. Sinter 825
Syntex machine (Kawasaki, Japan) was used to sinter the
glass powders to obtain amorphous bulks as well as glass-
ceramics. Different protocols were tested to avoid the graphite
contamination. First, the amorphous powder was introduced
in an 8-mm-diameter graphite die with or without carbon dif-
fusion barrier (alumina under and above the glass powder
and tantalum foil). Second, prior to the SPS experiment, a
pressureless sintering at Tg + 30°C for 1 h was performed.
WC (tungsten carbide) die as well as platinum environment
Vol. 97, No.
have also been used for some experiments. For all the SPS
runs, the temperature was measured with a thermocouple
positioned at the close vicinity of the sample, through the die.
The SPS parameters were defined as follows:
1. Temperature: 370°C.
2. Pressure: 50 MPa.
3. Dwell time: From 0 to 10 min.
4. Atmosphere: Ar or air.
The density of the different glass and glass-ceramic bulks
was determined through the Archimedean principle using a
Kern balance. This balance enables weighing solids in air
(mair) as well as in a solvent (in our case, absolute ethanol
methanol). If the density of the buoyancy medium is known
(q0) the density of the solid (q) is calculated as follows:
mair
q¼ q
mair
methanol 0
The microstructure of a fresh polished fracture on the cross
section of SPS glass and glass-ceramics was observed using a
Cambridge electronic microscope. The nature of the crystal-
line phases was determined using a D8 Bruker equipment
(Billerica, MA) operating in the 2h range 10°–60° with the
CuKa1 radiation.
The optical transmission measurements were carried out in
the 300–3300 nm range, at normal incidence, using a Varian
Cary 5000 spectrophotometer (Palo Alto, CA) operating in a
dual beam configuration.
The schematic representation of the setup employed to
carry out the SHG experiments is shown in Fig. 1. The light
source employed was an Infrared passively Q-switched Pow-
erChip NanoLaser, emitting a radiation at k = 1064 nm. It
was operated at a repetition rate of 1 kHz and had a pulse
width of 500 ps. We operated with an unfocused laser beam,
with a beam diameter at the laser output of 2 mm. The fun-
damental (1064 nm) beam energy was controlled by rotating
a half-wave plate. The maximum output energy that could be
delivered at the sample was 50 lJ/pulse. The SH light inten-
sity generated by the sample was detected by a photomulti-
plier tube, connected to an oscilloscope. Any residual
fundamental light was removed using a 10-nm band pass
interference filter centered at 532 nm (F2). In addition, care-
ful attention was paid to thoroughly control that the detected
signal was actually SHG (Cf. log–log plot) and not due to
any residual fluorescence.
We finally emphasize that the SHG intensities displayed in
this study correspond only to the signal collected in reflection
H P
S
LASER
1064
1064
532
L
L
F2
Oscilloscope
532
PMT
Fig. 1. Sketch of the experimental setup used to detect SHG from
the SPS samples. The measurements are carried out only in reflection
geometry. H, half-wave plate; L, lenses; P, polarizer; PMT,
photomultiplier tube; F2, 10-nm band pass interference filter
centered at 532 nm.