166 Journal of the American Ceramic Society—Bertrand et al. Vol. 97, No.

glass transition temperature, Tg, is constant for the three
experiments and is equal to 335°C. The increase in the mean
particle size from 6 lm (fine) to 167 lm (coarse) causes a
shift of the crystallization peaks toward higher temperatures
(a)
ranging from 420°C to 435°C, suggesting surface crystalliza-
tion as the dominant mechanism in the investigated composi-
tion.22 The broadening of the crystallization peaks for the
bulk as well as the study of Cß elikbilek et al.20 also confirms
this observation.
To identify the nature of the different crystalline phases
appearing upon heating, Raman spectroscopy data were col-
lected as a function of temperature applying the same heat-
ing rate as the DSC runs, that is, 10°C/min. The Raman
shifts evidenced for these crystalline phases associated with
the different crystallization peaks, respectively, corresponds
to c-TeO2, a-TeO2, and WO3 for the coarse particles and
c-TeO2, WO3, and a-TeO2 for the fine particles (Fig. 4).23

(b)
(2) SPS of the 85TeO2–15WO3 Amorphous Powder
The SPS parameters (pressure, temperature, vertical displace-
ment of punches) during the sintering process are shown in
Fig. 5. The sintering temperature was chosen accordingly to
lie between the glass transition and the first crystallization
temperatures. The sintering process starts in the temperature
(c) range 310°C–325°C and ends around 350°C or 370°C
depending on the pressureless sintering treatment made or
not prior to the SPS experiments. The dwell temperature of
370°C was therefore chosen. Different experiments were car-
Fig. 3. DSC curves of coarse (a), fine (b) 85TeO2–15WO3 glass ried out at constant pressure (50 MPa) and temperature
particles, and (c) glass bulk. (370°C) but different dwell times were applied (ranging from

(a) Heat flow (a.u.)

300

1) TeO2γ 2) 0.35

TeO2 α
350

0.30
WO3
0.25
400
Temperature (°C)

Intensity
0.20
450

(1)
(2) 0.15
(3)
500

0.10

0.05
550

40
0.00
200 400 600 800 1 000
Wavenumber (cm–1)

(b) Heat flow (a.u.)

300

0.30
1) TeO2γ 2)
TeO2 α
350

0.25
WO3
400

0.20
Temperature (°C)

Intensity

(1) 0.15
450

(2) 0.10
500

(3)
0.05
550

40
0.00
200 400 600 800 1 000
Wavenumber (cm–1)

Fig. 4. Temperature-dependent Raman spectroscopy data recorded for coarse (a) and fine (b) 85TeO2–15WO3 glass particles showing the
appearance sequence of the different crystalline phases. The Raman data are compared to the DSC thermograms of the corresponding powder.