J. Am. Ceram. Soc.
, 97 [1] 163–172 (2013)
Journal
A Comprehensive Study of the Carbon Contamination in Tellurite Glasses and
Glass-Ceramics Sintered by Spark Plasma Sintering (SPS)
Anthony Bertrand,‡,§ Julie Carreaud,‡,§ Gaëlle Delaizir,‡,§,† Jean-René Ducl
ere,‡,§ Maggy Colas,‡,§
Julie Cornette,‡,§ Marion Vandenhende,‡,§ Vincent Couderc,§,¶ and Philippe Thomas‡,§
‡
Sciences des Procedes Ceramique et de Traitements de Surface (SPCTS), UMR 7315 CNRS, Centre Europeen de la Ceramique,
¶
XLIM, UMR 7252 CNRS, Universite de Limoges, Limoges, France
Highly transparent tellurite glasses and glass-ceramics based
on the 85TeO2–15WO3 composition (mol%) were produced by
spark plasma sintering (SPS) from powders previously pre-
pared by the conventional melt-quenching technique and then
grinded. We report a study based on the understanding of car-
bon contamination that is commonly observed by this noncon-
ventional sintering technique and which constitutes a drawback
for optical applications. First, the influence of the particle size
of the initial amorphous powders as well as an additional pres-
sureless sintering step prior to SPS experiments and the use of
a physical carbon diffusion barrier have been investigated to
reduce the carbon contamination in glass bulks. Second, once
reducing the carbon contamination, glass-ceramics were
obtained by varying the SPS conditions. The noncentrosym-
metric c-TeO2 phase crystallized within the bulk volume while
maintaining good optical transparency and led to the genera-
tion of second harmonic. This approach paves the way to fur-
ther applications in the domain of linear and nonlinear optics.
I. Introduction
T glasses are very attractive materials for optical
ELLURITE
applications due to their good transmission in the mid-
infrared range (up to 6 lm). These glasses also exhibit high
linear and nonlinear refractive indices and they can easily be
doped with rare-earth ions for laser applications.1,2 The first
transparent tellurite glass-ceramics were developed by Koma-
tsu et al. at the beginning of the 1990s, in the system
TeO2–LiNbO33 in which they studied the second-order optical
nonlinearity provided by the noncentrosymmetric crystalline
phases. Indeed, due to their isotropic nature, glassy materials
do not generate any second harmonic (SH) signal, which is
one of the basic phenomena in nonlinear optics (NLO).
Therefore, materials which combine the advantages of both
glass and crystalline compounds constitute some source of
great attention, explaining why glass-ceramics research
remains a key focus of the scientific community interested in
NLO properties.
Among highly nonlinear crystals, LiNbO3 remains the
most attractive as it is extremely efficient to generate SH and
matches well the refractive index value of tellurite glasses.
Other nonlinear phases were finally crystallized, or inserted,
in various tellurite glasses (e.g., BaTiO3, c-TeO2). Among
J. Ballato—contributing editor
Manuscript No. 33438. Received June 27, 2013; approved September 17, 2013.
†
Author to whom correspondence should be addressed. e-mail: gaelle.delaizir@
unilim.fr
163
DOI: 10.1111/jace.12657
© 2013 The American Ceramic Society
Limoges, France
§
Labex Sigma-Lim, Universite de Limoges, Limoges, France
them, one is of particular interest to us, that is, c-TeO2, as
its crystal structure was determined in our laboratory.4
The control of the partial crystallization remains a chal-
lenge for the targeted applications especially for optical
applications. Indeed, the crystals size must remain small
enough to avoid too much light scattering according to the
Rayleigh theory to keep transparent glass-ceramics. Another
approach consists in matching the refractive indices of
both the crystals and the glassy matrix which also leads to
transparent glass-ceramics5 and ceramics.6
There are basically different types of kinetics crystal growth
such as: crystals which nucleate at the surface and grow in the
bulk, surface nucleated crystals which grow two dimensionally
at the surface, internal crystals which grow in the bulk, etc.7
The kinetics of crystals growth for one given glass composi-
tion can be predicted by either isothermal or nonisothermal
treatments thanks to, respectively, the well-known Mehl–Av-
rami equation and the Ozawa and Kissinger equations.8–10
The kinetics is dependent upon several parameters such as the
glass composition, the presence of nucleating agent, the qual-
ity of the surface, etc. If the surface crystallization is a major
advantage in increasing the mechanical strength of the base
glass, it dramatically affects the optical properties by scatter-
ing light preventing the glass from any optical-related applica-
tions. However, starting from glassy powder instead of bulk
could overcome this limitation. Indeed, grained glass samples
devitrify more easily than bulk glass samples due to the gener-
ation of imperfections at the surface of each grain and upon a
process of simultaneous amorphous state sintering and crys-
tallization, glass-ceramic materials can be obtained. This pro-
cess is known as sinter crystallization.11
Recently, the nonconventional sintering technique, namely,
the spark plasma sintering (SPS) also known as field-assisted
sintering technique (FAST) appeared as a promising route
for obtaining glass-ceramics from powders.12 If metallic and
chalcogenide glasses have been studied so far,12,13 no study
reports the SPS sintering of tellurite glasses to the best of our
knowledge. The main advantages of SPS over others sintering
techniques are the fast heating rates (up to 600°C/min) due
to Joule heating and the online control of parameters (sinter-
ing through displacement of punches, pressure, temperature,
vacuum, etc.) allowing to obtain glass-ceramics with desired
crystalline fraction within few minutes while several hours
are required for a conventional heat treatment in a furnace.
The main drawback of SPS remains the graphite pollution in
the samples which is commonly observed. Several groups
have reported on significant carbon contamination in samples
such as in MgAl2O4 transparent ceramics,14 in soda lime15
or GeS2 chalcogenide glasses16 having undergone a SPS den-
sification treatment. This contamination was attributed to the
proximity of the graphite dies that conduct the high electric
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. 1
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.
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.
166 Journal of the American Ceramic Society—Bertrand et al. Vol. 97, No. 1

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.
January 2014 Highly Transparent Tellurite Glasses and Glass-Ceramics Prepared by Spark Plasma Sintering
0 to 10 min) to obtain either a glass bulk material or glass-
ceramics with different crystalline fractions. The amplitude of
the displacement of punches related to the sintering is limited
in the case of the bulk prepared by pressureless sintering
treatment prior to SPS. At the opposite, the shrinkage
observed is more important for the “free” powder as also
shown in Fig. 5. The density of SPS amorphous bulk is
5.83 g/cm3 which corresponds to more than 99% of the theo-
retical density (the reference is the density of a glass obtained
by melt quenching). It is noteworthy that the density of the
pressureless sintering pellet prior to SPS is more than 95%.
Figure 6 shows the photographs of the different glass and
glass-ceramic bulks obtained by SPS from the coarse and fine
particles as well as from the pressureless pellets heat-treated
at Tg + 30°C for 1 h prior to SPS. Figure 6(a) corresponds
to the reference glass bulk obtained by the conventional MQ
technique. Figures 6(b)–(e), respectively, show the photo-
graphs of glass bulks obtained from fine particles (b and c)
and coarse particles (d and e) with or without the presence
of some carbon diffusion barrier (carbon comes from the die
and/or the papyexâ; Mersen, Paris, France) such as platinum
Fig. 5. Shrinkage rate and load applied as a function of
temperature during the SPS experiments.
(a)
(b) (c) (d) (e)
(f) (g) (h)
Fig. 6. Photographs of (a) melt-quenching (MQ) glass (reference),
(b) and (c) SPS glasses prepared without any pressureless sintering
step prior to SPS from fine particles, respectively, without (b) and
with (c) a carbon diffusion barrier, (d) and (e) SPS glasses elaborated
without any pressureless sintering step from coarse particles,
respectively, without (d) and with (e) a carbon diffusion barrier, (f)
(g), and (h) SPS glass and glass-ceramics prepared with a
pressureless sintering step prior to SPS (from coarse particles). The
inset highlights the strong impact of the SPS step for the
transparency.
167
environment, alumina, tantalum foil, or both. The use of a
carbon diffusion barrier listed previously has then a very
positive effect on the carbon contamination as the bulks turn
from dark or brownish color to lighter color. However, even
with the use of a carbon diffusion barrier, many black spots
are still visible in the glass bulks. These black spots can be
related to some carbon contamination as no periodic lattice
exists in a glass enabling the creation of lattice point defects.
SEM observation and Energy-Dispersive X-ray Spectroscopy
analysis of samples displayed in Figs. 6(d) and (e) lead to the
confirmation of the presence of graphite particles [Figs. 7(a)].
Figure 7(b) shows the Raman signatures of both samples
corresponding to Figs. 6(e) and (f). In particular, for the
sample depicted in Fig. 6(e), the Raman spectrum has been
recorded after focusing into a black spot, revealing clearly
the carbon contamination. Indeed, the Raman spectrum evi-
dences the so-called D and G bands, respectively, at 1380
and 1590 cm
1 reflecting undoubtedly the presence of carbon
in materials.24 The origin of these bands will be explained
later in the study.
The sintering of fine particles leads to a darker homoge-
neous color than the sintering of coarse particles which
exhibits brownish color with dark spots [Figs. 6(b) and (d)].
This is not fully understood at this point, but we may attri-
bute this phenomenon to the higher number of pores that is
higher in the packing of fine particles which would act as
more carbon diffusing centers through the bulk leading to
the black color in comparison with coarse particles as
explained later in the text (CO gas contained in the pores).
The carbon diffusion kinetic rate is as well higher in the case
of fine particles.
The combination of the pressureless sintering at Tg + 30°C
followed by a SPS treatment permits to eliminate efficiently the
carbon contamination as described by Fig. 6(f). Indeed, the
yellow color is predominant in the glass bulk and the quantity
of black spots is strongly reduced. It is noteworthy that a
single pressureless heat treatment at Tg + 30°C is not sufficient
to get the glass transparency as shown in the insert of Fig. 6,
therefore proving the importance of the SPS treatment.
The source of graphite precipitation is believed to be the
atmosphere within the SPS apparatus as well as its graphite
tools that serve as heating element (spacer, die, etc.). This
source can explain the G band in the Raman spectra in
Fig. 7(b).
During heating and densification (even under vacuum or
Ar atmosphere), when an open pore system is present, the
gaseous phase may consist of CO and CO2 which results
from the interaction between carbon and residual oxygen.25
As the pores close up, each pore is filled by this gas, which
undergoes a composition change as a function of tempera-
ture and pressure (due to decreasing pore volume). The
process, which takes place within the closed pores, may be
described by the exothermic reaction25:
2COðgÞ ¼ CO2 ðgÞ þ CðsÞ (1)
with the corresponding equilibrium constant K:
PCO2 xCO2
K¼ ¼ (2)
ðPCO Þ2 x2CO  Ptot
P
(ðPtot ¼ PCO þ PCO2 þ Pargon or Pair Þ; xCO ¼ PPCO
tot
; xCO2 ¼ PCO 2
tot
;
xCO and xCO2 are respectively the molar fraction of CO and
CO2 species) The forward reaction of Eq. (1) is favored at
low temperatures, that is, below 700°C. Then, during viscous
sintering, the diffusion of gas (especially CO) out of the pore
into the glass is rapid relative to the surface-tension-induced
viscous flow of material.26 Therefore, with increasing densifi-
cation, the total pressure Ptot within the pores decreases as
the volume of the pores decreases due to the gas dissolution
168 Journal of the American Ceramic Society—Bertrand et al. Vol. 97, No. 1

(a)

Te
Glassy
matrix
C particle
Te

c w Te
o Te
Te
5 μm

0 1 2 3 4 5
KeV

(b) SPS glass (with pressure-less sintering prior to SPS)

SPS glass (without pressure-less sintering prior to SPS)
Average Raman intensity (a.u.)

G band

D band

900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900
Wavenumber (cm–1)
Fig. 7. (a) SEM image and EDXS analysis of a carbon particle embedded in the glassy matrix, (b) Raman spectra of glass bulks sintered by
SPS with and without pressureless sintering prior to SPS.

4
Intensity (arb. units)

(e)

2 (d)

(b)
(c)
(a)
(b)

(a)
Fig. 8. Raman spectra collected for glass bulks prepared (a) by 0
melt quenching (MQ), (b) by SPS combined with a pressureless 20 25 30 35 40
sintering step prior to SPS. 2θ CuKα1 (°)

Fig. 9. XRD patterns collected for various samples sintered by

SPS: (a) glass (370°C, 50 MPa, 0 min), (b)–(e) glass-ceramics
into the viscous flow. The precipitation of carbon at the free sintered by SPS (370°C, 50 MPa, from 1 to 10 min). The symbols ✱
surface of the pores may therefore take place at the interface and ○ correspond, respectively, to the presence of c-TeO2 and
gas–glass. This source of carbon could be the signature of a-TeO2 phases.
January 2014 Highly Transparent Tellurite Glasses and Glass-Ceramics Prepared by Spark Plasma Sintering 169

both the G bands and D bands in the Raman spectra in become more and more opaque [Figs. 6(g) and (h)].
Fig. 7(b). The disordered carbon characterized by the D Figure 6(h) even shows the aspect of a sample that was almost
bands could result from the combined presence of the viscous completely crystallized.
flow during the sintering and the variation in pressure inside For the following part of this study, we will focus on the
the closed porosity. glasses and glass-ceramics made by a pressureless sintering
A pressureless sintering prior to SPS at Tg + 30°C in a step prior to SPS followed by an SPS experiment from coarse
conventional furnace with no graphite environment allows particles which are of particular interest as they do not
first the densification of the sample (>95%) and reducing the present any detectable and visual carbon contamination.
amount of CO and CO2 trapped in the closed porosity due
to the nongraphite environment. It is noteworthy that graph-
ite pollution in refractory oxide ceramics or glasses can be (3) Characterizations of Glass and Glass-Ceramics
easily suppressed by a thermal treatment above 600°C.27 In Prepared by SPS
our case, the very low Tg of tellurite glasses prevents any The structure of the glasses made by melt quenching
treatment at such a temperature. [Fig. 6(a)] and SPS [Fig. 6(f)] have been compared by Raman
Increasing the dwell time at constant pressure and temper- spectroscopy and a perfect match between the two spectra is
ature during the SPS experiments leads to glass-ceramics that shown in Fig. 8. This information is crucial to prove that

(a) (b) (c)

100 µm 100 µm 100 µm

(d) (e)

100 µm 20 µm

(f)
-200
0.30
-150

0.25
-100

-50 0.20
Intensite (coups)

(1)
Y (µm)

0 0.15
(2)
50 0.10

100
0.05
50 µm
150
10 µm 0.00
200
–200 –100 0 100 200
X (µm)

1,4
0,3 (1) (2)
1,2
I (arbritrary unit)

0,25
I (arbritrary unit)

1
0,2
0,8
0,15 0,6
0,1 0,4
0,05 0,2
0
0 300 400 500 600 700 800 900
300 400 500 600 700 800 900
wavenumber (cm–1)
wavenumber (cm–1)

Fig. 10. (a, b, c, and d) EDXS-SEM pictures of glass and glass-ceramics prepared by SPS (370°C, 50 MPa, dwell time of, respectively, 0, 1, 3,
and 5 min), (e) Higher magnification of the picture displayed in (d), (f) Raman mapping of a glass-ceramic prepared by SPS (370°C, 50 MPa,
5 min) associated with the optical image and the corresponding spectra. (1) and (2) correspond to the labels denoting, respectively, the core or
the surface of the glass particles.
170 Journal of the American Ceramic Society—Bertrand et al.
SPS experiments do not modify the structure of this tellurite
glass. The Raman shifts evidenced in these spectra are sum-
marized in Fig. 8. Further details about the structure of this
glass composition can be found in.28
XRD measurements were carried out first to establish the
crystalline/amorphous nature of the SPS samples. The XRD
pattern depicted in Fig. 9(a) is obviously typical of an amor-
phous sample, whereas Figs. 9(b)–(e) represent XRD pat-
terns characteristic of glass-ceramics. As mentioned above,
the latter XRD pattern [Fig. 9(e)] even corresponds to a SPS
sample that was almost completely crystallized. The well-
defined Bragg peaks showing up correspond to the crystalli-
zation of the c-TeO2 phase (marked by ✩). Additional peaks
appearing for longer dwell time (marked by ○) corresponds
to the a-TeO2 phase.
As previously mentioned, surface crystallization occurs
upon heating the glass bulks obtained by the conventional
MQ technique between Tg and Tc, thus preventing this com-
position to be used in any potential optical applications.20 In
our present study, crystals are found to be disseminated
within the whole volume of the glass-ceramics prepared by
SPS from amorphous powders. To evaluate which sintering
mechanism is likely at play and to study the microstructure,
we observed by SEM analysis some various freshly polished
glass-ceramics with different crystalline fraction obtained by
varying the dwell time during the SPS experiments.
Figure 10(a) corresponds to the amorphous bulk of Fig. 6(f)
and serves as a reference. Figures 10(b)–(e) reveal a chemical
contrast at the grain boundaries characteristics of the surface
devitrification phenomenon leading to the coast-and-island
microstructure.29,30 Such phenomenon can be confirmed
based on Raman mapping data displayed in Fig. 10(f) which
unambiguously demonstrate the localization of crystals (c-
TeO2) at the grain boundaries, whereas the grains remain
amorphous. Moreover, SEM photographs [Figs. 10(b)–(d)]
perfectly corroborate the XRD data (Fig. 9) by showing
that, as the crystalline fraction increases when longer dwell
time is applied during SPS, the number of crystals increases
at the amorphous particle boundaries. As a first estimation,
only the relative part the crystalline domain was determined
using image analysis software on these EDXS–SEM pictures.
The percentage obtained should therefore be regarded as an
upper bound of the actual crystalline fraction due to the den-
dritic shape of crystals that are embedded in the glass.
Within this rough approximation, the results indicate an
increase in the crystalline fraction from 3% [Fig. 10(b)], 5%
[Fig. 10(c)] to 40% [Fig. 10(d)] as the dwell time increases
up to 5 min under the same temperature and pressure
conditions.
The data were collected for three samples elaborated by
SPS and they were compared to the optical transmission
curve measured for one reference glass sample elaborated by
the conventional MQ technique. First, we started comparing
the optical transmission curve measured for a MQ glass with
that measured for a typical glass made by SPS. Based on the
Raman spectroscopy data commented in Fig. 8, which indi-
cate that the structure of (MQ) and SPS glass samples is
identical, the reduction in the optical transmission in the
short wavelengths noticed for a SPS glass sample is attrib-
uted to light scattered by residual porosity, small inclusions/
crystals or residual pollution. However, despite this reduc-
tion, the optical transmission value appears already high (up
to 70% transmission) for these first tellurite glasses prepared
by SPS.
The formation of c-TeO2 crystals at the surface of amor-
phous grains in the very first steps of the sintering process
partially hinders further densification of the samples due to
viscosity considerations, explaining the scattering of light evi-
denced in the optical transmission spectra represented in
Fig. 11.
For glass-ceramics SPS samples, the optical transmission
drops with the increasing crystalline volume fractions. For
Vol. 97, No. 1
these samples, the effect of light scattering produced by the
c-TeO2 crystals is mainly due to their 2D dendritic shape
[Fig. 10(e)].
It is noteworthy that the broad absorption band around
3300 nm is attributed to the presence of OH groups intro-
duced by the water content of the glass.
As testified by both XRD and Raman spectroscopy data
[Figs. 9 and 10(f)], the crystals located at the surface of
amorphous grains and disseminated within the whole volume
of the glass-ceramics correspond to the c-TeO2 phase. The
latter crystallizes into an orthorhombic unit cell with the
P212121 space group and is, as a consequence, noncentrosym-
metric. Therefore, for SPS glass-ceramics, it is expected to
detect some SHG signal.
Four SPS glass-ceramics samples were tested: their corre-
sponding XRD patterns are represented in Figs. 9(b)–(e),
respectively, and the pictures of two of them are displayed in
Figs. 6(g) and (h). Thus, from the XRD data, it is obvious
that the crystalline fraction progressively increases.
Figure 12(a) displays the variation in the SHG amplitude
as a function of the approximate crystalline volume fraction
estimated from the processing of EDXS–SEM images and
described before. Considering that the shape (according to
SEM observations) and size (based on similar full-width at
half maximum values) of crystals remain more or less con-
stant, the SHG amplitude should then be proportional to the
volume fraction of crystals. The experimental observation
clearly confirms this statement: a linear fit [Fig. 12(a)] is pro-
vided as a guide for the eyes to highlight this tendency. Only
the first three points were fitted, as they correspond to glass-
ceramic samples containing uniquely c-TeO2 crystals. The
last point corresponds to the sample which is almost com-
pletely crystallized (i.e., such point was placed at an abscissa
equal to 100%), and where a-TeO2 and c-TeO2 crystals are
both present (see Fig. 9). The SHG of the base glass is equal
to zero and is not represented. As the SHG efficiency is dif-
ferent between a-TeO2 and c-TeO2 crystals, it is unfortu-
nately impossible to include this last data in the fitting
procedure.
The threshold for detecting SHG is difficult to define accu-
rately, but can be, however, estimated. Indeed, the linear fit
to the data should go through the origin of the graph (as for
Fig. 11. Visible and near-IR optical transmission curves of (a) glass
bulk obtained by the conventional melt-quenching (MQ) technique
(reference), (b) glass bulk obtained by pressureless sintering step
prior to SPS + SPS (370°C, 50 MPa, 0 min), and (c, d) two glass-
ceramics obtained by pressureless sintering step prior to SPS + SPS
(370°C, 50 MPa and two different dwell times).
January 2014 Highly Transparent Tellurite Glasses and Glass-Ceramics Prepared by Spark Plasma Sintering
(a)
(b)
Fig. 12. (a) Evolution of the SHG amplitude detected for the
various samples tested within this study, as a function of the volume
fraction of crystals. The linear fit of the first three points serves only
as a guide for the eyes. The dashed line corresponds to the
“continuity” of the linear fit. The last point is not fitted and the
SHG of the base glass equal to zero is not represented, (b) log
(second harmonic (SH) intensity)–log (pump laser intensity) plot.
The straight line corresponds to the linear fit of the data.
a volume fraction of crystals equal to zero, there is abso-
lutely no SHG). It is almost, but not exactly, what we
observe. Thus, the slight shift evidenced corresponds to the
SHG amplitude detected at the ordinate at the origin. Such
value can be directly related to a volume fraction approxi-
mately equivalent to 1.5%, which constitutes the volume
fraction of crystals beyond which it will become possible to
detect SHG. It is finally important to undermine that the
SHG signal measured for a glass sample (Figs. 6(f)–10(a)] is
strictly equal to zero.
As the SHG phenomenon is a second-order nonlinear pro-
cess, the dependence of the SH energy must be strictly a
quadratic function of the fundamental energy.31 In,32 the
authors have expressed the SH power, P (2x), as follows:
K:l2c :P2 ðxÞ
Pð2xÞ ¼ (3)
A (2008).
where lc is the coherence length, A the area beam, K a mate-
rial-dependent constant proportional to d2(2x) (d being the
second-order NLO susceptibility), and P(x) the fundamental
power. If one applies the logarithmic function to Eq. (3), it
turns out that:
log Pð2xÞ ¼ logðK0 Þ þ 2: log PðxÞ (4)
171
with K′ being another constant including the previous con-
stants. Thus, theoretically, if the observed physical phenom-
enon is actually SHG, the curve representing the logarithm
of the SH power versus the logarithm of the fundamental
power must be a straight line with a slope strictly equal to
two.
For the sample displaying the highest signal, Fig. 12(b)
indicates that the log–log curve can be clearly fitted by a
straight line (the goodness of fit parameter r2 = 0.9989,
whereas a perfect fit gives r2 = 1) with a slope equal to 2.03.
The experimental value matches extremely well that of the
theory, demonstrating by this way that the detected signal
actually corresponds to SHG and is not due to any residual
fluorescence.
IV. Conclusion
Glasses and glass-ceramics based on the 85TeO2–15WO3
composition have been prepared through the SPS technique.
Several parameters have been studied to limit the carbon
contamination that is common with this nonconventional
technique and which is detrimental for optical applications.
The influence of the initial amorphous particles size as well
as the effect of a pressureless sintering step prior to SPS has
been investigated. The carbon contamination is higher in the
case of the fine particles leading to dark glass bulks. The use
of a diffusion barrier such as platinum, tantalum foil or alu-
mina has a limited effect on the carbon pollution. The best
results were obtained by a pressureless sintering step around
Tg prior to SPS experiment. Yellow glasses with relatively
high optical transparency properties were obtained which
enlighten the positive influence of such a pressureless sinter-
ing step. The carbon contamination is mainly due to graphite
environment (die, papyexâ) which diffuses into the material
and which also lead to residual CO or CO2 inside the SPS
chamber even operating under argon atmosphere. By increas-
ing the dwell time at constant pressure and temperature dur-
ing the SPS experiments, the noncentrosymmetric c-TeO2
phase crystallized through the matrix which leads to the gen-
eration of a SH signal.
Further experiments will be now carried out to improve
the optical performances by reducing the proportion of scat-
tered light induced by residual porosity or graphite particles.
Acknowledgments
Authors would like to thank Dr. Claude Godart and Dr. Judith Monnier from
ICMPE, Thiais (France) as well as Dr. Alain Largeteau from ICMCB,
Bordeaux (France) for some SPS experiments. This work is supported by the
Labex Sigma-Lim (no. ANR-10-LABX-0074-01).
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