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Orthorhombic phase stabilization and transformation phase process

in zirconia tantalum-doped powders and spark plasma sintering
systems
G. Sponchia a , M. Boffelli b , M. Back a , W. Zhu b , A. Domnguez Rodrguez c , G. Pezzotti b ,
G. De Portu d , P. Riello a , A. Benedetti a,
a
Department of Molecular Sciences and Nanosystems and Centro di Microscopia Elettronica Giovanni Stevanato, Universit Ca Foscari di Venezia, via
Torino 155/B, 30172 Venezia, Mestre, Italy
b
Kyoto Institute of Technology and Research Institute for Nanoscience, Sakyo-ku, Matsugasaki 606-8585, Kyoto, Japan
c
Department of Condensed Matter Physics, Universidad de Sevilla, Avda. Reina Mercedes, 41012 Sevilla, Spain
d
ISTEC, Institute of Science and Technology for Ceramics, via Granarolo 64, I-48018 Faenza, Ravenna, Italy

a r t i c l e i n f o a b s t r a c t

Article history: The role of different amount (from 1 to 20 mol%) of tantalum Ta(V) into the zirconia lattice has been
Received 14 October 2016 investigated in different powders systems prepared via co-precipitation and after calcination. The X-ray
Received in revised form 5 April 2017 diffraction and Raman analyses, have conrmed the presence of an orthorhombic phase in all the samples.
Accepted 7 April 2017
The stability of this phase has been investigated by in situ X-ray diffraction analysis from 100 C to
Available online xxx
1000 C and after the subsequent cooling. A phase transformation mechanism, with the formation of a
poor (monoclinic) and a rich phase (orthorhombic) in Ta has been consider in order to explain the XRD
Keywords:
patterns obtained at different temperatures. The characterization of the orthorhombic phase on bulk
Zirconia
Tantalum
ceramic specimens prepared via Spark Plasma Sintering (SPS) has been also investigated. SEM analysis
Orthorhombic has conrmed the presence of a two-phase system.
Raman 2017 Elsevier Ltd. All rights reserved.
Spark plasma sintering

1. Introduction and Ce4+ have been employed as stabilizing ions. Zirconium is a

Zirconium oxide or zirconia (ZrO2 ) is an interesting and use-
ful metal-oxide. Many different applications elds are involved
on zirconia-based materials research, thanks to its good mechan-
ical, thermal, functional and sometimes unique properties [1,2].
Common uses for these ceramic materials are thermal barrier coat-
ings (TBCs) [3], dental and bone prostheses [4,5], high resistance
laminates [69], solid oxide fuel cells (SOFCs) [10,11], gas sen-
sors [1214] and optical devices [15,16], catalysis and luminescent
materials [1719] and new nanoparticles (NPs) [2023].
The technological importance of zirconia as structural material
is related to the tetragonal-to-monoclinic martensitic transition.
Yttria-stabilized zirconia is the most used doped system since
having superior mechanical properties [1]. The tetragonal phase,
partially or fully stabilized, can be prepared doping with a con-
trolled percentage of Y3+ , but also other cations such as Mg2+ , Ca2+
Corresponding author.
E-mail address: benedett@unive.it (A. Benedetti).
tetravalent cation, so charge compensation is necessary when a
trivalent or bivalent cation is introduced into the zirconia crys-
talline structure. Due to such compensation, oxygen vacancies are
formed as amply described in literature [2]. These vacancies seem
to stabilize the tetragonal zirconia ceramics compounds. However,
this stabilization is also the source of two mean cracking pro-
cess due to a retransformation to a monoclinic phase with larger
volume: transformation toughening and low temperature degra-
dation (LTD) [4,24,25]. This is an important drawback: aging and
moisture could determine unexpected (brittle) cracking in zirco-
nia ceramic devices. Therefore, in the last years, the limitations of
partially tetragonal stabilized zirconia in engineering and medical
applications have been thoroughly discussed [24,2629].
As a possible solution, since the oxygen vacancies are induced
by trivalent (or bivalent) cations, pentavalent doping cations (Ta5+ ,
V5+ and Nb5+ ) have been used to prevent this type of defect [30,31].
The possibility to prepare a stable vacancies-free zirconia ceramic
with good mechanical properties represents an excellent approach
in order to refresh the appeal of zirconia as a structural mate-
rial. Some technological advantages have been already reported in

http://dx.doi.org/10.1016/j.jeurceramsoc.2017.04.017
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Please cite this article in press as: G. Sponchia, et al., Orthorhombic phase stabilization and transformation
phase process in zirconia tantalum-doped powders and spark plasma sintering systems, J Eur Ceram Soc (2017),
http://dx.doi.org/10.1016/j.jeurceramsoc.2017.04.017
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2 G. Sponchia et al. / Journal of the European Ceramic Society xxx (2017) xxxxxx
literature such as a better hot corrosion resistance for TBCs [3134]
concerning zirconia tantalum-doped materials.
In parallel to the research of new ZrO2 based systems with
enhanced macroscopic properties, some papers have evidenced the
presence of three orthorhombic phases into zirconia systems, sta-
bilized also by some dopant such as MgO, at high pressure and
temperature. For some of these systems, with specic composi-
tion, detailed structural studies have been reported [3538 and
reference therein]. In particular, pure zirconia system shows Pbca
(3.515 GPa) and Pnam (over 15 GPa) orthorhombic phases sta-
ble at high-pressure [36]. Moreover, different doped and co-doped
zirconia systems with Ca or Mg [39], or some alloy systems evi-
dence the Pbc21 (an allowed transformation of the Pca21 space
group) orthorhombic phase as reported by Kisi et al. [36]. Even
though zirconia Ta-doped systems have been previously studied,
very scarce and not always coherent data are available on phase
analysis [30,33,4043]. The homogeneity range of orthorhombic
phase was found to be up to 33 mol% of Ta2 O5 in ZrO2 [44]. In
particular, on samples with low Ta content, some paper reports
that the addition of Ta brings about the gradual stabilization of the
tetragonal ZrO2 , meanwhile, some others show the presence of an
orthorhombic phase. Probably, since the differences between the
two phases are particularly evident at angles higher than 35 in 2,
the X-ray diffraction results have been variously interpreted due
to the too limited range of the patterns investigated [45]. Recently,
we have reported a detailed X-Ray diffraction analysis on a ZrO2
sample doped with 16 mol% of TaO2.5 [46] and we have identied
the high pressure Pca21 orthorhombic structure reported by Kisi
et al. [36] as the main crystalline phase.
Despite the extensive Raman knowledge of the well-known
zirconia polymorphs (i.e. monoclinic, tetragonal and cubic) the
orthorhombic phase, in all his forms (Pnam, Pbca, Pca21 ) has not
been investigate in details. The only system published, in which
both calculated vibrations and experimental data match, concerns
the orthorhombic Pnam system, which identies the cotunnite-
type phase [48,49]. Generally, other attempts, performed to
discriminate the orthorhombic Pbca, cannot be considered fully
reliable. The main difculty arises from the restricted number of
high pressure-induced polymorphs, transformed from either mon-
oclinic [50,51] or tetragonal [52] zirconia, studied so far. Different
pressure-annealing treatments involves different grade of lattice
distortions, leading to different crystallographic systems and con-
sequently different Raman mode shifts.
Aim of the paper is to investigate the role of Ta as a dopant
agent, in a specic range of composition into the ZrO2 structure as
stabilizer of the orthorhombic phase in the powder and in the con-
solidated specimens. In detail, the study was carried out as follows:
a) Seven ZrO2 -TaO2.5 doped powdered systems, with the amount of
Ta ranging from 1 to 20 mol% of TaO2.5 (ZT1, ZT3, ZT4, ZT5, ZT8, ZT12,
ZT20), were prepared by a catalyzed co-precipitation route; b) the
thermal evolution and the stabilization of the crystalline phases
were analyzed in situ and ex situ by XRD patterns using also
a synchrotron line; c) a detailed Raman spectroscopy analysis was
performed; d) the three more signicant powdered systems were
consolidated via Spark Plasma Sintering (SPS) at two different tem-
peratures and pressures; e) a detailed XRD and SEM analysis of the
consolidate systems were conducted to dene the role of Ta in the
nal microstructure.
The present study have also showed that the lower limit rela-
tive to the stabilization of the orthorhombic phase, in the system
ZrO2 -TaO2.5 , is 16 mol% instead of 25 mol% of TaO2.5 as reported
in literature [31,34,43,47]. The XRD analysis of the two systems
show that the same orthorhombic phase (Pca21 ) had to be used to
describe both the crystalline structures.
Please cite this article in press as: G. Sponchia, et al., Orthorhombic phase stabilization and transformation
phase process in zirconia tantalum-doped powders and spark plasma sintering systems, J Eur Ceram Soc (2017),
http://dx.doi.org/10.1016/j.jeurceramsoc.2017.04.017
2. Material and methods
2.1. Materials
Zirconyl chloride octahydrate (ZrOCl2 8H2 O; Aldrich 98%), tan-
talum(V) chloride anhydrous (TaCl5 ; Aldrich 99.8%), ammonium
hydroxide (NH4 OH; Fluka 28 wt%), ethanol (EtOH; Aldrich 99.8%),
and distilled water. All reagents were used as received without
further purication.
2.2. Synthesis of the powders
Ta-doped ZrO2 powders were prepared via the base catalyzed
coprecipitation method, already used for other similar works [21].
Briey, ethanolic solutions 0.1 M ZrOCl2 8H2 O and 12.5 mM TaCl5
were mixed together in different amounts while stirring at ambi-
ent temperature. Co-precipitation to the corresponding hydroxides
was achieved by drop-wise addition of excess aqueous ammonia.
After 20 min of stirring at room temperature, the co-precipitated
hydroxides were centrifuged (9000 rpm for 30 min) and washed
once with distilled water and three times with EtOH to remove
excess ammonia and unreacted precursors, then dried at 130 C for
12 h. The as-obtained powders were calcined in air at 1000 C for
6 h to promote the crystallization and transformation to the mixed
oxides.
2.3. Powder consolidation
The consolidation process of the zirconia Ta-doped powders
(ZT5, ZT8, ZT12) via Spark Plasma Sintering (SPS) has been per-
formed with a Dr. Sinter Lab SPS 515S equipment at two different
experimental conditions sets: a) T = 1250 C, P = 75 MPa, t = 5 min
(SPS1250 series), b) T = 1150 C, P = 100 MPa, t = 5 min (SPS1150
series). Lower sintering temperature needs higher sintering pres-
sure in order to reach a good nal density of the specimen.
2.4. Characterization
The microstructure of the powders was studied by means of X-
ray powder diffraction (XRPD). A Philips diffractometer with a PW
1319 goniometer (Almelo, The Netherlands) with BraggBrentano
geometry, connected to a highly stabilized generator (40 kV), was
used for the preliminary XRPD measurements. A Bruker D8I-90
with BraggBrentano geometry, connected to a highly stabilized
generator (40 kV), was used for the Wide-Angle X-Ray Scatter-
ing (WAXS) measurements of the sintered specimens. The in
situ temperature XRPD measurements were collected at the ELET-
TRA Laboratories of Sincrotrone Trieste S.C.p.A (Line MCX) using
a quartz glass capillary as sample holder [53]. The patterns were
acquired in the range 1001000 C every 100 C with a temperature
ramp of about 0.17 C/sec. Before any measurements, the temper-
ature of the samples was kept constant for 10 min.
Grain size distribution, compositional Energy Dispersive X-ray
Spectroscopy (EDS) analyses, Backscattered Electrons (BSE) and
Secondary Electrons (SE) images on the sintered specimens have
been preformed with a Zeiss Sigma VP FE-SEM c/o the Centro di
Microscopia Giovanni Stevanato in Venezia-Mestre (VE, Italy). In
order to evidence the grain boundaries the surfaces have been pol-
ished (lapping with diamond paste till 1 m) and then have been
annealed at one hundred degree lower respect to the SPS temper-
ature.
Raman spectra were acquired with using a confocal (optical)
microprobe from different areas of the samples. All Raman spectra
were collected at room temperature using a single monochromator
(T-64000, Jobin-Ivon/Horiba Group, Kyoto, Japan) equipped with
a nitrogen-cooled 1024 256 pixels CCD camera (CCD3500 V,
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ZT20
ZT12
ZT8

ZT5
ZT4

ZT3

ZT1
15 20 25 30 35 40 45 50 55 60 65 70 75 80
2 ()

Fig. 1. XRPD patterns of powder samples calcinated at 1000 C.

Horiba Ltd., Kyoto, Japan), and analyzed by using commercially Table 1

Weight fractions of zirconia phases for the powder samples, as obtained by the
available software (Labspec, Horiba/Jobin-Yvon, Kyoto, Japan). The
Rietveld renements.
excitation frequency used in the experiment was the 532 nm green
line of an Nd:YAG diode laser operating with a power of 12 mW. Sample P21 /c (%) Pca21 (%)
The spectrum integration time was typically 30s, averaging the ZT1 88 12
recorded spectra over three successive measurements. A confocal ZT3 69 31
conguration of the Raman probe was adopted throughout all the ZT4 24 76
ZT5 18 82
experiments, using of a 100 x objective lens in order to exclude pho-
ZT8 0 100
tons scattered from out-of-regions of the probe. Width and spectral ZT12 0 100
positions of selected Raman bands were obtained upon tting the ZT20 0 100
raw collected spectra with Lorentzian curves.

3. Results and discussion
3.1. Ex situ X-ray powder diffraction
As shown in Fig. 1 the X-ray powders diffraction patterns can be
grouped in three different sets according to the crystalline phases
evidenced by the samples. To the rst group belong the two samples
(ZT1 and ZT3) richer in the monoclinic phase; to the second group,
the samples (ZT4 and ZT5) that show the co-presence of monoclinic
and the orthorhombic phase, as prevalent phase; to the last group,
the three samples (from ZT8 to ZT20) that show only the presence
of orthorhombic phase.
The Rietveld analysis, of all the samples, has been performed on
the full-range X-ray patterns (5 < 2 < 140 ). After a careful evalua-
tion of the different zirconia polymorphs, the orthorhombic Pca21
(space group no.29, ICSD 67004) phase has been selected by the
tting procedures [46,54]. Fig. S1, into Supporting Information (SI),
shows an example of a full prole renement of the patterns per-
formed by the Rietveld method (DBWS9600 computer program
written by Sakthivel and Young and modied by Riello et al. [55]).
The same gure shows also the single contributions of the two
phases (orthorhombic Pca21 and monoclinic P21 /c) on the total t
of the sample ZT3. Table 1 reports the weight fractions of the two
phases for all the powder samples.
The analysis of the patterns can be summarized as follow: when
the Ta content increases, the monoclinic phase decreases and the
orthorhombic phase increases; in the samples with a Ta content
higher than 8 mol%, only the orthorhombic phase is stable till
1000 C; in all the samples no tetragonal phase is clearly detectable.
As reported in the introduction, this last nding disagrees with
some results [30,33,4042] published on similar systems, but
where a detailed phase analysis is only partially reported.
The reason why the Ta(V) stabilizes the orthorhombic, and
not the tetragonal or cubic, phase could be explained in terms of
internal stress and lacking of oxygen vacancy. In particular: a)
the Ta(V) doping seems to generate internal local compressive
stresses that prevent the monoclinic to tetragonal transformation
and stabilize the orthorhombic form of zirconia [54]; b) unlike
the well-known case of Y(III) doping, in which two yttrium atoms
introduce one oxygen vacancy in the zirconia structure leading the
tetragonal or cubic stabilization, Ta(V) does not introduce any com-
pensating vacancy. The Zr(IV) maintains its sevenfold coordination
and only structural changes are introduced due to the size of the
doping cations.
3.2. In situ X-ray powder diffraction
The three most signicant samples of each group, ZT3, ZT5
and ZT8, were further investigated in situ by synchrotron XRPD
measurements. Fig. 2 shows the thermal evolution of the XRPD pat-
terns of the three samples, from 100 C to 1000 C and after the
subsequent cooling to room temperature (RT). The patterns were
recorded every 100 C.
All the as prepared powders are amorphous at RT. The crys-
tallization process starts above 400 C for all the samples. At
500 C, crystalline peaks are clearly detectable in the patterns. The
orthorhombic phase starts to grow at the same temperature for
all the samples, evidencing the role of the Ta(V) cation as stabi-
lizer of this phase. As expected, the RT patterns, after the thermal
treatments at 1000 C in situ and ex situ, are the same.
The analysis of the patterns conrms that the amount of Ta
in the samples ZT3 and ZT5 is not enough to stabilize only the
orthorhombic phase. The increase of the monoclinic phase, at the
higher temperature and during the cooling, can be consistent with
the formation of a zirconia structure containing an amount of
Ta distributed in a non-homogeneous way. In particular, the Ta
can be simply heterogeneously dispersed in the sample or it can
form a two-phase system with a poor (monoclinic) and a rich

Please cite this article in press as: G. Sponchia, et al., Orthorhombic phase stabilization and transformation
phase process in zirconia tantalum-doped powders and spark plasma sintering systems, J Eur Ceram Soc (2017),
http://dx.doi.org/10.1016/j.jeurceramsoc.2017.04.017
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Fig. 2. In situ XRPD thermal patterns of the samples from 100 C to 1000 C and after cooling. ZT3 (A), ZT5 (B) and ZT8 (C).

(orthorhombic) phase in Ta that, during the heating, start to develop
and to growth. The absence of the monoclinic peaks relative to the
ZT5 sample, at the lower temperatures, can be due to the small
amount of the phase into the sample. At higher temperatures the
monoclinic polymorph is well detectable and growth until 1000 C
and during the cooling. When the Ta increases, from ZT3 to ZT5, the
amount of the monoclinic phase reduces. A more detailed picture of
the process can be found in the Sintered SPS specimens paragraph. In
the sample with a higher content of Ta (ZT8), only the orthorhom-
bic phase is stable in all the range of the temperatures from 500 C
to 1000 C and from1000 C to RT.
The analysis of the cooling process is particularly interesting
and very useful for the study of the thermal stability of crystalline
phases, but also for determining some other useful properties of
ceramic materials. From the Rietveld analysis the unit cell param-
eters can be rened and the cell volume can be determined at
different temperature for both the phases. When a material is
heated, the thermal agitation causes the bonds lengthening, the
volume of crystalline materials increases and a correlation between
volume and temperature, known as the volume Coefcient of Ther-
mal Expansion (CTE) , can be determined. All the details of our
analysis are reported in the SI. Fig. 3 shows well-dened linear
behaviors as reported by Kisi and Howard [56].
The very similar slopes of the straight lines suggest the same
behavior for each phase independently from the doping amount
and that a higher doping amount corresponds to a bigger cell
volume, underling the presence of tantalum inside the cells. Consid-
ering the properties for a good blades protection and for an active
Thermal Barrier Coating (TBC), the top coat should have a) high
melting point, b) low density, c) low coefcient of thermal con-
ductivity, d) good corrosion, oxidation and wear resistance and e)
a volume CTE value very similar to the substrate one [57]. Usu-
ally the zirconia YSZ, employed for this application, has a CTE of
31.5106 K1 . This value has to be compared with the values of
3644106 K1 relative to superalloy metal substrates of the tur-
bine blades, such as Hastelloy or Inconel . As shown in Table 2,
the orthorhombic phase has a CTE higher than the YSZ one, con-
sequently the difference between the substrate and the coating
CTE values is smaller and a better adhesion should be achieved.
On similar issues, some examples in literature have been reported
the improvement of the corrosion resistance in the Ta-doped zir-
conia materials [3134] and the lowering the thermal conductivity
coefcient [58].

A 146
B 141
ZT3 ZT3
ZT5 ZT5
145 Literature 140 ZT8
Cell Volume Pca21 ( )
Cell Volume P21/c ( )

3
3

144 139

143 138

142 137

141 136

140 135
200 400 600 800 1000 1200 1400 200 400 600 800 1000 1200 1400
Temperature (K) Temperature (K)

Fig. 3. Zirconia monoclinic (A) and orthorhombic (B) unit cell volume dependences with temperature.

Please cite this article in press as: G. Sponchia, et al., Orthorhombic phase stabilization and transformation
phase process in zirconia tantalum-doped powders and spark plasma sintering systems, J Eur Ceram Soc (2017),
http://dx.doi.org/10.1016/j.jeurceramsoc.2017.04.017
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Table 2
Linear t parameters for P21 /c and Pca21 phases volume CTE calculation.

P21 /c Intecept Slope R-Square V0 (3 ) (106 K1 )

Literature 139.339 0.001 0.003234 0.000001 1.000 140.287 23.1

ZT3 140.6 0.1 0.0035 0.0001 0.989 141.6 24.7
ZT5 140.8 0.1 0.0037 0.0001 0.988 141.9 26.1

Pca21 Intecept Slope R-Square V0 (3 ) (106 K1 )

ZT3 134.0 0.1 0.0048 0.0001 0.994 135.4 35.4

ZT5 134.28 0.01 0.00454 0.00001 0.998 135.61 33.5
ZT8 135.0 0.1 0.0044 0.0001 0.986 136.3 32.3

3.3. Raman spectroscopy Table 3

The Raman spectroscopy results are in complete agreement
with the ndings obtained from X-ray powder diffraction. As shown
in Fig. 4, for the sake of simplicity, it is possible to divide the Raman
spectra into three different groups: low (ZT1 and ZT3), middle (ZT4
and ZT5) and high dopant-content spectra. At a rst glance, the rst
group reveals the presence of the monoclinic structure as the dom-
inant phase. This symmetry is distinguishable by 18 Raman peaks
corresponding to 18 Raman modes of the monoclinic structure [59].
Unlike the XRPD pattern, a second phase is still not detectable in
the Raman spectrum of sample ZT3, even though we observe a peak
broadening.
The second group, ranging from 4 to 5 mol% of tantalum dop-
ing (ZT4 and ZT5), clearly shows the coexistence of the monoclinic
structures with a different polymorph. In particular, we can observe
new weak lines in the low-frequency range at 146, 170, 180,
208 cm1 (marked with a cross +) that could be characteristics of
an orthorhombic system [39,50,52]. Moreover, also the 359, 405
and 593 cm1 peaks can be ascribed to the new phase referred
from now as orthorhombic. At the same time we can notice that
the intensity of the isolated monoclinic Raman modes at 96 and
475 cm1 (marked with a star *) contemporaneously decrease. This
spectral features indicates that the orthorhombic phase content
increase, while progressively decrease the monoclinic one. Above
5 and up to 20 mol% of Ta doping, the related peaks to the mono-
clinic polymorph is not clearly detectable, especially those at 96 and
475 cm1 , so its presence can be ruled out. Finally, the third group
(ZT8, ZT12 and ZT20) spectra proles differ slightly among them,
maintaining the features of the orthorhombic symmetry discussed.
Raman spectroscopy spectra, keeping in mind the XRPD results
and literature data, are now discuss. First, the Pbcm geometry can
be excluded as a candidate for the orthorhombic phase, since sev-
eral authors [33,52] consider it not a reliable structure for a stable
polymorph of zirconia [60]. Also the Pnam, structure, seems to
give a quite different spectrum pattern, having different vibration
modes [49], and thus can be excluded as well. Moreover, the Pbca
Raman spectrum reported by different authors does not exactly
match with the spectra obtained experimentally in this work, even
though, in the rst range of the spectra, new frequencies are not
clearly distinguishable due to the overlap with those of the mon-
oclinic symmetry. Therefore, according to the results obtained by
the analysis of the XRPD patterns, we focused our attention only
on the Pca21 symmetry for the description of the phase. In fact,
if we look at the Raman spectra of the high concentration dopant
series (i.e 820 mol%), the main change in the Raman spectra, as a
result of subsequent Ta doping, consists in a continuous broaden-
ing and shifts of the peaks frequency. This is a common observation
Bulk density of SPS specimens. In brackets are reported the percentage of the bulk
density with respect to the theoretical density calculated account of the phases
content estimated by Rietveld renement.
Bulk density (g/cm3 )
SPS1150 series SPS1250 series
ZT5SPS 5.965 (96.8%) 6.094 (98.9%)
ZT8SPS 6.262 (98.8%) 6.340 (99.5%)
ZT12SPS 6.505 (98.1%) 6.547 (98.8%)
monoclinic (P21 /c) to orthorhombic transformation requires only
a slight structural change, being the coordination the same for the
two structures. Nevertheless, it has only been observed in his pure
form as a high-pressure polymorph [39,41,42,52,60] or as isolated
island on a sapphire substrate [33]. In this work we observed for
the rst time the Raman spectrum of this new intermediate phase
at room temperature and at normal pressure. Of course, prediction
of the Pca21 Raman modes by rst-principles calculations will help
to elucidate and conrm the spectra associated to this structure.
3.4. Sintered SPS specimens
Two series of specimens have been prepared labeled as SPS1150
and SPS1250. The experimental conditions for the preparation of
the two series are a compromise to prepare high-density material
at the lower temperature possible.
As clearly reported in Table 3, the density of the specimen with
the same composition, determined by weight measurements, is
higher in the SPS1250 series. Fig. 5 shows the WAXS patterns of all
the samples. The volume fractions of the crystalline phases were
calculated from the Rietveld analyses. Table 4 reports the values
relative to the monoclinic phase. The values are similar for the two
series. Conversely to the patterns of the powder samples, the mon-
oclinic phase is present also in the samples with the higher amount
of Ta (8, 12 mol%) and its amount decreases increasing the dopant
from 5 to 12 mol%.
The two sintering temperatures do not stabilize only the
orthorhombic phase, even if they are higher than 1000 C. Fig.
S2 shows the different crystalline phases content for the differ-
ent experimental conditions. This nding suggests that in the
more dense sintered material, a higher doping content is neces-
sary to stabilize completely the orthorhombic phase. Probably the
Table 4
Confrontation between statistical estimation of dark zones in SEM images and
volume fractions of monoclinic phase calculated by Rietveld renement in SPS
specimens.

in Raman spectroscopy of solid solutions when disorder due to SPS1150 series SPS1250 series
a substituting dopant is introduced in the crystal structure [61].
BSE dark zones% WAXS P21 /c% BSE dark zones% WAXS P21 /c%
As different authors recently suggested [62,63], the orthorhom-
bic phase should be considered as mandatory intermediate step ZT5SPS 55 4 53 3 61 4 59 3
ZT8SPS 38 4 41 3 40 4 42 3
in the monoclinic to tetragonal phase transformation. Actually
ZT12SPS 11 2 10 3 13 4 11 3

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ZT20

Normalized Intensity (a.u.)

ZT12

ZT8
+
+ +
++ + + + +
* ZT5

+ +
+ *
++ + + +
* + ZT4
*
* ZT3
*
* ZT1

100 200 300 400 500 600 700 800

-1
Raman Shift (cm )

Fig. 4. Raman spectra of the powder samples. The star-marked (*) peaks are related to monoclinic phase, the cross-marked (+) peaks are related to orthorhombic one.

A B

ZT12 ZT12

ZT8 ZT8

ZT5 ZT5

15 20 25 30 35 40 45 50 55 60 65 70 15 20 25 30 35 40 45 50 55 60 65 70
2() 2()

Fig. 5. WAXS patterns of SPS specimens sintered at 1150 C (A) and 1250 C (B).

equilibrium temperatures of the phases for the powder and the
sintered samples are strongly related to the preparation method.
A SPS sample prepared at 1000 C with a uniaxial pressure of pre-
consolidation at 1.24 GPa (10tf ) showed the presence only of the
orthorhombic phase. However, its low bulk density (around 80%)
prevented any further mechanical tests. This underlines that ther-
modynamic equilibrium needs high temperature for a complete
stabilization of the phase.
Fig. 6 shows the FE-SEM images of the polished and annealed
surface of SPS specimens. In order to emphasize a compositional
contrast, the images have been recorded in Backscattered Electrons
(BSE) mode.
An evident weight contrast is visible on the polished surface of
the sintered specimens. This result supports the presence of a two-
phase system as anticipated by the XRD analysis of the powder
samples. The lighter zones are related to the heavier composition
grains, so they are richer in heavier element, i.e. Ta. The punctual
Energy Dispersive X-ray Spectroscopy (EDS) analyses of the two
zones (see SI Fig. S3), conrm a higher percentage of Ta on the
lighter grains. As reported in the discussion of the powder sam-
ples and considering tantalum as orthorhombic phase stabilizer,
the lighter grains are associated to the orthorhombic phase and the
darker to the monoclinic one. The results of the statistical analysis
of the volume fractions of the two phases, based on the grayscale
quantication of the two zones and made with the ImageJ pro-
gram, has been reported in Table 4. The quantitative estimation
matches very well also with the phase volume fractions calculated
by Rietveld renements.
In order to emphasize the grain boundaries the Secondary Elec-
trons (SE) mode, which displays a morphological contrast, has also
been used. Fig. 7 reports the comparison between the BSE and SE
mode of the same surface. It is evident that the two compositional
zones correspond perfectly to the grain structure and no mixed
phase grain are detectable. From the picture, the grain size D and the
shape factor F for the two different EDS zones have been estimated
(for the complete analysis see also SI) and reported in Table 5.
The larger size of the dark grains could be related to a faster
growth of the monoclinic phase or to a smaller number of nucle-
ation seed, meanwhile the shape factor indicates, for both the
phases, a similar growth path, without any preferential elongation.
From EDS analysis an estimation of the elemental percent-
age composition has also been determined. The quantitative

Please cite this article in press as: G. Sponchia, et al., Orthorhombic phase stabilization and transformation
phase process in zirconia tantalum-doped powders and spark plasma sintering systems, J Eur Ceram Soc (2017),
http://dx.doi.org/10.1016/j.jeurceramsoc.2017.04.017
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Fig. 6. FE-SEM images of SPS polished surfaces in BSE mode. Sample ZT5SPS1150 (A), ZT8SPS1150 (B), ZT12SPS1150 (C), ZT5SPS1250 (D), ZT8SPS1250 (E) and ZT12SPS1250
(F).

Table 6
Tantalum molar estimation from EDS peaks for different zone (dark ang light) and
global content (bulk).

SPS1150 series SPS1250 series

Ta% bulk Ta% dark Ta% light Ta% bulk Ta% dark Ta% light

ZT5SPS 51 21 15 1 51 21 15 1
ZT8SPS 81 21 16 1 81 21 16 1
ZT12SPS 12 1 21 16 1 12 1 21 15 1

It is worth noting that dark and light zones have a constant con-
tent of Ta independently from the main Ta content. In particular, the
dark zones, poor in Ta, can be associated to the monoclinic phase.
The light zone, instead, have a Ta content around 16 mol% that could
be identied as the minimal amount necessary to stabilizes the
orthorhombic phase in the sintered materials.
Keeping in mind also the results of the powder samples anal-
ysis, we can conclude that the heating treatments on ZrO2 -TaO2.5
Fig. 7. Comparison between FE-SEM image of polished surface of sample
structures induces the formation of a two-phase system of a poor
ZT8SPS1250 in SE (right) and BSE (left) modes. and a rich phase in Ta. The results of the sintered samples agree
with the previous evidences [46] and support also the ndings rel-
Table 5 ative to the powder samples [64]. For a system with 16 mol% of
SPS specimens grain size D statistical estimation and shape factor F. TaO2.5 , the heating treatments induce the formation of a single crys-
talline phase: the Pca21 orthorhombic phase. This seems contradict
SPS1150 series SPS1250 series
the literature on the existing ZrO2 -TaO2.5 phase diagram, where is
Dark grain Light grain Dark grain Light grain foreseen a single crystalline phase (orthorhombic) for sample with
D(nm) F D(nm) F D(nm) F D(nm) F an amount of TaO2.5 close to 25 mol% and corresponding to the
Zr6 Ta2 O17 phase reported by Kim [47]. In order to give a useful
ZT5SPS 550 80 0.69 320 60 0.66 600 80 0.69 350 40 0.68
ZT8SPS 560 70 0.69 340 50 0.67 580 60 0.70 330 60 0.67 contribution to the problem, we prepared a powder sample with
ZT12SPS 540 50 0.68 350 40 0.67 590 30 0.69 340 30 0.68 25 mol% of TaO2.5 (Zr6 Ta2 O17 ), labeled in Fig. S4 as ZT25, using the
same co-precipitation synthesis reported in the present paper and
we compared it with a sample with 16 mol% of TaO2.5 labeled as
evaluation has been made on the peaks areas relative to Zr and Ta ZT16 sample. The Fig. S4 shows that the patterns are quite simi-
energy lines. In order to work on a more supercial signal, minimiz- lar and the orthorhombic Pca21 crystalline phase is the same for
ing the pear-shaped interaction volume, the lowest beam energy the two compositions, meanwhile the lattice parameters and the
(5 keV) has been used. The quantitative results, on the average com- atomic coordinates (see Table S1) are slightly different due to the
position of the specimens reported in Table 6, match very well the different doping amount. This can considered a signicant result,
nominal content of the as prepared powders. All the EDS spectra since we have evidenced that the range of stability of the single
are reported in Fig. S3 in SI. orthorhombic phase relative to the ZrO2 -TaO2.5 system has a lower

Please cite this article in press as: G. Sponchia, et al., Orthorhombic phase stabilization and transformation
phase process in zirconia tantalum-doped powders and spark plasma sintering systems, J Eur Ceram Soc (2017),
http://dx.doi.org/10.1016/j.jeurceramsoc.2017.04.017
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Fig. 8. Sintered zirconia (ZT12SPS1250) crack fractures FE-SEM image in BSE mode
(left) and normal mode (right).
limit (16 mol% instead of 25 mol% of TaO2.5 ) than the value reported
in literature [31,34,43,47]. The different dopant content was also
veried by EDS analyses (Fig. S5).
Finally, another interesting experimental feature related to
the different thermal behavior of the two phases, i.e. the mon-
oclinic phase expanded less than the orthorhombic phase, has
been observed. This means that, during the cooling, a detachment
between the two phases boundaries occurs. It could produce radial
micro-fractures around the inclusion, whose CTE is lower than that
of the main phase. In Fig. 8 fractures inside the sintered material
is clearly visible. It is also evident, as the fractures are correlated
with the lower weight fraction grains, i.e. the darker zone. These
fractures are probably generated during the cooling process, by the
lower thermal expansion of the monoclinic inclusion respect to the
matrix one. Once more, the dark zone, in the left BSE side of Fig. 8,
could be related to the monoclinic fraction of the materials.
4. Conclusions
Zirconia Ta-doped powders were prepared in order to explain
the pentavelent cation behavior into the zirconia lattice. No
extreme conditions were used during the synthesis of seven pow-
der samples with different amount of TaO2.5 ranging from 1 to 20
mol%. The samples with an amount of Ta higher than 8 mol% show
the stabilization only of the orthorhombic Pca21 phase. Below this
amount, the monoclinic phase P21 /c was also present. Three signif-
icant samples (ZT3, ZT5 and ZT8) were investigated also by in situ
synchrotron XRPD measurements, in order to compare the thermal
evolution of the orthorhombic phase respect to the monoclinic one.
Two-phase system, with the formation of a poor (monoclinic) and a
rich phase (orthorhombic) in Ta was consider in order to explain the
XRD patterns obtained at different temperatures. The phase rich in
Ta shows a higher Coefcient of Thermal Expansion. A Raman study
was also performed for all the samples. Sintered samples were also
prepared by SPS technique. SEM measurements evidence the pres-
ence of a two-phase system. Keeping in mind also the results of the
powder samples analysis, we can conclude that the heating treat-
ment on Ta-doped zirconia structures induces the growth of two
phases, one poor and one rich phase in Ta. The results of the sin-
tered samples, suggest a threshold amount (16 mol%) in order to
have the presence only of orthorhombic phase.
Please cite this article in press as: G. Sponchia, et al., Orthorhombic phase stabilization and transformation
phase process in zirconia tantalum-doped powders and spark plasma sintering systems, J Eur Ceram Soc (2017),
http://dx.doi.org/10.1016/j.jeurceramsoc.2017.04.017
Acknowledgements
The authors thank N. Mazzucco for the FE-SEM images and PhD
E. Ambrosi for EDS spectra. Financial support from Junta de Andalu-
cia under grant no. P12-FQM-1079 is gratefully acknowledge.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.jeurceramsoc.
2017.04.017.
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