Materials Characterization 132 (2017) 83–91

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Materials Characterization
journal homepage: www.elsevier.com/locate/matchar

Chemical segregation in a 12Ce-ZrO2/3Y-ZrO2 ceramic composite T

a,b,⁎ c,d c,d a,b c,d a,b
J.J. Roa , H. Aboulfadl , J. Barrirero , M. Turon-Vinas , F. Mücklich , M. Anglada
a
Universitat Politècnica de Catalunya, CIEFMA, Campus Diagonal Besòs - Edif. DBI, Av. d'Eduard Maristany, 10–14, 08019 Barcelona, Spain
b
Universitat Politècnica de Catalunya, Research Center in Multiscale Science and Engineering, Campus Diagonal Besòs - Edif. DBC, Av. d'Eduard Maristany, 10–14,
08019 Barcelona, Spain
c
Functional Materials, Saarland University, Campus D3-3, D-66123 Saarbrücken, Germany
d
Materials Engineering Center Saarland, Steinbeis Research Center, Campus D3-3, D-66123 Saarbrücken, Germany

A R T I C L E I N F O A B S T R A C T

Keywords: In restorative dentistry, 3Y-ZrO2 ceramics are widely accepted for fabricating dental crowns, bridges and im-
12Ce-ZrO2/3Y-ZrO2 composite plants due to their good biocompatibility, excellent mechanical properties and high aesthetics potential.
Chemical composition analysis However, they suffer from low temperature degradation (LTD) in the presence of water species, which generates
Wavelength-dispersive spectroscopy a loss in their surface mechanical integrity. If ceria is used instead of yttria, as in 12Ce-ZrO2, both higher fracture
Transmission electron microscopy (TEM)
toughness and resistance to LTD are achieved. The composition of solutes inside the grains and at the grain
TEM-electron energy loss spectroscopy
Atom probe tomography
boundaries is essential for understanding their role in LTD. In the present work, a microstructural study by
means of wavelength-dispersive spectroscopy, transmission electron microscopy and atom probe tomography
has been conducted by investigating the distribution of elements such as Ce, Y, Al and Zr in the solid solution of
zirconia that results from mixing 85 wt% 12Ce-ZrO2 and 15 wt% 3Y-ZrO2 and sintering at two different tem-
peratures, 1450 and 1600 °C. It is shown that the solid solution inside the grains after sintering at any of the two
temperatures is not homogenous, being closer to the expected equilibrium concentration when sintering at
1600 °C. Segregation of Ce, Y and Al to the grain boundaries is also analysed by atom probe tomography showing
that the segregations are stronger in the specimens sintered at the higher temperature.

1. Introduction toughness (KIC) of zirconia, is by doping with ceria instead of yttria.

Polycrystalline tetragonal zirconia stabilised with 3 mol% yttria
(3Y-ZrO2) is widely used for dental applications due to its extraordinary
mechanical properties, biocompatibility and aesthetics [1]. At room
temperature, the metastable tetragonal phase (t) can transform to the
monoclinic equilibrium phase (m) either activated by stress or by the
presence of water in the environment [2]. In the last case, the phe-
nomenon is referred to as hydrothermal ageing or low temperature
degradation (LTD), inducing surface micro-cracking and loss of surface
mechanical properties [3]. It starts at the surface and extends slowly
into the bulk with time, forming a thin surface layer of transformed and
micro-cracked material. This humidity assisted phase transformation
process is detrimental for those biomedical implants whose surface
integrity is of paramount importance for their functionality [4]. The
depth of the transformed and micro-cracked layer is of several microns
and is affected by the exact chemical composition of 3Y-ZrO2, porosity,
grain size, degradation temperature, time and pressure, as reported in
Ref. [3].
One way to improve both, the resistance to LTD and the fracture
Thus, zirconia with 12 mol% ceria (12Ce-ZrO2) results in substantially
higher resistance to LTD and higher KIC as compared to 3Y-ZrO2 [5,6],
being also more tolerant to damage by monotonic and cyclic contact
loading [7]. With respect to 3Y-ZrO2, the elastic modulus is very si-
milar, but the hardness and strength of 12Ce-ZrO2 are significantly
lower [8].
Alternatively, both higher KIC and resistance to LTD of zirconia
could also be achieved by preparing composites by mixing powders of
12Ce-ZrO2 and 3Y-ZrO2 with the objective of achieving a compromise
between the properties of the two stabilised zirconia solid solutions.
Thus, Nakahira and co-workers [9] prepared such composites by pres-
sureless sintering at 1400 °C and subsequently post-hot isostatic
pressing at 1350 °C in order to optimize KIC and the flexure strength.
For some compositions, they found an improvement in KIC and in the
resistance to LTD with respect to 3Y-ZrO2, with acceptable strength and
hardness. The sintered powder mixtures of yttria and ceria stabilised
zirconia had smaller grain size than 12Ce-ZrO2 with large inter-diffu-
sion between the Ce- and Y- rich powder particles, so that the sintered
material was considered rather a solution of Y and Ce elements in the

⁎
Corresponding author at: Universitat Politècnica de Catalunya, CIEFMA, Campus Diagonal Besòs - Edif. DBI, Av. d'Eduard Maristany, 10–14, 08019 Barcelona, Spain.
E-mail address: joan.josep.roa@upc.edu (J.J. Roa).

http://dx.doi.org/10.1016/j.matchar.2017.07.045
Received 6 March 2017; Received in revised form 25 July 2017; Accepted 31 July 2017
Available online 02 August 2017
1044-5803/ © 2017 Elsevier Inc. All rights reserved.
J.J. Roa et al.
zirconia matrix than a true composite. However, it is well known that
when processing zirconia with coated powders at similar or higher
temperatures, often significant different properties in terms of KIC are
found with respect to zirconia processed from co-precipitated powders
[10,11]. Furthermore, it is necessary to emphaticize for the Ce-ZrO2
system that the phase stabilization ability of CeO2 can deteriorate due
to a reduction process, from Ce+ 4 ➔ Ce+ 3 under the reaction of many
factors (e.g., sintering, local stress or glucose in oral cavity) and the
colour of Ce-ZrO2 will change, which are unfavourable for Ce-ZrO2
crowns from both mechanical and aesthetic point of views as reported
in Refs [12,13].
Within this context, these differences may be associated to non-
homogenous distribution of stabiliser solutes inside the grains and to a
higher segregation of solutes to the grain boundaries (GBs) in zirconia
processed from coated zirconia powders [14]. Therefore, it is of interest
to study whether by mixing powders of yttria and ceria stabilised zir-
conia the mixture is actually homogeneous at the nanometric scale after
sintering at the usual temperatures. Furthermore, segregation effects at
GBs in ceramic materials play an important role in many technologi-
cally important phenomena such as ionic conduction, corrosion, cata-
lysis, among others [15]. Segregation may also have an effect on
strengthening the GB as it has been observed, for example, with seg-
regation of aluminium in 3Y-ZrO2 [16,17].
The current report is then an attempt to evaluate the distribution
and segregation of elements such as Ce, Y and Zr through the grains and
the GBs of a 12Ce-ZrO2/3Y-ZrO2 mixture (with a fixed weight fraction
composition of 85/15), pressureless sintered at higher temperatures
than in Ref. [9], which leads to improve the ageing resistance and the
fracture toughness with respect to 3Y-ZrO2. In addition, the distribution
of elements usually added in small concentrations to 3Y-ZrO2 has
proven to be effective to increase the resistance to LTD and improve
densification.
In doing so, advance characterization techniques like wavelength-
dispersive spectroscopy (WDS), transmission electron microscopy
(TEM) as well as high resolution-TEM (HRTEM) and atom probe to-
mography (APT) are used. TEM and HRTEM have been previously
employed to investigate the chemical distribution in a local region in
zirconia [18]. APT is applied for the first time in tetragonal zirconia for
3D element mapping with near atomic resolution to detect local fluc-
tuations in concentration of solutes.
2. Experimental Procedure
2.1. Sample Preparation
The starting commercial powders, supplied by Daiichi Kigenso
Kagatu Kogyo (Japan), used in the preparation of the specimens were
12Ce-ZrO2 (ZrO2 with 12 mol% CeO2, CEZ-12 SD), 3Y-ZrO2 (ZrO2 with
3 mol% Y2O3, HSY-3FSD), with a purity ranged between the
99.0–99.8%. Both present small concentrations of Al2O3 (about 0.25 wt
%).
Two different sets of experiments were performed for determining
the chemical composition, diffusion and segregation effects. First,
layers of 12Ce-ZrO2/3Y-ZrO2 were prepared by depositing one powder
in a mould, uniaxially pressing to 100 MPa, and repeating the process
with the other powder. The layers formed in this way were later sin-
tered at 1450 and 1600 °C for 2 h in order to determine the diffusion
through the interface at these two sintering temperatures.
At the same time, powders of 12Ce-ZrO2 and 3Y-ZrO2 were mixed
and the chemical composition of the resulting grains and GBs were
analysed after sintering at the same temperatures as for the layers. In
this case, ceramic powders were mixed in the proportion 85 wt% 12Ce-
ZrO2 and 15 wt% 3Y-ZrO2 (from now on, referred to as “the mixture”)
and they were ball milled during 24 h in ethanol by using as grinding
media 10 mm diameter zirconia balls.
After drying, specimens in the shape of short pellets were uniaxially
84
Materials Characterization 132 (2017) 83–91
cold pressed at 100 MPa and sintered for 2 h at the same temperatures
and time as the layers. Heating and cooling rates were always main-
tained constant at 3 °C·min− 1, obtaining disks of 9 mm diameter and
2 mm thick. According to the nominal composition and weight fractions
of the powders employed, the average composition of the main ele-
ments in the sintered specimens should be close to 29.50 Zr, 66.50 O,
3.36 Ce and 0.32 Y in at. %, which gives Y/Zr and Ce/Zr ratios of 0.011
and 0.114, respectively.
Prior to the microstructural and chemical characterization, the
specimens were initially ground and polished using silicon carbide
paper, diamond suspensions until 1 μm, and colloidal silica as final step.
The quality of the final surface was carefully checked by confocal laser
optical microscopy in order to avoid the presence of scratches on the
surfaces prior to testing. Finally, all specimens were cleaned ultra-
sonically with acetone for 10 min and dried with pure air.
2.2. Microstructural Characterization
2.2.1. Wavelength Dispersive Spectrometry
Electron probe X-ray microanalysis (EPMA) using WDS was used to
conduct chemical profiles through the 12Ce-ZrO2/3Y-ZrO2 layer inter-
face after sintering using a JEOL JXA-8230 microprobe. The X-ray
profiles were recorded in high-resolution mode, using a channel width
of 1 eV. Electron currents were selected to ensure that counting rates
were < 104 counts·s− 1. More information about the protocol followed
to conduct this analysis can be found elsewhere [19,20].
For each sample, at least ten measurements along the interface
profile and three different profiles across the interface were conducted
per specimen. The distance between each measurement was kept con-
stant and equal to 2 μm, with counting times that ensured a statistical
uncertainty lower than 1%.
2.2.2. Transmission Electron Microscopy
A lamella for TEM was extracted by focused ion beam (FIB, Zeiss
Neon 40) from the composite resulting from mixing the powders for
each sintering temperature, and the milling was carried out at 30 kV
and 2 pA. Existing microstructures within the FIB-milled lamellas were
examined by scanning transmission electron microscopy (STEM) cou-
pled to the same FIB equipment mentioned above. Chemical analysis
through the GB was assessed first by means of TEM using a field
emission tube with electron energy loss spectrometer (EELS, in a JEOL
JEM 2100) for the sintered sample at 1600 °C. More information related
to EELS technique is described elsewhere [21].
2.2.3. Atom Probe Tomography
A dual-beam FIB (FEI Helios nanolab 600) was employed to prepare
APT specimens by the lift out technique, described in Ref. [22]. A final
milling step at low voltage (2 kV) was performed to minimize Ga+
implantation. APT measurements were conducted in a LEAP™ 3000X
HR (CAMECA) at specimen temperature of about 40 K, laser energy of
0.4 nJ, pulse repetition rate of 100 kHz, and target evaporation rate of
0.005 ions·pulse− 1. An average of 15 million ions was detected in all
the measurements carried out. The data collected were analysed using
the IVAS™ 3.6.8 software package. Chemical analyses of regions close
and across the grain boundary were carried out using one dimensional
concentration profiles and proximity histograms.
2.2.4. Low Temperature Degradation and XRD Analysis
Two samples of the mixture sintered at 1450 and 1600 °C were
subjected to accelerated hydrothermal ageing in an autoclave in contact
with water vapour atmosphere at 134 °C and 2 bar during 72 h, which
is roughly equivalent to a longer degradation time than a human life-
span [23]. Monoclinic content was analysed by means of X-ray dif-
fraction (XRD), with a diffractometer (Philips MRD) using Cu Kα1
(40 kV and 30 mA) radiation. The spectra analysed were obtained at a
scan rate of 10 s·step− 1, with a scan size of 0.017° over the range of 20
J.J. Roa et al.
Fig. 1. EPMA/WDS quantitative concentration profiles of Y (black) and Ce (blue) through
the 12Ce-ZrO2/3Y-ZrO2 interface after sintering at 1450 °C (a) and 1600 °C (b). (c)
Corresponding Zr profile at the two sintering temperatures. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this
article.)
85
Materials Characterization 132 (2017) 83–91
to 80° 2θ.
3. Results
The density of the mixture after sintering was above 98% of the
theoretical density for both sintering temperatures. The grain size after
sintering at 1450 °C (from now on referred to as MS1450) was
0.85 ± 0.1 and 2.35 ± 0.2 μm after sintering 1600 °C (referred to as
MS1600) as was already reported [8].
3.1. Inter-diffusion in the 12Ce-ZrO2/3Y-ZrO2 Layers
Fig. 1 presents quantitative concentration profiles for Zr, Y and Ce
through the 12Ce-ZrO2/3Y-ZrO2 interface obtained by WDS chemical
analysis after sintering at 1450 and 1600 °C, respectively, in air atmo-
sphere. Other temperatures (1350 and 1400 °C) were also used for
sintering the layers, but only those employed for sintering the mixtures
of powders are presented here in order to gain insight on the magnitude
of diffusion of the above elements at these temperatures. They exhibit
clearly a diffusion zone around the interface (marked by vertical dashed
lines) with a width of about 7.2 μm at 1450 °C and 14.4 μm at 1600 °C,
while the composition away from the interface remains constant and
consistent with average concentration ratios calculated from the nom-
inal composition of the raw powders from which the layers were pre-
pared (see Table 1).
It can be seen that inside the diffusion zone of Fig. 1 the chemical
composition has substantially changed by the diffusion of Ce in 3Y-ZrO2
and of Y in 12Ce-ZrO2. This region is wider after sintering at 1600 °C as
shown in Fig. 1b. The concentration profile of Zr measured through the
12Ce-ZrO2/3Y-ZrO2 interface is presented in Fig. 1c, where it is evident
a diffusion from the 3Y-ZrO2 to 12Ce-ZrO2 layer for the specimen sin-
tered at 1600 °C (see red arrow).
3.2. Sintered Powder Mixtures: Solid Solution and Segregation Effects at the
Grain Boundary
Additional information on high temperature processes may be
gathered from examining the chemical composition and segregation
effects of the sintered powder mixtures in the microstructure by means
of advanced characterization techniques, e.g. STEM, TEM + EELS and
APT.
3.2.1. Composition Within the Grains of the Sintered Powder Mixtures
A local compositional analysis for the main elements present after
sintering the powder mixtures was made by means of APT in 6 APT
specimens of MS1450 and in 4 APT specimens of MS1600. Fig. 2 shows
a tomographic slice from an APT reconstruction inside a MS1450 grain.
The distribution of the elements of interest (Al, Zr, O and Ce) is
homogeneous. The datasets were examined using frequency distribu-
tion analysis [24] where the Pearson coefficient showed near zero va-
lues, confirming a random distribution of the main elements.
It is important to note that in the MS1450 sample the Y peaks were
sometimes not detected in the mass spectrum. Although from the
nominal chemical concentration of the powders, the nominal average
concentration of Y, if a homogenous solution was formed, should be
about 0.32 at.%. The mass spectrum background level of these mea-
surements was about ~ 60 ppm/ns, which can indicate that Y peaks
might be below the background level. Mass spectrum quality of laser
assisted APT is discussed in Ref. [25].
Table 2 shows the composition measured inside the grains of
MS1450 sample which all showed to be homogeneous. The grains were
1–2 μm in size but the GBs were not clearly visible during the lift out
preparation, therefore there is a chance that two measurements are
from within the same grain. Relatively large differences in Ce content
were found in the different volumes analysed with an average value
equal to 3.86 ± 0.34 at.%.
J.J. Roa et al. Materials Characterization 132 (2017) 83–91

Table 1
Zr, Y, and Ce content together with Y/Zr and Ce/Zr ratios.

Position T (°C) Zr (at.%) Y (at.%) Ce (at.%) Y/Zr Ce/Zr

Nominal composition of 3Y-ZrO2 – 31.7 1.96 – 0.062 –

Nominal composition of 12Ce-ZrO2 – 27.82 – 3.81 – 0.137
Sintered 3Y-ZrO2 layer 1450 °C 29.3 ± 0.5 2.0 ± 0.1 – 0.068 ± 0.005 –
1600 °C 30.3 ± 0.3 – 0.066 ± 0.004
Sintered 12Ce-ZrO2 layer 1450 °C 28.1 ± 0.6 – 4.1 ± 0.1 – 0.146 ± 0.007
1600 °C 28.9 ± 0.3 – – 0.142 ± 0.005

Because of the higher sintering temperature used for MS1600, a
more similar composition to the equilibrium value is expected in the
specimens analysed due to homogenization. Indeed, the mean compo-
sition from the four measurements show Ce levels closer to the expected
equilibrium concentration (3.36 at.%), see Table 3. This is also reflected
in the average ratio Ce/Zr which is now 0.114 as expected if the re-
sulting mixture of powders was a homogeneous solution. In this case,
because of the larger grain size, it is more likely that two measurements
here were extracted from the same grain.
In the APT analysis of the 1600 °C sample clear Y peaks (Y+ 3) were
detected in the mass spectrum, nevertheless the concentration of Y was
still lower than the nominal composition expected (0.32 at.%) for a
homogenous solution, so that Y was non homogenously distributed.
The APT analysis has also revealed traces of Hf and Al in the
samples. Hf is commonly found mixed with Zr in most minerals that
contain Zr [26], whereas Al has migrated from the alumina in the
starting powders. The level of Al inside the grains of MS1450 and
MS1600 given in Tables 2 and 3, respectively, tend to be more homo-
genous than the levels of Ce and Y, since both starting powders have
similar alumina composition. However, the measured Al level is lower
than expected, which may be related to the low solubility of alumina in
zirconia [27], and partly to segregation to the GBs (shown below).
3.2.2. Segregation at the Grain Boundary
It is well known that combining TEM and EELS, it is possible to
characterize the chemical segregation at the grain boundaries for ZrO2
based ceramic materials as reported in Ref. [14]. For this reason, in this
section the distribution of stabilizing elements in the resulting 12Ce-

Fig. 2. APT reconstructions of the MS1450 sample. A tomo-

graphic slice of the 3D map atom map is show for Al, Zr, O and
Ce atoms. Similar results (not shown here) are found for the
MS1600 specimen.

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J.J. Roa et al. Materials Characterization 132 (2017) 83–91

Table 2
Composition for the main elements investigated (O, Zr, Ce, Al and Hf) obtained by APT inside the specimens of MS1450.

Element (at.%) Specimen 1 Specimen 2 Specimen 3 Specimen 4 Specimen 5 Specimen 6 Mean

O 69.78 ± 0.03 69.04 ± 0.03 70.98 ± 0.03 69.25 ± 0.03 70.73 ± 0.03 69.10 ± 0.03 69.81 ± 0.85
Zr 25.60 ± 0.02 26.52 ± 0.02 25.24 ± 0.02 26.42 ± 0.02 25.07 ± 0.02 27.05 ± 0.02 25.98 ± 0.79
Ce 4.28 ± 0.02 4.13 ± 0.01 3.47 ± 0.01 4.02 ± 0.01 3.77 ± 0.02 3.50 ± 0.02 3.86 ± 0.34
Hf 0.25 ± 0.01 0.24 ± 0.01 0.23 ± 0.01 0.23 ± 0.01 0.37 ± 0.01 0.29 ± 0.01 0.27 ± 0.05
Al 0.06 ± 0.01 0.06 ± 0.01 0.07 ± 0.01 0.07 ± 0.01 0.05 ± 0.01 0.06 ± 0.01 0.06 ± 0.01
Si < 0.01
Fe < 0.01

Table 3
Composition for the main elements investigated (O, Zr, Ce, Al and Hf) obtained by APT inside the grains of MS1600.

Element (at.%) Specimen 1 Specimen 2 Specimen 3 Specimen 4 Mean composition

O 69.27 ± 0.05 68.95 ± 0.04 69.41 ± 0.04 70.88 ± 0.04 69.63 ± 0.86
Zr 26.96 ± 0.03 27.20 ± 0.03 26.90 ± 0.03 25.68 ± 0.03 26.69 ± 0.68
Ce 3.27 ± 0.02 3.46 ± 0.02 3.33 ± 0.02 3.04 ± 0.03 3.28 ± 0.18
Hf 0.23 ± 0.01 0.19 ± 0.01 0.23 ± 0.01 0.18 ± 0.01 0.21 ± 0.03
Y 0.15 ± 0.01 0.06 ± 0.01 0.02 ± 0.01 0.11 ± 0.01 0.10 ± 0.06
Al 0.09 ± 0.01 0.12 ± 0.01 0.09 ± 0.01 0.08 ± 0.01 0.10 ± 0.02
Si < 0.01
Fe < 0.01

Fig. 3. STEM micrographs (dark field mode) of the

composite sintered at: (a) 1450 °C and (b) 1600 °C. (c)
a) c) b) Magnification from the white square region marked in
Fig. 3a. (d) EELS profile through the interface and
spectra from the region marked in Fig. 3c.

1 μm 1 μm

c) d)
EELS map
Intensity (a.u)

Energy (eV)

87
J.J. Roa et al. Materials Characterization 132 (2017) 83–91

a) exhibiting several grains with a band along the GB (Fig. 3c) which could
Grain A
be related to segregation of impurities. By analysing the region of the
insert shown in Fig. 3a, it can be seen that the width of the band ranges
between 1 and 2 nm. From the chemical analysis of this region by EELS,
a chemical map presented in Fig. 3d was obtained, which exhibits a
doublet Ce peak signal (880.5–889 and 898.5–908.5 eV) which does not
change when crossing the GB. In this regard, it is not possible to discern
whether Ce segregation occurs at the GB or whether it changes its
Grain B oxidation state (see Fig. 3d). On the other hand, using EELS, the Y L2,3
peak could not be detected because it appears at an energy loss around
2080 eV [28].
Therefore, as the spot size employed in these measurements through
the interface was of similar size as the region of interest, it was not
possible to quantify the amount of Ce at the GB as well as the change of
chemical composition in the region of interest, see white square present
in Fig. 3a. For this reason, APT was used since this technique can yield
reliable chemical composition determinations on GB segregations.

3.2.3. APT Analysis of GB Region for MS1450

APT reconstruction images of part of two grains, A and B, with a
common GB, are shown in Fig. 4a for MS1450. The compositional one
dimensional profiles of Zr, Y, Al and Ce across the GB are shown in
Fig. 4b. In the reconstruction with a GB present, Y+ 3 peak was detected
b) in the mass spectrum, where traces of Y are detected in the grain, at the
proximity GB region, but more segregated at the GB. This is in contrast
with the previously analysed MS1450 specimens extracted from the
interior of the grains (distant from GBs). It can be seen also that Al and
Ce segregate to the GB and that the width over which segregation is
observed for both elements has a thickness of nearly 5 nm, similar to
GB that observed by STEM (Fig. 3a). The maximum concentrations of Al
and Ce at the GB are about 0.5 and 1 at.% higher, respectively, than in
the grain interior close to the GB. At the same time, there is a very slight
decrease of about 0.6 at.% in the concentration of Zr in the GB (not
shown here). Fine traces of Fe and Si impurities were also segregated to
the GB (Fig. 4c). The concentration difference between the GB and the
grain interior was small for Y, Fe and Si, being 0.018, 0.020 and
0.073 at.%, respectively.

3.2.4. APT Analysis of GB Region for MS1600

c)
Fig. 4. APT analysis of GB region for MS1450 sample. (a) A tomographic slice showing
the distribution of Zr, Al, Y and Ce. (b) Concentration profiles plotted across the GB (c)
Low chemical concentration profiles across a GB for Y, Fe and Si.
ZrO2/3Y-ZrO2 mixtures was characterized by STEM and TEM + EELS
and the influence of the doping elements (e.g. Al and Ce) distribution
on the microstructure were also investigated.
Firstly, STEM observations and TEM analyses were conducted in
MS1450 and MS1600 in order to gain a clear picture of the composition
inside the grain and at the GBs. Fig. 3 displays the STEM micrographs
For the MS1600 mixture, the 3D-reconstruction of the main ele-
ments, as well as the proximity histogram showing the concentration
profiles of O, Al, Y, Zr, Hf, Si, Ce and Fe across the GB are presented in
Fig. 5. Now the relative concentrations of Y close to the GB are different
in two neighbouring grains as shown in Fig. 5, being several times
higher in one grain than in the adjacent grain. Other elements in
MS1600 show also stronger segregations to the GB than in MS1450 (see
Fig. 5a). The composition of Y and Al at the GB is about 0.3 and 0.7 at.
%, respectively. This level of Al is more than seven times higher than
the concentration measured inside the grain. Regarding the Ce level, its
concentration profile is plotted on a finer scale in Fig. 5c. Note that the
Ce content is close to 4.5 at.% at the GB, while inside the two adjacent
grains, A and B, is 0.8 and 1.5 at.% lower, respectively. Finally, in
contrast with the segregation of Ce to the GB in MS1600, there is a
depletion in Zr as is highlighted in Fig. 5d.
Table 4 summarizes the average chemical composition of the main
elements in two neighbouring grains A and B, for MS1450 and MS1600
mixtures from small volumes in the interior but not far away from the
GB. Again, the level of Y is lower than the composition expected for a
full homogeneous solution.
3.3. Resistance to LTD
MS1450 and MS1600 have very strong resistance to LTD. This is
evidenced by the absence of monoclinic peaks in the X-ray diffraction
patterns after 72 h ageing in autoclave (see Fig. 6).

88
J.J. Roa et al. Materials Characterization 132 (2017) 83–91

Grain A Fig. 5. APT analysis of GB region in MS1600 sample. (a) Tomographic slice showing the
a) distribution for Zr, Al and Ce. (b) Chemical concentration profile across a GB. (c)
Concentration profile magnified across the GB showing that the local concentration of Ce
is up to about 1 at.% higher. (d) Concentration profile magnified across the GB for Zr.

Table 4
Chemical composition of two neighbouring grains A and B analysed by APT in the vicinity
of the common GB. Balance is formed mainly by traces of Si and Fe.
Grain B
Element (at. MS1450 MS1600
%)
Grain A Grain B Grain A Grain B

O 69.70 ± 0.03 69.10 ± 0.03 70.64 ± 0.06 69.70 ± 0.06

Zr 26.30 ± 0.03 26.90 ± 0.03 25.35 ± 0.06 26.30 ± 0.06
Ce 3.60 ± 0.02 3.60 ± 0.02 3.15 ± 0.04 3.50 ± 0.05
Y 0.02 ± 0.01 0.02 ± 0.01 0.16 ± 0.02 0.04 ± 0.01
Al 0.06 ± 0.01 0.08 ± 0.01 0.33 ± 0.01 0.18 ± 0.01
Hf 0.28 ± 0.01 0.31 ± 0.01 0.31 ± 0.01 0.39 ± 0.01
Others Balance Balance

• (101)t • (002)t ‡ (200)t ▲ (112)t ■ (202)t □ (220)t

♦ (113)t ◊ (331)t ○ (222)t ▼ (004)t ► (400)t

b)
*

Grain A GB Grain B ■
‡ ◊
Intensity (a.u.)

□
• ♦
▲ ○ ▼►

■
‡ ◊
□
• ♦
○ ▼►
c) ▲

∆C [Ce] = 0.8 at.%

2θ (º)
∆C [Ce] = 1.2 at.% Fig. 6. XRD analysis of MS1450 and MS1600 after being exposed to autoclave for 72 h.

4. Discussion

The present results provide insight into the diffusion of the main
GB elements of 12Ce-ZrO2/3Y-ZrO2 layers at micrometric length scale, as
Grain A Grain B well as GB solute segregation phenomena at the atomic scale. The
present WDS data show that inter-diffusion of the main elements of
both powders at 1450 or 1600 °C is in principle rapid enough for drastic
changes in concentration at depths of several microns below the initial
d) layer interface.
Distribution of the stabiliser elements in the sintered powder mix-
tures will depend on the homogeneity of the distribution of the powders
after compaction. If the mixture 85/15 of the starting powders was fully
homogenous and all particles were of the same small size, one could
∆C [Zr] = 5.7 at.% think of the powder mixture as one where each Y-rich particle is in
contact with about six neighbouring particles of the preponderant Ce
∆C [Zr] = rich powder. At the two sintering temperatures, both powders are
3.6 at.% capable of being sintered to near full density so that diffusion at the
point of contact is large enough to produce strong joins and the usual
GB large sintering shrinkage of the pellets. Then, diffusion between parti-
Grain A Grain B cles of the different powders will take place reducing locally the ori-
ginal gradient concentration in Ce and Y. At longer times, this gradient
will be further decreased and eventually a homogenous concentration
might be reached in all the volume, as far as the tetragonal phase is the

89
J.J. Roa et al.
only equilibrium phase at the sintering temperature. Then the resulting
composition, neglecting grain boundary segregations, can be calcu-
lated.
Solute compositions appeared homogenous inside the APT re-
constructions of all specimens analysed, but the composition levels
changed from specimen to specimen. This is related to the fact that APT
datasets have very small volumes of the order of 10− 4 μm3, that is,
about 4 orders of magnitude smaller than the actual volume of a grain.
At this scale the composition is homogenous.
In spite of the important diffusion observed in the layers, homo-
genization in the mixture of powders was not reached, even in MS1600.
The reason may be, at least in part, agglomeration of particles of the
same powder, so that the distribution of particles at the microscale is far
away from the ideal homogenous distribution described above. For
example, the presence of agglomerates of mainly Ce-rich particles will
make diffusion of Y more difficult from the minority Y-rich particles to
the centre of the Ce-agglomerates. This may be the reason for the Ce/Zr
ratio determined in MS1450, which is similar to that of the starting Ce-
rich powder.
Apart from the possibility of having extremely low Y content in
MS1450 which could be below the mass spectrum background level,
another reason for the very low Y concentration that was generally
detected in those APT specimens might be from agglomerates to the
starting Ce-rich powder without sufficient diffusion of Y to the matrix.
However, in APT specimens for which the level of Ce is found below the
initial composition of the Ce-rich powder, the presence of Y by diffusion
from Y-rich particles should be detected. The reason why this is not
generally the case may be that the six APT specimens of MS1450 were
never extracted from regions originated from the Y-rich powder, as this
is the minor constituent of the mixture.
In MS1600 there is the possibility of the appearance of small
amounts of stable cubic phase with different composition. There is al-
ways some uncertainty on the border between the tetragonal field and
the tetragonal + cubic field in the ZrO2- the CeO2-Y2O3 phase diagram,
but it is clear that if the solution was homogeneous at both sintering
temperatures the corresponding concentration is inside the tetragonal
field of the equilibrium phase diagram [10,29]. The Y + Ce composi-
tion is the highest at the GBs of MS1600 (4.5 at.% Ce, 0.3 at.% Y and
only 22 at.% Zr, with Ce/Zr and Y/Zr ratios of 0.2 and 0.014, respec-
tively). The stabiliser content is then high enough for cubic phase nu-
cleation at the GB at 1600 °C [30]. However, the specimens analysed
with high Ce content also had low Y content so that impoverishment in
both Ce and Y in some regions and enrichment in others has not been
detected, which would be the consequence of the nucleation of cubic
grains.
The resistance to stress-activated phase transformation and to
moisture-activated phase transformation (resistance to LTD), are very
different in the two components of the mixtures. In 12Ce-ZrO2 t-m is
easily activated by the stress, but it has a strong resistance to LTD, while
the opposite occurs in 3Y-ZrO2. Since after sintering, the grain size of
the mixture is intermediate between the grain sizes of monolithic 3Y-
ZrO2 and 12Ce-ZrO2 [8], and the chemical composition is not homo-
geneous at the grain size scale, the overall effect could change locally
the resistance to LTD and the fracture toughness of the mixture. The
details will depend on the local composition achieved of mainly Y + Ce
and also on the volume scale in which the chemical composition is
changing. It is then important to know the distribution of the main
stabiliser elements after the different sintering temperatures. From the
results of LTD and from the fracture toughness of the mixture which is
intermediate between that of the monolithic ceramics, it is clear that
the distribution of solute is such that both LTD resistance and fracture
toughness increase with respect to 3Y-TZP [8].
In MS1450 grains with composition still very close to the initial Y-
rich powder are not expected to be resistant to LTD, but this has not
been detected. The reason may lie in the small fraction of Y-rich powder
in the mixtures (15%) as well as the volumes where this take place are
90
Materials Characterization 132 (2017) 83–91
probably very small so that the stress for producing a plate of mono-
clinic phase is high. This explains why no monoclinic phase is detected
after 72 h of hydrothermal degradation.
At atomistic level, the different data presented in the above section
clearly show the GB segregation of Al, Y and Ce for both sintering
temperatures. Segregations detected at the GBs may shed light on the
understanding of the role of GBs for retarding the LTD of ZrO2 based
ceramic materials. These results are consistent with previous works that
have shown that alumina segregates to the GBs and can retard the
degradation of ZrO2 materials [31–33] due to the oxygen vacancy de-
pletion at the GB [34,35] without compromising the mechanical
properties [14,36]. The presence of Al and Y at the GB has been de-
tected before using high-resolution transmission electron microscopy
techniques [37,38]. The qualitative and quantitative segregations to the
GB reported here in MS1600 for Y and Al, respectively, are in agree-
ment with the work of Ross and co-workers [14] on the study of seg-
regation to the GB of Y-TZP by means of EELS.
Segregation at the GB is accelerated when sintering at 1600 °C,
finding high concentrations of Y, Ce and Al, as shown in Fig. 5 and
summarized in Table 4. APT analysis highlights that the main elements
investigated here are segregated to the GB, while for Zr there is a re-
lative impoverishment (see Fig. 5c). Qualitatively this result is in the
line of the work of Zhang et al. [39], who found by EDS-STEM that Zr+ 4
was slightly depleted around the GB. This result highlights that at the
GB the composition is rather different from the interior and closer to the
composition expected for a cubic phase.
With respect to the influence of Si segregation to GBs on the me-
chanical properties and resistance to LTD, it has been shown that the
addition of small amounts of silica improves greatly the resistance to
LTD of 3Y-ZrO2 because of the presence of a glassy phase at triple
junctions which acts to reduce the internal stresses [40]. Iron, an im-
purity in the powders, was found also to segregate to the GBs, which
might also contribute to LTD resistance, but requires further studies.
Regarding the presence of Ce in the GBs it should be noticed that
Ce+ 4 and Zr+ 4 have the same valence and not very different atomic
radii (0.97 and 0.84 Å) so that no strong driving force for segregation
may be present. This has been shown in the past by Boutz et al. [41]
who could not find significant segregation of cerium in Y, Ce-TZP in the
range of temperatures between 1150 and 1400 °C by studying the in-
tergranular fracture surfaces by X-ray photoelectron spectroscopy
(XPS). However, it is well known that the oxidation state of Ce, above
1400 °C may be increasingly present in two possible oxidation states,
tetravalent and trivalent [41,42]. The fraction of Ce+ 3 in ceria in-
creases strongly above 1400 °C. Besides different valence than Zr+ 4,
has a much larger ionic radius (1.143 Å) so that if Ce+ 3 is increasingly
present at temperatures higher than 1400 °C, its concentration into the
GBs should increase for decreasing their electrostatic and strain energy.
This also agrees with the observation with the larger presence of Ce+ 3
at higher temperatures.
5. Conclusions
From the chemical analysis for Ce, Y and Zr by means of WDS, TEM
+ EELS and APT of the 85 wt% 12Ce-ZrO2 and 15% 3Y-ZrO2 mixtures
sintered at two different temperatures (1450 and 1600 °C), we can draw
the following conclusions:
- APT analysis reveals a homogeneous distribution of the elements
inside the small volume specimens analysed. However, the compo-
sition measured in each specimen is, in general, different. In the
mixture sintered at 1450 °C, they are specimens for which the con-
centration is close to the original Ce-rich powder, while in others is
lower but always higher than the expected homogeneous mean
homogeneous composition. Smaller fluctuations in the concentra-
tion of Ce are still present after sintering at 1600 °C but the mean
composition is closer to the equilibrium homogenous value.
J.J. Roa et al.
- For both sintering temperatures, a significant segregation to the GB
takes place. Sintering at 1600 °C results in higher concentrations of
impurities segregated to the GB, mainly Al, but also Y and Ce, as
well as other minor elements such as Fe and Si. Segregations are
expected to vary according to the nature of the GB.
- Ce was found to be a common segregation element along the GBs for
both temperatures, which might have also some influence on the
strength of the GB. More work is needed to explore this possibility.
Acknowledgements
Authors greatly acknowledge the MAT2014-60720-R and the
European project CREATe-Network (RISE Project N° 644013), sup-
ported by the Spanish “Ministerio de Economía y Competividad” and by
the European Commission within the RISE Program, respectively. We
are grateful to “Secretaria d'Universitats i Recerca de la Generalitat de
Catalunya” for financial support (2014-SGR-130). The atom probe in-
strument was financed by the Deutsche Forschungsgemeinschaft (DFG)
and the Federal State Government of Saarland (INST 256/298-1 FUGG).
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