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Lifetime estimation of a zirconia-alumina

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Lifetime estimation of a zirconiaalumina

composite for biomedical applications

Paride Fabbri a, , Corrado Piconi b,c , Emiliano Burresi a , Giuseppe Magnani a ,

Francesca Mazzanti a , Claudio Mingazzini a
a Faenza Technical Unit on Material Technologies (UTTMATF), ENEA, Faenza, Italy
b GHIMAS S.p.A. MeLab, Brindisi, Italy
c Institute of Orthopedics and Traumatology, Catholic University, Roma, Italy

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

Article history: Objectives. In this work long term stability of a zirconia toughened alumina (ZTA) composite
Received 5 April 2013 was investigated.
Received in revised form Methods. Accelerated aging tests under hydrothermal environment, in autoclave and hot
18 July 2013 water, at different temperature, was conducted on material sample. Tetragonal to mono-
Accepted 18 October 2013 clinic transformation was evaluated by XRD analysis and the monoclinic content was plot
Available online xxx as a function of the exposure time. The kinetic of transformation was studied by means
Mehl-Avrami-Johnson (MAJ) nucleation and growth model.
Keywords: Results. An activation energy for tetragonal to monoclinic transformation of 99 kJ/mol was
ZTA zirconiaalumina composite found by the Arrhenius plot of reaction rate, value in agreement with other bibliography
Low temperature degradation works regarding Y-TZP and alumina-zirconia composites. The in vivo hydrothermal stabil-
aging ity simulation, estimated by the obtained activation energy, predicts in 65 years the time
Tetragonal to monoclinic necessary to reach 25 vol% of monoclinic phase.
transformation Signicance. These results support the material suitability in biomedical eld, especially in
Lifetime prediction dentistry applications as implantology.
2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

components on 2000 lead to the practical abandon of this

1. Introduction
Yttria stabilized Tetragonal Zirconia Polycrystals (Y-TZP) were
introduced as load-bearing biomaterials several years ago,
with the aim to overcome the limitations in device design
due to the brittle fracture mechanics of monolithic alumina
[1]. The success of Y-TZP as a biomaterial was due to the
combination of high fracture toughness, strength, high wear
resistance and excellent biocompatibility [2]. However, it is
known that Y-TZP behavior is depending on environment and
condition of use. For this reason, its employ in ball heads for
Total Hip Replacements (THR) has given controversial results
[3] and the worldwide withdrawal of this kind of ceramic
material in orthopedics. Nowadays Y-TZP is mainly used in
dentistry for xtures, crowns and bridges, obtained by the
CAD/CAM milling of blanks [4].
Mechanical behavior of polymorph zirconia is strongly
dependent on the metastable nature of the tetragonal phase.
The stress-induced tetragonal-to-monoclinic (tm) transfor-
mation, in the zone ahead of a crack tip, results in increased
mechanical properties by energy-dissipative mechanisms and
in the inhibition of crack tip propagation [5]. Nevertheless,
due to the metastable nature, tetragonal zirconia based mate-
rials are susceptible to an unfavorable phase transformation
at low temperature, rst reported by Kobayashi et al. [6]. The
physico-chemical mechanism of the tetragonal to monoclinic

Corresponding author at: Via Ravegnana 186, 48018 Faenza (Ra), Italy. Tel.: +39 0546 678615; fax: +39 0546 678503.
E-mail address: paride.fabbri@enea.it (P. Fabbri).
0109-5641/$ see front matter 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.dental.2013.10.006

Please cite this article in press as: Fabbri P, et al. Lifetime estimation of a zirconiaalumina composite for biomedical applications. Dent Mater
(2013), http://dx.doi.org/10.1016/j.dental.2013.10.006
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transformation is now widely accepted and highlights the rel-
evance of oxygen vacancies in yttria stabilized zirconia. In
hydrothermal environment the water species (oxygen, hydro-
gen and/or hydroxyls) initially locate on oxygen vacancy sites
on the material surface, due to the yttria doping. It leads to
the contraction of lattice parameters, accumulation of ten-
sile stresses in the tetragonal grains and then stress-assisted
transformation [7]. The process, that starts on the surface,
than progresses into the material bulk, eventually leading to
the pullout of the surface grains [8].
The main consequences of LTD for Y-TZP materials are
the degradation of mechanical properties and wear resis-
tance. In view of their use as biomaterials, the kinetic of
LTD should be carefully assessed because this behavior is the
main limiting factor of the lifetime of zirconia-based com-
ponents and may result in catastrophic failures. So far, the
most promising application of zirconia as biomaterial is as
reinforcement in aluminazirconia composites [9]. The mate-
rials of this class are called zirconia toughened alumina (ZTA)
when alumina is the main component, either Alumina Tough-
ened Zirconia (ATZ), when zirconia is the main component.
The benets of alumina zirconia composite are the combi-
nation of the characteristics of alumina (high hardness, high
stiffness) with the above mentioned properties of zirconia, i.e.
the high strength and high toughness, with improvement of
slow crack growth resistance [10]. In addition, several studies
on aluminazirconia composite have remarked the positive
effect of alumina on the hydrothermal stability of tetrago-
nal zirconia phase [11,12]. This is mainly due to the elastic
modulus of alumina, almost twice the one of Y-TZP. Namely,
the introduction of alumina increases the matrix stiffness,
then the constraint that the matrix exerts on zirconia parti-
cles maintains them in the metastable tetragonal state [13],
thus acting as mechanical stabilizer. ATZ materials show
improved aging resistance vs Y-TZP; nevertheless these com-
posites still exhibit a certain degree of aging [14], whereas
ZTA materials can exhibit much better aging resistance than
monolithic Y-TZP [14,15]. Up to now, the major application of
ZTAs as biomaterials is in devices for hip and knee arthro-
plasty, while, in our knowledge, only a few aluminazirconia
composites are commercially available as structural ceram-
ics for dental devices [16]. During the past years, ENEA Faenza
Research Laboratories developed and tested a number of com-
positions in the zirconiaalumina system [17] that had been
showing excellent mechanical behavior joined to excellent
biological safety [18,19], making them suitable for the manu-
facture of implantable medical devices. The aim of this paper
is to evaluate, by accelerated aging tests, the resistance to the
hydrothermal degradation in a ZTA material with composi-
tion zirconia/alumina 40/60 wt%, selected among the ones in
above.
2. Materials and methods
Disk-shaped samples of zirconiaalumina composite
(40/60 wt%) have been obtained from powders of yttria-
stabilized zirconia (3YB, Tosoh, Japan), monoclinic zirconia
(TZ0, Tosoh, Japan), alumina (Baikalox SM8, Baikowski Chimie,
France) and chromia (Carlo Erba, Italy). The powders were
Please cite this article in press as: Fabbri P, et al. Lifetime estimation of a zirconiaalumina composite for biomedical applications. Dent Mater
(2013), http://dx.doi.org/10.1016/j.dental.2013.10.006
wet-mixed in a Turbula mixer, using distilled water and suit-
able dispersant agent to form stable dispersion. The resulting
stabilizer content in zirconia grains is 2 mol%. After batch
preparation, cylindrical samples were obtained by uniaxial
press at 60 MPa of the dry powder, followed by cold isostatic
press (CIP) at 150 MPa. Pressureless sintering was carried out
in air at 1550 C.
Hydrothermal degradation tests were performed in steam
and hot water, in accordance with the method proposed by
Chevalier et al. [20], that allows to obtain a reasonable pre-
diction of the increase of monoclinic fraction in vivo as a
function of the time [21]. Before aging tests, the samples were
ground and lapped with diamond paste up to 1 m. Densities
of sintered samples were determined by Archimedes method.
Microstructural characterization was performed by SEM-EDS
(Leo 438 VP, Leo Electron Microscopy Ltd ISIS 300, Oxford
Link) and by XRD analysis, in order to evaluate the monoclinic
phase content in the ceramic materials. Diffraction patterns
were collected by using Philips X-ray powder diffractometer
with BraggBrentano geometry and Cu K radiation (40 kV
and 35 mA). Low temperature degradation kinetics of the com-
posite was estimated by accelerated aging tests in saturated
steam in an autoclave (Vapor Matic 770/A, ASAL) at 134 C,
121 C and in hot water at 90 C.
Monoclinic content was assessed according to the follow-
ing equation, proposed by Toraya et al. [22]:
1.311 Xm
f = (1)
1 + 0.311 Xm
The integrated intensity ratio, Xm , was calculated using the
Garvie and Nicholson method [23] as follows:
Im (1 1 1) + Im (1 1 1)
Xm = (2)
Im (1 1 1) + Im (1 1 1) + It (1 0 1)
where Im (h k l) is the area of the peak associated to the plane
(h k l) of the monoclinic phase and It (h k l) is the area of the peak
associated to the plane (h k l) of the tetragonal phase.
The apparent activation energy Q was calculated by Arrhe-
nius equation:
 Q
b = b0 exp (3)
RT
where b is the reaction rate, b0 is a material constant, R is the
gas constant and T is the absolute temperature. The slope of
ln b plotted in function of the reciprocal of temperature gives
the apparent activation energy value for phase transforma-
tion.
3. Results
The nal density of the composite tested is close to 99.9%
of the theoretical density (4.6 g/cm3 ), calculated by the phase
method.
The microstructure of the composite (Fig. 1) is character-
ized by equiaxial grains. The average grain size, measured by
the linear intercept method according to the standard EN623-3
[24], are 0.5 m for zirconia and 0.8 m for alumina.
DENTAL-2268; No. of Pages 5
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Fig. 1 SEM image of the ZTA composite surface after

thermal etching.

Fig. 3 Monoclinic phase content, respect to the total

Table 1 Summary of the characteristics of the ceramic volume of zirconia, as function of aging time at different
material tested. temperatures. Solid lines represent the tting of the
Property Unit Value experimental data by the MAJ law. The dotted line
3 represents the in vivo aging simulation.
Density g/cm 4.6 (0.5)
Alumina grain size m 0.8
Zirconia grain size m 0.5
Bending strength (4 points) [17] MPa 800 (90) peaks at low 2theta angle correspond to the monoclinic phase,
Citotoxicity, citocompatibility [18,19] Passed whereas the peaks intensity of the tetragonal phase is consid-
Carcinogenicity, mutagenicity [18,19] Passed
erably decreased. At this exposure time the surface monoclinic
Tissue reactions (local & systemic) [18,19] Passed
content reaches the saturation level, about 90% of the total
The main characteristics of the material are summarized zirconia, i.e. 28% of the entire volume of the ZTA composite.
in Table 1. In Fig. 3 the relations between monoclinic phase content and
The XRD pattern of a sintered sample, after grinding and aging time in the temperature range 90134 C are reported.
lapping, is shown in Fig. 2a. About 95% of the zirconia in the It can be noted that the amount of monoclinic phase, as
composite is in tetragonal phase, the balance being mono- function of the exposure time in hydrothermal environment,
clinic. These values represent the starting condition, before is represented by a sigmoidal curve. This trend could be related
the LTD tests. The XRD pattern of the sample after aging for to the nucleation and growth kinetics of the monoclinic phase.
3000 h in steam at 134 C is also shown in Fig. 2b. The highest First, the nucleation occurs in the most unstable grains on
the surface (with less stabilizer content and/or with large size
and/or subject to higher internal stresses). Then, in the growth
phase, the transformation propagates preferentially toward
the adjacent grains subject to tensile stresses [9].
This kinetics of transformation can be described by the
modied MehlAvramiJohnson (MAJ) law [25]:

n
f = fmin + (fmax fmin ) (1 exp((bt) )) (4)

where f is the monoclinic volume fraction, fmax is the max-

Fig. 2 XRD pattern of a ZTA sample before (a) and after (b)
3000 h of hydrothermal aging at 134 C. Unlabelled peaks
correspond to alumina phase.
imum volume fraction reached, fmin is the initial volume
fraction, t is the time, the Avrami exponent n is a constant
and b factor is the temperature dependent reaction rate.
The saturation level, fmax , which was derived by the curves
at 134 C and 121 C, was set equal to 0.9 and assumed constant
for the three LTD curves. The saturation level at 90 C was not
experimentally veried, because to obtain the complete trans-
formation of the isotermal curve would be necessary more
than 10 years.
The previous factors, n and b, were calculated by Eq. (4) with
an iterative procedure for each temperature. More in detail, the
MAJ exponent n, obtained by the iterative procedure for the
two complete curves, was found to be 0.85. The n factor could

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transformation occurs in preferential way by a nucleation

mechanism, rather than by growth of existing nuclei.
This behavior is reasonable for a ZTA composite, where the
propagation to the neighboring zirconia grains of the phase
transformation is limited by the presence of the alumina
grains. Similar value of n (0.78) was reported by Chevalier et al.
[21] for a commercial femoral head ZTA material.
The b value at 37 C was extrapolated from the Arrhenius
plot (Fig. 4) and used for calculating the in vivo aging behavior,
reported by the dotted line in Fig. 3. The in vivo aging sim-
ulation, obtained through accelerated tests in this range of
temperatures (90134 C), has been proved to be accurate and
useful for Y-TZP ceramics [9]. On the basis of the calculated
in vivo aging behavior, the time necessary to reach 25 vol% of
monoclinic phase, i.e. the amount indicated by the ISO stan-
dards [28], on Y-TZP based ceramic materials, as the acceptable
monoclinic content after accelerated tests, could be predicted
in 65 years. It is a much higher time than the reasonable life-
Fig. 4 Arrhenius plot of ln(b) versus 1/T allows the time of medical devices used in dentistry [29].
determination of the apparent activation energy Q. The favorable effect of alumina addiction in terms of LTD
resistance is conrmed, despite the aging process could not
be completely suppressed in 2 mol% yttria stabilized zirconia.
be assumed constant in the range of temperature 90134 C, Nevertheless, there are several aspects of the overall pro-
in agreement with the study reported by Chevalier et al. [26]. duction process that have to be taken into account for further
The b parameter for each temperature was deduced by improvements of the LTD resistance. Properties like density,
means of the above mentioned procedure. grain size as well as residual stress can dramatically affect the
According to the Arrhenius equation (3), the relation long term stability of the zirconia based-materials.
between ln(b) and 1/T should be linear and its slope gives the Even though it is expected that the effects of the
apparent activation energy. Arrhenius plot is shown in Fig. 4 microstructure should be more relevant in TZP materials
and provides an activation energy Q = 99 kJ/mol. rather than in aluminazirconia composites due to the stabi-
lization effect of alumina, future work should be addressed to
4. Discussion the change of the process parameters with the aim to obtain a
ner microstructure. Indeed, it is well-known that LTD resis-
The apparent activation energy obtained for this ZTA com- tance is strictly dependent on the zirconia grains size [9,34].
posite is very close to 100 kJ/mol, which is the mean value The best compromise in terms of improvement of degradation
for different kinds of zirconia based materials (3Y-TZP, ZTA, resistance and decreasing of mechanical properties will have
ATZ), as shown in Table 2. Our results conrm that the main to be dened considering the effects of the microstructure
mechanism of the tm transformation in humid environment renement on the phase transformation toughening [35].
is the same [26], even if the kinetic results slower, due to the
presence of alumina in the material. The increase in stiffness 5. Conclusions
of the matrix, due to the presence of alumina, enhances the
energy threshold for tm transformation of the grains, i.e. The low temperature degradation behavior of a zirconia tough-
the accumulation of higher tensile stresses is necessary to ened alumina composite was evaluated by accelerated aging
trigger the transformation [13]. Values of Avrami exponent tests in water and steam. The ZTA composite considered in
lower than 1, as obtained in this work (n = 0.85), are indicative this work exhibits an excellent resistance to hydrothermal
of an high nucleation/growth ratio [27]; in other words, the aging, i.e. the same monoclinic content is reached after
a much longer time than in other commercial 3Y-TZP or
aluminazirconia composites, as demonstration of the slower
Table 2 Activation energy for tm phase transformation kinetic process. The apparent activation energy mesured for
reported in literature. Value obtained in this work is YTZP in the composite is consistent with the values reported
reported for comparison. in the literature for other materials. The extrapolated lifetime
Author Ref. Material kJ/mol of the tested ZTA material conrms its suitability for the appli-
cation in endosseous implants and dental devices.
Chevalier J et al. [20] 3Y-TZP 106
Chevalier J et al. [21] ZTA 108
Shimizu K et al. [30] 3Y-TZP 89.9 Acknowledgements
Sato T, Shimada M [31] 3Y-TZP 93.8
Ueno M [32] 3Y-TZP 106.59
Schneider J et al. [33] ATZ 96.5 The authors are grateful to Dr. Paola Nitti (GHIMAS S.p.A.
Chevalier J et al. [26] 3Y-TZP with porous layer 96; 104 MeLab, Brindisi, Italy) for performing low temperature
This work ZTA 99 degradation and Dr. Alida Brentari (ENEA Faenza Technical

Please cite this article in press as: Fabbri P, et al. Lifetime estimation of a zirconiaalumina composite for biomedical applications. Dent Mater
(2013), http://dx.doi.org/10.1016/j.dental.2013.10.006
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Unit on Material Technologies UTTMATF, Faenza, Italy) for SEM
images. Prof. Zhijian James Shen (Arrhenius Laboratory, Stock-
holm University, Stockholm, Sweden) is kindly acknowledged
for his helpful comments on the manuscript.
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