The influence of grain size on low-temperature degradation

of dental zirconia

Lubica Hallmann,1 Albert Mehl,2 Peter Ulmer,3 Eric Reusser,3 Johannes Stadler,4
Renato Zenobi,4 Bogna Stawarczyk,1 Mutlu Özcan,1 Christoph H. F. Hämmerle1
1
Clinic of Fixed and Removable Prosthodontics and Dental Material Science, Center of Dental Medicine,
University of Zürich, Zurich, Switzerland
2
Clinic of Preventive Dentistry, Periodontology and Cariology, Computer Assisted Restorations,
Center of Dental Medicine, University of Zürich, Zurich, Switzerland
3
Institute of Geochemistry and Petrology, ETH Zürich, Switzerland
4
Department of Chemistry and Applied Biosciences, ETH Zürich, Switzerland

Received 13 July 2011; revised 29 August 2011; accepted 6 September 2011

Published online 25 November 2011 in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/jbm.b.31969

Abstract: The purpose of this study was to evaluate the
influence of grain size and air abrasion on low-temperature
degradation (LTD) of yttria stabilized tetragonal zirconia poly-
crystalline (Y-TZP). Disc-shaped specimens were sintered at
1350, 1450, and 1600
C. Air abrasion was performed with dif-
ferent abrasive particles. The specimens were stored for 2 h
at 134
C under 2.3 bar water vapor pressure. All specimens
were characterized by X-ray powder diffraction analysis
(XRD), Raman spectroscopy, X-ray photoelectron spectros-
copy (XPS), atomic force microscopy (AFM), and field emis-
sion scanning electron microscopy (FESEM). Y-TZP sintered
at a temperature of 1350
C did not undergo the t–m phase
of Zr-OH and Y-OH bonds. No increase of yttrium concentra-
tion on the grain boundaries of Y-TZP was detected, which
could be responsible for the destabilization of dental zirconia
ceramics. A slight increase of diffusion-controlled t–m phase
transformations was observed for all abraded specimens sin-
tered at 1350 and 1450
C. The size of abrasive particles did
not play a crucial role on LTD of Y-TZP. The retardation of
diffusion-controlled t–m phase transformation was evident
for all abraded specimens sintered at 1600
C by comparison
to non-abraded specimens. Conclusion: The LTD of Y-TZP
can be suppressed when the sintering temperature is set
between 1350 and 1450
C. VC 2011 Wiley Periodicals, Inc. J Biomed

transformation during accelerated aging. The diffusion-con-
trolled t–m phase transformation initiated with the specimens
sintered at 1450
C. This transformation was remarkable for
the specimens sintered at 1600
C. X-ray photoelectron spec-
troscopy (XPS) measurements did not confirm the generation
Mater Res Part B: Appl Biomater 100B: 447–456, 2012.
Key Words: dental zirconia (Y-TZP), degradation, grain size,
air abrasion, tensile stress

How to cite this article: Hallmann L, Mehl A, Ulmer P, Reusser E, Stadler J, Zenobi R, Stawarczyk B, Özcan M, Hämmerle CHF. 2012. The
influence of grain size on low-temperature degradation of dental zirconia. J Biomed Mater Res Part B 2012:100B:447–456.

INTRODUCTION of a number of zirconia hip joints has drawn the attention

Dental zirconia ceramic, consisting of 3 mol % yttria stabi-
lized tetragonal polycrystalline zirconia (Y-TZP), has excel-
lent mechanical, biomedical, aesthetic properties with its
semitranslucent and radiopacity features.1–3 The develop-
ment of CAD/CAM systems, the increase in aesthetic
demand and, worries about metallic hypersensitivity have
increased the application of Y-TZP in dentistry. Y-TZP has
extraordinary strength and toughness due to the transfor-
mation from the tetragonal to the monoclinic polymorph
when external stress is applied.4,5 For these reasons, Y-TZP
is used to substitute the traditional metal-based fixed dental
prosthesis (FDPs). Zirconia full-ceramic copings, FDP frame-
works, and implant suprastructures are introduced to
replace the traditionally used metals.4 However, the failure
of researchers to the behavior of Y-TZP ceramics in humid
environments. Fractures are often associated with a large
amount of monoclinic phase created during tetragonal–
monoclinic phase transformation in the human body.6,7 This
transformation reduces the mechanical properties of Y-TZP
and is known as low-temperature degradation (LTD).6 The
spontaneous transformation from the tetragonal into mono-
clinic structure initiates on the surface of Y-TZP via a stress
corrosion type mechanism and proceeds to the bulk of the
ceramic.4,7 The principal mechanism of LTD is diffusion-con-
trolled, while the t–m modification transformation, once
nucleated, is martensitic.4 The transformation proceeds
most rapidly at temperatures of 200–300
C.8 The destabili-
zation of the tetragonal phase is accompanied by the

Correspondence to: L. Hallmann; e-mail: lubica.hallmann@zzm.uzh.ch

V
C 2011 WILEY PERIODICALS, INC. 447
formation of micro- and macrocracks and is dependent on
the concentration of the stabilizer, and the grain size of ce-
ramic.6–10,11
Y-TZP undergoes a stress-induced volume-expansion
phase transformation during air abrasion. Flaws or micro-
cracks can thereby be introduced in the Y-TZP surface.12,13
The pre-existing monoclinic phase on the air-abraded Y-TZP
surface hinders the propagation of the diffusion-controlled
transformation during accelerated aging.4
The aging of zirconia is a serious problem for the ortho-
pedic community.4 In conventional dental applications, the
zirconia core or framework is not in contact with the oral
environment and hard dental tissues due to veneering and
luting materials and the problem seems not to be predomi-
nant.4 However, the luting resin could absorb water via den-
tal tubules and the zirconia core and framework exposed to
water may suffer from aging degradation.4 Additionally,
more and more fully ceramic zirconia restorations are
inserted, where zirconia surfaces are directly opposed to
the intraoral environment.
Several theoretical causes have been proposed to explain
the mechanism of LTD. Sato et al. suggested the chemical
reaction of water with Zr-O-Zr bonds at the pre-existing sur-
face flaws.9 This reaction is associated with the formation of
Zr-OH bonds, releasing the strain that stabilizes the tetragonal
phase, thus promoting the t–m phase transformation.9 The
phase transformation starts at the surface and propagates
into the interior.9 According to Lange et al., the water reacts
with Y2O3 at the surface of the zirconia and clusters of
Y(OH)3 are formed, leading to the depletion of stabilizers
from the grains and the spontaneous t–m transformation
takes places in the grains.10 Yoshimura et al. explained the
degradation of Y-TZP with the annihilation of oxygen vacan-
cies and about 60% of these vacancies are occupied by OH–
anions.14 The OH– anions would migrate faster than O2–
because of less charge and similar size.14 These authors did
not accept the depletion of yttrium as the result of Y(OH)3
formation or the dissolution of Y3þ during hydrothermal
treatment. According to Hughes et al., the generation of O2– is
responsible for the rapid annealing of surface oxygen vacan-
cies.15 The penetration of O2– into the lattice destabilizes the
t-phase and the transformation or nucleation of the m-phase
domains occurs.15 Oxygen vacancies play an important role in
the stabilization of the metastable tetragonal and cubic struc-
ture.16 Fabris et al. employed a self-consistent tight-binding
model to constrain that the stabilization of the cubic and tet-
ragonal structure could be achieved by introducing oxygen
vacancies into the zirconia lattice.17 Guo related the LTD with
annihilation of oxygen vacancies that stabilize the metastable
tetragonal phase through the OH– group.18 Chevalier proposes
that the filling of oxygen vacancies with O2– and not OH– ions
may be responsible for low-temperature degradation of zirco-
nia.6 The O2– ions originate from the dissociation of water on
the surface of Y-TZP ceramic.6
The processes of low-temperature degradation (LTD)
can effectively be simulated at 134
C, under a water vapor
pressure of 2 bar. One hour of this treatment corresponds
roughly to 4 years of aging in human environment.7
448 HALLMANN ET AL.
Therefore, the purpose of the present study was to
evaluate the effect of grain size, flaws, and pre-existing
monoclinic phase created during air abrasion on the low-
temperature degradation (LTD) of dental Y-TZP ceramic
under above-mentioned conditions. One of the most impor-
tant factors on LTD mechanism of dental zirconia is tensile
strain, which is grain size dependant. An additional goal of
this study was to test the idea that flaws, micro-cracks, and
pre-existing monoclinic phase play a certain role on the LTD
of Y-TZP, but the most important factor is the critical grain
size. An attempt was made to ascertain the proper mecha-
nism of LTD during the accelerated aging of Y-TZP ceramic.
The working hypothesis was that the resulting LTD of Y-TZP
ceramic under hydrothermal condition is not primarily con-
trolled by the concentration gradient of yttrium on grain
boundaries and/or the Zr-OH and Y-OH bonds formation
resulting from OH– anion diffusion, but critically depends on
the species that diffuse rapidly in the lattice of Y-TZP
ceramic.
MATERIALS AND METHODS
Specimen preparation
Y-TZP ceramic blanks (Cercon base, DeguDent, Hanau, Germany)
(ZrO2, 5% Y2O3, < 2% HfO2, < 1% Al2O3 þ SiO2) were cut
with a cutting machine (Precision Diamond Wire Saw, Well,
Switzerland) into discs (diameter: 25 mm, thickness: 3 mm)
under copious water (n ¼ 216). The specimens were
sintered in a programmable oven (Cercon heat, DeguDent,
the sinter temperature was set to 1350
C for 2 h). Other
specimens were sintered at 1450 and 1600
C for 2 h
with heating and cooling rates of 10
C/min (Nabertherm,
Switzerland). The specimens were divided randomly into six
main groups and each main group was divided into four
subgroups (see Table I). The specimens were abraded with
different air-borne particles (50 and 110 lm alumina,
30 and 110 lm silica-coated alumina particles) at a pres-
sure of 2.5 bar for 15 s/cm2 from a distance of 10 mm
(LEMAT NT4, Wassermann, Germany).
After air abrasion, all specimens were first air-blown at
a pressure of 3 bar for 1 min and then ultrasonically
cleaned in 99.8% isopropanol (Merck, Darmstadt, Germany)
for 20 min (Brasonic Ultrasonic Cleaner, Danbury) at a
frequency of 42 kHz.
The acceleration aging of specimens was performed
under autoclave conditions of 134
C and a water vapor
pressure of 2.3 bar for a duration of 2 h (GETINGE industriv
5 SE-471 31 Skärhamn, Sweden).
Ceramic veneering simulation was performed in an oven
(Austromat M, Dekema, Freilassing, Deutschland) at 830
C
for 1 min. The heating rate was set to 55
C/min. Additional
ceramic veneering simulations were conducted at 820, 810,
and 800
C. The holding time for these temperature treat-
ments was 1 min and the heating rate was 45
C/min.
Phase transformation
Tetragonal (t)–monoclinic (m) phase transformations of Y-
TZP ceramics were analyzed with X-ray powder diffraction
technique (Bruker, AXS D8 Advance) using Cu Ka1 X-rays.
LOW-TEMPERATURE DEGRADATION
 ORIGINAL RESEARCH REPORT

TABLE I. Preparation of Specimens (72 Groups With Each n ¼ 3 Specimens)

Specimens Treatment

Y-TZP sintered at 1350, Main group a

1450, and 1600
C Subgroups:
a0 control specimens
a00 aged specimens
a000 aged specimens þ first ceramic veneering stimulation
a0000 aged specimens þ fourth ceramic veneering stimulations
Main group b
Subgroups:
b0 abraded specimens with 50 lm alumina particles
b00 abraded specimens þ aging
b000 abraded and aged specimens þ first ceramic veneering stimulation
b0000 abraded and aged specimens þ fourth ceramic veneering stimulations
Main group c
Subgroups:
c0 abraded specimens with 110 lm alumina particles
c00 , c000 , c0000 the specimens are treated as specimens of main group b
Main group d
Subgroups:
d0 abraded specimens with 30 lm silica-coated alumina particles
d00 , d000 , c0000 ; the specimens are treated as specimens of main Group b
Main group e
Subgroups:
e0 abraded specimens with 110 lm silica-coated alumina particles
e00 , e000 , c0000 the specimens are treated as specimens of main group b
Main group f
Subgroups:
f0 abraded specimens with 110 lm alumina particles followed by 110 lm silica-coated
alumina particles (Rocatec system)
f00 , f000 , f0000 the specimens are treated as the specimens of main group b

Ceramic veneering simulation was performed at 830
C with heating rate of 55
C/min and 820, 810, and 800
C with heating rate of 45
C/min.
The holding time was 1 min for each temperature.

The diffraction profiles were acquired from 25.5 to 29
(2h)
with a step size of 0.001
and counting time of 2 s/step,
and from 25 to 37
(2h) with a step size of 0.006
and
counting time of 2 s/step.
Raman spectroscopy was additionally employed to inves-
tigate the t–m phase transformation. High-resolution AFM
and confocal Raman measurements were conducted on a
combined confocal Raman system and AFM instrument
(Spectra Ntegra upright, NTMDT, Russia) equipped with a
100  0.7 NA objective (Mitutoyo, Japan), a 632.8 nm HeNe
laser (up to 3 mW), a 100  100  10 lm piezo scanner,
and non-contact cantilever-based AFM probes (ATEC-NC,
NanoSensors, Switzerland) for atomic force microscopy.
Surface elemental composition
The surface chemistry of the specimens was investigated by
means of X-ray photoelectron spectroscopy (XPS). The anal-
yses were performed with a PHI Quantera SXM (ULVAC-PHI,
Chanhassen, MN) spectrometer. All XPS spectra were
collected at an emission angle of 45
using a beam size of
200 lm with a power of 50 W in the constant–analyzer–
energy (CAE) mode. High-resolution spectra were acquired
using a pass energy of 55 eV and a step size of 0.1 eV (full-
width-at-half-maximum (FWHM) of the peak height for Ag
3d5/2 0 0.64 eV). Survey spectra were collected with a pass
energy of 280 eV and a step size of 1 eV. A high-perform-
ance, floating-column ion gun, and an electron neutralizer
were used for charge compensation. The residual pressure
in the analysis chamber was below 5  10–7 Pa. The spec-
trometer was calibrated according to ISO 15472:2001 with
an accuracy of 60.1 eV.
Surface topography
The topography of the Y-TZP ceramic surface before and af-
ter aging was investigated using AFM and FESEM. The
images were acquired using a BRUKER N8 RADOS scanning
probe microscope as follows:
• Aged specimens which were sintered at 1350 and
1600
C: N8 RADOS equipped with NANOS 806, 80  80
lm2 maximal scan area, 6 lm Z-range, active vibration
isolation, acoustic enclosure.
• Sintered specimens at 1350 and 1600
C: N8 NEOS
equipped with NANOS 806, (80  80 lm2) maximal scan
area, 6 lm Z-range.
• Measurement Parameters:
* Dynamic (intermittent contact) mode.
* Free amplitude was varied between 10 and 170 nm.
* Damping set point was varied 58 and 70%.
* Scan speed: 0.5 line per second.
The phase images were acquired simultaneously with
the topography images.

JOURNAL OF BIOMEDICAL MATERIALS RESEARCH B: APPLIED BIOMATERIALS | FEB 2012 VOL 100B, ISSUE 2 449
FIGURE 1. XRD patterns of Y–TZP specimens before and after aging at the range of 27.5–29
(2y). [Color figure can be viewed in the online
issue, which is available at wileyonlinelibrary.com.]
FESEM experiments were carried out with a Carl Zeiss
Supra 50 VP FESEM (Oberkochen, Germany). The accelera-
tion voltage of the cathode was 5–30 kV. All specimens
were palladium gold coated before FESEM examinations.
RESULTS
Phase identification
Figure 1 displays the X-ray diffraction pattern (XRD) of Y-
TZP sintered at various temperatures (1350, 1450, and
1600
C) over the range 27.5–29
(2h) before and after
aging. The profiles are zoomed in this range because the
t–m phase transformation can visually be identified. For
specimens sintered at 1350
C, the t–m phase transformation
after aging for 2 h at 134
C and under water vapor pres-
sure of 2.3 bar, was not observed [Figure 1(a), plot a00 ],
whereas the specimens sintered at 1450 and 1600
C
showed the t–m transformation [Figure 1(b,c), plots a00 ].
After air abrasion with different air-borne particles, a
detectable monoclinic peak with orientation m(11-1) was
discernable [Figure 1(a–f), plots; b0 –f0 ]. The intensity of this
peak was increased after accelerated aging for abraded
specimens [Figure 1(a–f), plots b00 –f00 ]. In contrast, the inten-
sity of these peaks decreased after the ceramic veneering
simulation at 830
C for 1 min. [Figure 1(b–f), plots a000 –f000 ].
The highest extent of t–m phase transformation was
observed for Y-TZP sintered at 1600
C. A retardation of the
450 HALLMANN ET AL.
t–m phase transformation was evident for all the abraded
specimens sintered at 1600
C in comparison with non-
abraded specimens [Figure 1(c,f)].
Figure 2 reveals the effect of low-temperature degrada-
tion (LTD) at 134
C under a water vapor pressure of 2.3
bar of Y-TZP ceramic sintered at different temperatures over
a range of diffraction angles from 25 to 39
(2h). The X-ray
diffraction patterns of non-aged and aged specimens sin-
tered at 1350
C are similar and clearly indicate the missing
of a t–m phase transformation [Figure 2(a)]. The effects of
accelerated aging on the t–m phase transformation for Y-
TZP ceramic sintered at 1450 and 1600
C are shown in Fig-
ure 2(c,e). Compared to the non-aged Y-TZP specimens, the
aged Y-TZP specimens sintered at 1600
C contains the high-
est concentration of the monoclinic phase. The reverse m-t
phase transformation took place after ceramic veneering
simulation. The intensity of the m(11-1) peak in this case
decreased accompanied by an increase of the t(111) peak
intensity. However, a small proportion of monoclinic phase
seems to be present in both cases, but for the specimen sin-
tered at 1600
C the amount of non-transformed monoclinic
phase was higher than for the specimen sintered at 1450
C
[Figure 2(c,e) and plots a0 , a00 , and a000 ]. After air abrasion,
the monoclinic peak m(11-1) and a remarkable t(111) peak
broadening accompanied by the reversed intensity of the
tetragonal t(002) and t(020) peaks were observed in all
LOW-TEMPERATURE DEGRADATION
 ORIGINAL RESEARCH REPORT

FIGURE 2. XRD pattern of Y–TZP specimens before and after aging at the range of 25–37
(2y). [Color figure can be viewed in the online issue,
which is available at wileyonlinelibrary.com.]

XRD patterns. After accelerated aging, the intensity of m(11-
1) peak was only slightly increased for the abraded speci-
mens sintered at 1350
C followed by the specimens sin-
tered at 1450
C, whereas the specimens sintered at 1600
C
resulted significantly higher t–m phase transformation [Fig-
ure 2(b,d,f,g)]. The intensity of the m(11-1) peak and
the broadening of the t(111) peak were reduced for all
specimens after the firths ceramic veneering stimulation.
After that no intensity change of the m(11-1) and t(111)
peaks was evident after the fourth ceramic veneering
stimulation.
Figure 3 presents Raman spectra of Y-TZP ceramic. It is
evident from the Raman spectra that major bands are
located at 141, 255, 315, 462, and 641 cm–1. The peak at
635 cm–1 has a shoulder at 603 cm–1. These peaks are char-
acteristic for the tetragonal phase of Y-TZP ceramic.19–22 The
peaks at 175 and 373 cm–1 are characteristic for a mono-
clinic structure.23–25 The weak peak at 550 cm–1 likewise is

JOURNAL OF BIOMEDICAL MATERIALS RESEARCH B: APPLIED BIOMATERIALS | FEB 2012 VOL 100B, ISSUE 2 451
 3d core level was not observed. Such a positive shift would
be indicative for the formation of M-OH bonds. No remark-
able change of the binding energy for the aluminium ion
was detected from the Al 2p spectra [Figure 4(e)]. Figure
4(f) shows the energy binding of the O 1s core level before
and after aging. The peak at low binding energy is assigned
to oxygen in the metal-O-metal bond. The shoulder at higher
binding energy 530.4–531 eV (Table III) could be assigned
to the OH bond, absorbed water, or oxygen–carbon bonds.

FIGURE 3. Raman spectra of Y-TZP specimens before and after aging.
[Color figure can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]
attributed to the monoclinic phase (Table II). Comparing plots
3a, b and c reveals that the distribution of the monoclinic
phase for aged Y-TZP sintered at 1600
C was not homogenous.
Surface elemental composition
The survey XPS spectra [Figure 4(a)] revealed that the ele-
mental composition of the Y-TZP ceramic surface did not
change after accelerated aging at a temperature of 134
C
under a water pressure of 2.3 bar for 2 h. The C 1s peak of
all the specimens resulted from an overlaying contaminating
hydrocarbon layer, which was unavoidable during XPS mea-
surement [Figure 4(b)]. Figure 4(c) compares the Zr 3d
spectra obtained before and after accelerated aging for the
Y-TZP sintered at three different temperatures. The binding
energies of Zr 3d3/2 and Zr 3d5/2 were 183.2–183.6 eV and
180.8–182.2 eV, respectively (Table III). The binding energy
of the Zr 3d core was shifted for 0.3 eV to negative values
for aged specimens sintered at 1600
C. The Y 3d spectra
are shown in Figure 4(d). The binding energy of Y 3d3/2
and Y 3d5/2 varied from 158.0 to 158.4 eV and 156.0 to
156.5 eV, respectively. The Y 3d core peaks were shifted for
0.4 eV to negative values for the samples sintered at
1600
C. A positive shift of binding energy for Zr 3d and Y
Surface topography
Figure 5 shows the AFM images of surface morphology of Y-
TZP ceramic, which was sintered at 1350 and 1600
C
before and after aging. No change of the surface morphology
and/or roughness of non-aged and aged Y-TZP ceramic, sin-
tered at 1350
C, was not observable. The roughness for
non-aged and aged Y-TZP ceramic surface was 10.37 and
8.97 nm, respectively. Figure 5(a0 –d0 ) presents AFM images
of the surface morphology of Y-TZP ceramic sintered at
1600
C, indicating that a change of grain topography
occurred as the grain surfaces were not flat after acceler-
ated aging. The monoclinic phase precipitated as dispersed
lenses in the tetragonal matrix phase. The roughness of Y-
TZP ceramic surface increased after accelerated aging to
9.75 and 15.3 nm for non-aged and aged Y-TZP ceramic
surfaces, respectively.
Figure 6 displays the FESEM images of non-aged and
aged Y-TZP ceramics, which were sintered at different tem-
peratures. The average grain size was small (about 0.21
lm) and not homogenous for the specimens sintered at
1350
C. The same applied to the specimens sintered at
1450 and 1600
C, with a grain size of 0.3 and 0.72 lm,
respectively. After accelerated aging, the grains of specimens
sintered at temperature1350 and 1450
C appeared not to
be uplifted in contrast to the specimen sintered at 1600
C.
The surface of aged Y-TZP sintered at 1600
C was damaged
as a result of volume increasing during t–m phase transfor-
mation and holes were created [Figure 6(f)]. Figure 6(h)
shows the precipitation of the monoclinic phase as dis-
persed lenses. The EDS measurements did not reveal any
change in the yttrium concentration before and after accel-
erated aging of Y-TZP ceramic sintered at different tempera-
tures. Screening of elemental composition for grain surface

TABLE II. Wave Number (in cm1) of Raman Vibration Bands for the Tetragonal and Monoclinic Structure of Y-TZP Ceramics

Specimens Tetragonal Phase

sh
Sintered specimen at 1350 C 141 254 314 458 601 637
Aged specimen (sintered at 1350
C) 141 254 314 458 601 sh
637
Sintered specimen at 1450
C 144 258 318 462 604 sh
641
Aged specimen (sintered at 1450
C) 143 257 316 462 604 sh
640
Sintered specimen at 1600
C 144 257 318 462 604 sh
640
(a) Aged specimen (sintered at 1600
C) 142 256 317 460 604 sh
639
(b) Aged specimen (sintered at 1600
C) 144 258 319 464 604 sh
640
(c) Aged specimen (sintered at 1600
C) 141 256 323 466 634
Specimens Monoclinic Phase
(b) Aged specimen (sintered at 1600
C 175 187 377
(c) Aged specimen (sintered at 1600
C) 175 187 374 549

452 HALLMANN ET AL. LOW-TEMPERATURE DEGRADATION

 ORIGINAL RESEARCH REPORT

FIGURE 4. XPS spectra of Y-TZP ceramic surfaces before and after aging. [Color figure can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]

and boundary concentration changes showed a homogenous
distribution of yttrium across the surface and no concentra-
tion gradient in the grain-boundary region was observed
(Table IV).
DISCUSSION
Low-temperature degradation (LTD) of dental zirconia by
annealing in water vapor is dependent on several factors
such as crystal structure, grain size, the amount of dopant,
residual stress. In this study, the stress-induced t–m phase
transformation of Y-TZP started at a sintering temperature
of 1450
C. The highest transformation rate observed for Y-
TZP ceramic sintered at 1600
C can be explained by
increased tensile stresses, as larger grain sizes correspond
to a larger tensile stress (this work will be soon submitted).
The grains of Y-TZP sintered at 1350
C were more spherical
than the grains of Y-TZP sintered at 1450
C, while the grains
of Y-TZP sintered at 1600
C were flattened and enlarged.
The stress distribution is more uniform for the spherical
grains than for the flat grains. The tensile and compressive
stresses are present in the sintered ceramic, but the ratios
of these stresses depend of the sintering temperature. The
slight increasing of the extent of the t–m phase transforma-
tion observed for aged ceramic sintered at 1450
C implies
that this ratio was changed in favor of tensile stress in com-
parison to the ceramic sintered at 1350
C.
Some groups of Y-TZP ceramic surfaces in this study
were abraded before accelerated aging. The aim was to
investigate the effect of micro-cracks that were introduced
on the Y-TZP ceramic surface during air abrasion. There are
studies which relate the propagation of the t–m phase
transformation to the creation of micro-cracks during accel-
erated aging.26,27 Micro-cracks served as preferential paths
for water diffusion inside the bulk of the Y-TZP ceramic.28
The air abrasion induced the t–m phase transformation,
plastic deformations, flaws, grooves, cracks, and impinging
of air-borne particles on the surface of the ceramic. The
compressive stresses created during the air abrasion serve
to inhibit micro-crack extension.4 Our study showed that
the air abrasion was responsible for the retardation of diffu-
sion controlled t–m phase transformation for Y-TZP ceramic
sintered at 1600
C. The slight increasing of the t–m phase

TABLE III. Binding Energies (in eV) of Zr 3d, Y 3d, Al 2p, and O 1s Core Levels

Specimens Zr 3d3/2 Zr 3d5/2 Y 3d3/2 Y 3d5/2 Al 2p O 1s O 1s

Sintered specimen at 1350 C 183.2 180.8 158.0 156.0 73.0 528.6 530.0
Aged sintered specimen at 1350
C 183.2 180.8 158.0 156.0 73.1 528.8 530.5
Sintered specimen at 1450
C 183.5 181.2 158.2 156.2 73.2 528.9 530.8
Aged sintered specimen at 1450
C 183.4 181.1 158.0 156.0 73.1 528.7 531.0
Sintered specimen at 1600
C 183.6 181.2 158.5 156.5 73.5 529.1 531.2
Aged sintered specimen at 1600
C 183.3 180.9 158.1 156.2 73.5 528.8 531.2

JOURNAL OF BIOMEDICAL MATERIALS RESEARCH B: APPLIED BIOMATERIALS | FEB 2012 VOL 100B, ISSUE 2 453
454
HALLMANN ET AL.
FIGURE 5. AFM images of Y-TZP ceramic surfaces before and after aging for specimens sintered at 1350 and 1600
C. [Color figure can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]

LOW-TEMPERATURE DEGRADATION

FIGURE 6. FESEM images of the specimens sintered at 1350, 1450, and 1600
C before and after aging.
transformation for aged Y-TZP sintered at 1350 and 1450
C
after air abrasion in comparison with non-abraded Y-TZP
ceramic can be explained by the different stresses which
predominate in these ceramics before and after air abrasion.
After air abrasion, this ratio changed in favor of tensile
stresses, which were responsible for contrasting behaviors
of sintered and abraded ceramics sintered at these tempera-
tures. The grain size of abrasive particles did not play a cru-
cial role on LTD of Y-TZP sintered at different temperatures.
The binding energy shift of a core-electron is related to
the change of the chemical environment of the element. The
negative shift of the Zr 3d binding energy for the specimen
sintered at 1600
C after aging in this study indicates a
change of the chemical state for the zirconium ion. Binding
energy reduction of a metal ion is an indication for an
increasingly covalent bond formation,29 whereas the forma-
tion of a Zr-OH bond shows a higher binding energy than
that of ZrO2 for the same oxidation state.30 It may therefore
be suggested that the partial reduction of Zr4þ to Zr3þ took
place and the conversion of ZrO2 to suboxides ZrOx
occurred during aging process.31 The lack of a positive shift
for the zirconium and yttrium ions shown in this study indi-
cated that Zr-OH and Y-OH bonds were not introduced into
the Y-TZP lattice. The lack of concentration gradients for yt-
trium ions at the grain boundaries does not support the
theory of LTD occurring through the depletion of yttrium
ions from the lattice of Y-TZP ceramic.
TABLE IV. Elemental Compositions in wt % of Non-aged and Aged Y-TZP Ceramic in Terms of Zr and Y
Zr (wt %)
Grain


Sintered zirconia at 1350 C 78.55
Aged zirconia (sintered at 1350
C) 78.37
Sintered zirconia at 1450
C 78.63
Aged zirconia (sintered at 1450
C) 79.35
Sintered zirconia at 1600
C 78.45
Aged zirconia (sintered at 1600
C) 78.69
JOURNAL OF BIOMEDICAL MATERIALS RESEARCH B: APPLIED BIOMATERIALS | FEB 2012 VOL 100B, ISSUE 2
ORIGINAL RESEARCH REPORT
The theoretical atomistic study of Kushima et al. con-
ducted to explain the mechanism of oxygen anion transport
in anion conducing ceramic reveled that the biaxial tensile
lattice stress is a very important factor for the migration of
oxygen vacancies by the hopping mechanism.28 The energy
barrier of migrating vacancies is affected by the migration
space, cation-oxygen bond strength, and additional factors.
The increase of cation–cation distances and the weakness of
the cation–oxygen bond strength decrease the migration
energy barrier of vacancies. The oxygen ions migrate after
the same mechanism as vacancies. These authors found that
the macroscopic oxygen diffusivity increases exponentially
in yttria stabilized zirconia up to a critical value of biaxial
tensile stress, especially at lower temperatures. Beyond this
critical value of lattice stress, the migration of oxygen
decreases due to local relaxation.28 The higher t–m phase
transformation rate during accelerated aging observed for
sintered Y-TZP at 1600
C in this study confirms their
calculations.
There is a debate32 about the species that are responsi-
ble for stress induced t–m phase transformation of Y-TZP ce-
ramic. The backward phase transformation m-t observed
during the first ceramic veneering simulation provides infor-
mation about these species. This transformation took place
very fast at the beginning and thereafter the reversible reac-
tion is retarded. The full reversible reaction took place at
higher temperatures only. This implies that the species that
Y (wt %)
Boundary Grain Boundary
78.70 7.08 7.12
77.97 6.85 6.91
78.48 7.04 7.35
79.27 7.12 7.21
78.31 7.47 7.78
78.96 8.53 7.78
455
are involved in this transformation moved very fast at first
and after that, due to the alteration of the lattice stress, the
migration barrier energy increased. The surface of Y-TZP
serves as a catalyst for the dissociation of water into O2–
and Hþ ions. Hþ ions, therefore, probably play a crucial role
on LTD of Y-TZP. For a full understanding of the LTD mecha-
nism, additional theoretical calculations at an atomistic scale
are required. The biaxial tensile stress is one of the factors
which control the diffusion of vacancies and oxygen into the
lattice of Y-TZP. The role of hydrogen on the LTD mecha-
nisms is not yet clear and request complementary measure-
ments which are beyond the scope of this article.
CONCLUSION
1. The degradation of Y-TZP ceramic at the condition of
accelerated aging is strongly dependent on the grain
sizes.
2. When the grain size has achieved the critical value, which
is about 0.3 lm, the t–m phase transformation occurred.
3. Y-TZP sintered at 1600
C resulted the highest rate of deg-
radation (average grain size was about 0.72 lm).
4. Flaws and cracks which were induced on the surface of
Y-TZP through the air abrasion process were not an im-
portant factor for the LTD. The size of air-borne particles
was not a crucial factor on the LTD. The retardation of
LTD caused by air abrasion was observed for sintered
specimens at 1600
C.
5. The formation of Y-OH and Zr-OH bonds was not
observed. The concentration gradient of yttrium ions on
the surface of grains or on the grain boundaries did not
take place.
6. A stable Y-TZP can be achieved from a sintering tempera-
ture ranging between 1350 and 1450
C.
ACKNOWLEDGMENTS
The authors thank Prof. N. Spencer and Mr. F. Mangolini from
the Surface & Science Technology, Department of ETH Zürich
for XPS measurements, Dr. Igor Nemeth Bruker Nano GmbH
Berlin for AFM measurements, Dr. L Völkl of Degudent for the
Y-TZP blanks, Prof. Gauckler from the Nonmetallic Inorganic
Materials, Swiss Federal Institute of Technology, Department
of Materials of ETH Zürich for his advice.
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