dental materi als 2 5 ( 2 0 0 9 ) 736743

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Effect of ion exchange on strength and slow crack growth of
a dental porcelain
Vinicius Rosa
a
, Humberto N. Yoshimura
b
, Marcelo M. Pinto
a
, Catia Fredericci
b
,
Paulo F. Cesar
a,
a
Department of Biomaterials and Oral Biochemistry, School of Dentistry, University of So Paulo, So Paulo, Brazil
b
Laboratory of Metallurgy and Ceramic Materials, Institute for Technological Research of the State of So Paulo, So Paulo, Brazil
a r t i c l e i n f o
Article history:
Received 2 July 2008
Received in revised form
19 September 2008
Accepted 17 December 2008
Keywords:
Dental porcelain
Ion exchange
Strength
Slow crack growth
Saliva
a b s t r a c t
Objectives. To determine the effect of ion exchange on slow crack growth (SCG) parame-
ters (n, stress corrosion susceptibility coefcient, and
f0
, scaling parameter) and Weibull
parameters (m, Weibull modulus, and
0
, characteristic strength) of a dental porcelain.
Methods. 160 porcelain discs were fabricated according to manufacturers instructions, pol-
ished through 1m and divided into two groups: GC (control) and GI (submitted to an ion
exchange procedure using a KNO
3
paste at 470

C for 15min). SCG parameters were deter-

mined by biaxial exural strength test in articial saliva at 37

C using ve constant stress

rates (n=10). 20 specimens of eachgroupwere testedat 1MPa/s to determine Weibull param-
eters. The SPT diagram was constructed using the least-squares t of the strength data
versus probability of failure.
Results. Mean values of m and
0
(95% condence interval), n and
f0
(standard deviation)
were, respectively: 13.8 (10.118.8) and 60.4 (58.562.2), 24.1 (2.5) and 58.1 (0.01) for GC and
7.4 (5.310.0) and 136.8 (129.1144.7), 36.7 (7.3) and 127.9 (0.01) for GI. Fracture stresses
(MPa) calculated using the SPT diagram for lifetimes of 1 day, 1 year and 10 years (at a 5%
failure probability) were, respectively, 31.8, 24.9 and 22.7 for GC and 71.2, 60.6 and 56.9 for
GI.
Signicance. For the porcelain tested, the ion exchange process improved strength and resis-
tance to SCG, however, the materials reliability decreased. The predicted fracture stress at
5% failure probability for a lifetime of 10 years was also higher for the ion treated group.
2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
1. Introduction
Ceramic restorations are widely used in restorative dentistry
due totheir capability tomimic the dental structure. Moreover,
these materials have excellent biocompatibility, low thermal
conductivity and good color stability. In spite of these qual-

Corresponding author. Departamento de Biomateriais e Bioqumica Oral Faculdade de Odontologia Universidade de So Paulo, Av.
Prof. Lineu Prestes, 2227 Cidade Universitria Armando Salles de Oliveira, So Paulo SP Brasil. Tel.: +55 11 55613042;
fax: +55 11 55613042.
E-mail address: paulofc@usp.br (P.F. Cesar).
ities, unwanted fracture rates have been reported in clinical
trials for porcelain inlays, onlays and crowns due to the brittle
nature of ceramic materials [1,2].
The mechanical strength of ceramic materials depends
mainly on the presence of aws, especially the ones located
on the surface, since they act as stress concentrators when
0109-5641/$ see front matter 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.dental.2008.12.009
dental materi als 2 5 ( 2 0 0 9 ) 736743 737
the material is loaded. When the stress intensity at the crack
tip is greater than the materials resistance to crack propa-
gation, catastrophic fracture occurs. Fracture toughness (K
Ic
)
is the material property that relates the critical aw size with
fracture strengthof a material. This property is directly related
to the amount of energy the material can absorb before fast
crack propagation occurs. In general, dental porcelains show
relatively low values of K
Ic
[3], especially when compared to
metals. Therefore, improving porcelains fracture toughness
is the key to increase its lifetime service in the oral cavity.
Various methods may be used to increase the mechanical
properties and avoid fast crack propagation in dental ceram-
ics, such as the addition of second phase particles, thermal
tempering and chemical strengthening [4]. The latter, also
known as the ion exchange process, consists of changing the
chemical composition of a supercial layer of the material,
making it different from the bulk composition, by means of
exchanging smaller sodiumions (1.90in diameter) for larger
potassiumions (2.66in diameter) froma molten salt, at tem-
peratures higher than 328

C(melting point of KNO

3
) but lower
than the materials strain point [57]. The resultant increased
molar volume in the modied surface layer leads to a two-
dimensional state of compression, since the expansion of the
surface structure is restrainedby the underlying bulk material.
Previous studies have shown that these compressive stresses
result in an increase in both exural strength and fracture
toughness [6,8]. The advantages of this technique over thermal
tempering are the relatively high magnitude of surface com-
pression, the non-existence of optical distortion and the fact
that it canbe done inthinrestorations withcomplex geometry
[5]. Moreover, the compressive layer is not lost in moist envi-
ronments, so improvements in the mechanical properties are
expected to be stable in the long term[9]. However, it is impor-
tant to note that the exchange depth is relatively small (up to
100m [10]) and the effectiveness of the method depends on
the amount and mobility of sodium ions present in the mate-
rial. In the conventional chemical strengthening method, a
long soaking time is applied to enhance both the strength
and exchange depth. For commercial soda-lime silica glass,
soaking times up to 24h (at 450

C in molten KNO
3
bath)
have been used [11]. Alternatively, the so-called paste method
uses shorter treatment times (up to 30min) to strengthenden-
tal porcelains. In this method, the KNO
3
paste is applied on
the surface of porcelain restorations before heat treatment
[8,10,12]. One disadvantage of this method is the fact that
chemical strengthening may increase the fracture energy that
is released during fracture of the restoration, leading to a
multiple crack branching process that generates progressively
smaller fragments further from the fracture origin. No reports
have been found to explain if these multiple fragments repre-
sent a clinical problem.
Another important property that may be affected by the
ion exchange process is the materials resistance to the slow
crack growth(SCG) phenomenon. SCGis the result of corrosion
of ceramics metallic oxides by water molecules when pre-
existing supercial cracks are under tensile stress [13]. This
phenomenon is responsible for the strength degradation of
ceramics over time. The dynamic fatigue method is anindirect
test used to characterize slow crack growth parameters. This
test consists of determining the fracture strengthas a function
of the stress rate applied in exural strength tests. Based on
the results, it is possible to determine the fatigue parameters
n (stress corrosion susceptibility coefcient) and
f0
(scal-
ing parameter). The stress corrosion coefcient indicates the
susceptibility of the material to the slow crack growth phe-
nomenon. The higher the n value, the lower the susceptibility
to SCG. The scaling parameter
f0
is an indication of the early
strength of the material. The results fromthe dynamic fatigue
test mayalsobe usedtoconstruct lifetime curves topredict the
materials strength after long periods under constant stress
(e.g. 10 years) [14]. A previous study reported an increase of
124%in the n value of a heat-pressed leucite-reinforced dental
glass-ceramic tested in air after a conventional ion exchange
treatment (11h at 450

C in KNO
3
) [6]. Nonetheless, the poten-
tial of this process to increase the resistance to slow crack
growth in moist environments still needs to be determined,
since it has been shown that for dental porcelains, the n value
is usually lower in articial saliva at 37

C than in air at room

temperature [15]. Moreover, there is a lack of information on
the effect of a moist environment in the long-term strength
behavior of chemically strengthened dental porcelains pre-
pared by the paste method.
The objective of this study was to determine the inu-
ence of the ion exchange process on the strength and SCG
parameters of leucite-reinforced feldspathic porcelain in arti-
cial saliva at 37

C. In addition, the strength degradation over

time will be assessed by the analysis of a strength-probability-
time (SPT) diagram. The hypothesis to be tested is that the
ion exchange process will improve the strength and the SCG
parameters of the porcelain tested.
2. Material and methods
All specimens used in this study were fabricated by one single
operator, mixing 1g of a leucite-reinforced porcelain pow-
der (Ultropaline Super Transparent, Jen Dental, Kiev, Ukraine,
batch: 1094) with 0.4mL of deionized water in order to
form a slurry that was poured into a metal mold to obtain
disk-shaped specimens 15mmin diameter and 3mmin thick-
ness. Specimens were vacuum-red in a porcelain furnace
(Keramat I, Knebel, Porto Alegre, Brazil) according to manufac-
turers instructions. After sintering, the specimens measuring
12.5mm in diameter and 2.4mm in thickness were machined
in a surface-grinding device (MSG-600, Mitutoyo, So Paulo,
Brazil) following the guidelines in ASTM C 1161 [16] to obtain
parallel surfaces and reduce thickness to 1.3mm. Then, one of
their surfaces was mirror-polished using a polishing machine
(Ecomet 2, Buehler, Lake Bluff, USA) with diamond suspen-
sions up to 1m to obtain the nal thickness of 1.0 ( 0.1)
mm.
The ion exchange strengthening treatment of choice was
the paste method. The paste was prepared by mixing 10g of
reagent grade KNO
3
salt (Merck, Darmstadt, Germany) with
4mL of deionized water; 0.4g of this paste was deposited on
the polished surface of each specimen and then heat treated
in an electric oven (FP-32, Yamato, Tokyo, Japan) at a heating
rate of 5

C/min, an intermediary step at 150

C for 20min for

paste drying, and a holding time of 15min at the maximum
temperature to promote the ion exchange process. A prelimi-
738 dental materi als 2 5 ( 2 0 0 9 ) 736743
Table 1 Mean and standard-deviations of biaxial
exural strength (
f
), as a function of ion exchange
temperature.
Group
f
(MPa)
Control 57.6 (8.9)
b
I (450

C) 124.2 (23.4)
a
II (470

C) 132.2 (10.9)
a
III (490

C) 136.8 (12.0)
a
Values followed by the same superscript are statistically similar
(p>0.05).
nary study was carried out to determine the ideal temperature
for ion exchange in the porcelain studied. Four groups (n=10)
were prepared according to the temperature used: I (control,
no ion exchange); II (450

C); III (470

C); and IV (490

C). The
property determined was exural strength, according to the
methodology described below. These results were analyzed by
one-way analysis of variance (ANOVA) and Tukeys test with a
global signicance level of 0.05.
Todetermine the inuence of ionexchange onstrengthand
SCG parameters, 160 disk-shaped specimens were produced
and 80 of them were subjected to the ion exchange process at
470

C. This temperature was chosen because no signicant

differences were observed in the exural strength as a func-
tionof ionexchange temperature (Table 1). Moreover, the work
by Zijlstra and Burggraaf [17] suggested an ion exchange treat-
ment temperature 100

C below the materials glass transition

temperature, which was 575

C for the porcelain used in the

present study.
The biaxial exure strength (
f
) was determined using the
piston-on-three-balls method (ASTMF394-78 [18]) in a univer-
sal testing machine (Syntech 5G, MTS, So Paulo, Brazil) at
constant stress rates with the specimen immersed in arti-
cial saliva [19] heated and maintained constant at 37

C. The
biaxial exure strength was calculated using the following Eq.
[20]:

f
=
3F(1 + )
4t
2

1 + 2ln
R
a
b
+
1
1 +

1
b
2
2R
2
a

R
2
a
R
2

(1)
where F is the fracture load, t is the disk thickness, is Pois-
sons ratio (0.22), b is the radius of the loading area (piston
radius, 0.85mm), R is the disk radius, and R
a
is the radius of the
support circle dened by the three balls (4.0mm). The value
of was determined by the ultrasonic pulse-echo method
[21], using a 200MHz ultrasonic pulser-receiver (Panametrics,
USA, 5900 PR), 20MHz longitudinal and shear transducers
with a delay material, and a coupling paste applied between
the sample and transducer [22]. No signicant differences
were observed between the values of the two experimental
groups. In the preliminary study a xed stress rate (10MPa/s)
was used to evaluate the effect of ion exchange temperature
on the exural strength. The SCG parameters were evaluated
by the dynamic fatigue test, and specimens were tested in
biaxial exure at each of ve stress rates: 10
2
, 10
1
,
10
0
,
10
1
and 10
2
MPa/s (n=30 at 1MPa/s and n=10 at the remaining
rates), immersed inarticial saliva (at 37

C) withthe following
composition: 100mL of KH
2
PO
4
(2.5mM); 100mL of Na
2
HPO
4
(2.4mM); 100mL of KHCO
3
(1.5mM); 100mL of NaCl (1.0mM);
100mL of MgCl
2
(0.15mM); 100mL of CaCl
2
(1.5mM); and 6mL
of citric acid (0.002mM). The parameters n (stress corrosion
susceptibility coefcient) and
f0
(scaling parameter) were cal-
culated according to the following Eq. [23]:
log
f
=

1
n +1
log +log
f0

(2)
where is the stress rate.
Strength results of the specimens tested at 1MPa/s (n=30)
were tted to the two-parameter Weibull distribution to cal-
culate the strength parameters m (Weibull modulus) and
0
(characteristic strength), based on the following Eq. [24]:
P
f
= 1 exp

(3)
where P
f
is the fracture probability. The parameter
0
corre-
sponds tothe strengthat the failure probability of 63.2%. Based
on Eq. (3), the parameter
5%
was also determined, which
corresponds to the strength at the more clinically relevant
failure probability of 5%. The Weibull parameters were cal-
culated based on the maximum likelihood method, according
to the ASTM C 1239 [25] and plotted in addition to their 95%
condence level and the 95% condence interval of Weibull
modulus matched to characteristic strength.
The introduction of the Weibull statistics and the time
dependency of strength makes it possible to build strength-
probability-time (SPT) diagrams, where the time to failure
under constant stress for different failure probability levels
can be estimated using the results obtained in the dynamic
fatigue test, according to the theory proposed by Davidge et
al. [26]. In the present study, the SPT diagram matches the
failure probabilities and the applied constant stress to three
different times to failure: 1 day, 1 year and 10 years.
Fracture surfaces of selected specimens broken in the biax-
ial exure test were examined using optical microscopy (OM)
and scanning electron microscopy (SEM) to investigate the
fracture origin. The critical aws were identied and their
sizes were determined based on fractographic principles [27].
Critical crack size (c) was calculated as follows:
c

= (a

)
1/2
(4)
where a

is the crack depth and b is its half crack width. For

this analysis, only three stress rates were considered: 0.01; 1
and 100MPa/s (n=4), since the objective was to observe the
occurrence of slow crack growth by comparing critical crack
sizes at different stress rates. The specimens selected for this
analysis were those with strength as close as possible to the
calculated mean value of their groups.
3. Results
Results of the preliminary study, i.e. mean values of exural
strength as a function of different ion exchange temperatures
are listed in Table 1. A signicant increase in exural strength
can be observed after the ion exchange treatment. Moreover,
it is possible to note that different ion exchange temperatures
dental materi als 2 5 ( 2 0 0 9 ) 736743 739
Table 2 Weibull parameters (95% condence intervals in parentheses).
Group m
0
(MPa)
5%
(MPa) n
f0
(MPa)
10
(MPa)
Control 13.8 (10.118.8) 60.4 (58.562.2) 48.7 (43.453.0) 24.1 (2.5) 58.1 (0.01) 31.1
Ion exchange 7.4 (5.310.0) 136.8 (129.1144.7) 91.6 (73.7107.8) 36.7 (7.3) 127.9 (0.01) 90.4
m: Weibull modulus,
0
: characteristic strength,
5%
: strength at 5% failure probability
,
and fatigue parameters (standard deviations), n: stress
corrosion coefcient;
f0
: scaling parameter;
10
: predicted strength after 10 years, for control and ion treated group.
Fig. 1 Weibull plot showing the results of the exural
strength test (1MPa/s, saliva, 37

C) for both experimental

groups. Dashed lines represent the 95% condence interval
of Weibull modulus and straight lines represent the 95%
condence interval of the Weibull modulus combined with
the characteristic strength.
resulted in similar exural strength for the porcelain tested.
Table 2 shows the Weibull parameters (
0
,
5%
and m),
subcritical crack growth parameters (n and
f0
), and the frac-
ture stress corresponding to a lifetime of 10 years (
10
) for
both groups (control and ion exchanged). Although the ion
exchange increased the characteristic strength (
0
) in 126%,
this process caused a 46% decrease in the m value. The 95%
condence intervals for both
0
and m values indicate that
these differences are statistically signicant as the intervals
failed to overlap. The Weibull plot for both experimental con-
ditions is presented in Fig. 1, where it is possible to note the
higher variability of the strength data in the ion exchange
group. In addition, it can be noted that at the failure proba-
bility of 5%, the strength of the ion exchange group (
5%
) was
88%greater than that of the control. However, if the 95%con-
dence interval of
5%
is considered, the lowest value of the ion
exchange group (73.7MPa) is only 40%higher than the highest
value of the control group (53.0MPa) (Table 2).
The results of biaxial exure strength at different stress
rates are shown in Fig. 2. Both slow crack growth parameters
(n and
f0
) increased signicantly after the ion exchange pro-
cess (Table 2). Fig. 3 represents the lifetime curves for both
conditions. The slopes of these curves are directly related to
Fig. 2 Flexural strength as a function of stress rate for
control and ion exchange groups measured in articial
saliva at 37

C.
the materials n value (the higher the n value, the lower the
slope). Thus, the lower n value of the control group compared
to ion exchanged material resulted in the higher slope of the
rst, denoting that the ion treatment increased in 50% the
n value of the porcelain tested. The fracture stresses corre-
sponding to a time to failure of 10 years (
10
) were calculated
using the equation obtained in the regression analysis shown
inFig. 3. The
10
values obtained were 90.4 and 31.1MPa for the
ion exchange group and control group, respectively (Table 2).
Fig. 3 Plots of the exural strength as a function of time to
failure for both experimental groups. The time axis is
labeled for l day (1d), l year (1y) and 10 years (10y).
740 dental materi als 2 5 ( 2 0 0 9 ) 736743
Fig. 4 SPT (strength-probability-time) diagram for both
experimental groups.
Table 3 Fracture stresses (MPa) corresponding to 5%
failure probability at different times for both
experimental groups. Values obtained from the SPT
diagram (Fig. 4).
Group Initial 1 day 1 year 10 years
Control 49.6 31.8 24.9 22.7
Ion exchange 94.6 71.2 60.6 56.9
The SPT diagram obtained from the dynamic fatigue data
at different times to failure is shown in Fig. 4. It is observed
that strength degradation over time is higher for the control
group as compared to the ionexchange group. Considering the
5% failure probability, the corresponding fracture stresses for
the times to failure of 1 day, 1 year and 10 years are shown in
Table 3. After 10 years, the predicteddecrease infracture stress
at such failure probability is approximately 40% and 54% for
the treated and control group, respectively.
Fractography revealed that the fracture origins in all eval-
uated specimens were surface aws of semi-elliptical shape,
locatedinthe polishedsurface (Fig. 5). Meancritical crack sizes
as a function of the stress rate are shown in Fig. 6. It is possible
to note a decrease in the critical crack size with the increase
in stress rate in both experimental groups. Moreover, all crack
sizes measured were higher in the control group, regardless of
the stress rate.
4. Discussion
The hypothesis of this work was accepted since the results
showed that the ion exchange process improved the exural
strength and the SCG parameters of the porcelain tested. The
increase in exural strength observed after the ion exchange
process in the preliminary results (Table 1) was expected
because of the development of a compressive layer in the
materials surface due to the replacement of small Na
+
ions
Fig. 5 Representative SEM image of a fracture surface of
one ion exchange specimen fractured in three pieces at
1MPa/s. The arrows indicate the crack front.
for larger K
+
ions in the porcelains glassy matrix. Because
of this surface modication, cracks in the porcelain will only
propagate when the stresses generated during loading over-
come the residual stresses induced by the compressive layer
at the surface. These results also indicated that in the tem-
perature range investigated, the strengthening effect caused
by the increase in the ion diffusion rate due to the increase
in temperature was compensated by stress relaxation caused
by the accommodation of these ions in the glass network, by
means of diffusionandviscous processes [28]. Previous studies
also showed that the exural strength of leucite-based porce-
lains was not affected by temperature variations in a range
similar to that tested in the present study [29,30].
The ion exchange process used in the present study
affected the Weibull parameters in different ways, since
the characteristic strength (
0
) increased and the Weibull
modulus (m) decreased signicantly after the ion exchange
(Table 2 and Fig. 1). In other words, although the treatment
resulted in a 126% increase in the materials strength, its
reliability decreased signicantly due to the high variability
in the strength results (from 89 to 161MPa). The conven-
tional extended ion exchange treatments usually result in an
increase in a materials reliability [31,32], although no signif-
icant changes [6] or a decrease in the Weibull modulus [33]
after the treatment have also been reported. In the case of
ion exchange treatments that use shorter times, the limited
Fig. 6 Critical crack size as a function of stress rate for
both experimental groups.
dental materi als 2 5 ( 2 0 0 9 ) 736743 741
Fig. 7 Residual surface stress proles expected from
different ion exchange (IE) methods: conventional extended
IE; two-step IE; and paste method (short IE treatment).
Vertical dotted lines represent the depths of a small and a
large surface crack.
exchange depth strengthens preferably the originally stronger
specimens (i.e. those with the smallest Grifth aws), thus
broadening the strength distribution [34]. In addition, con-
sidering that the compressive layer resulting from the ion
exchange by the paste method is less than 100m thick [10],
it is possible that while smaller defects were totally sur-
rounded by the compression stresses, larger aws were only
partially surrounded, thereby contributing for the variabil-
ity in the results. In order to increase the reliability of glass
materials, a two-step ion-exchange method was proposed, in
which a short second ion-exchange process in a 30% Na
2
O-
70% K
2
O bath was carried out for partial removal of the K
+
ions introduced in the rst extended treatment [35]. This
method produces a stress prole withthe maximumcompres-
sive stress shifted to a given distance from the surface, which
acts as a barrier to the crack propagation [31]. The second step
of this method, however, tends to lower the strength achieved
with the rst ion-exchange step [6]. Fig. 7 shows schematically
the residual surface stress proles expected fromdifferent ion
exchange methods [6,10,35,36], with the indications of two
crack sizes (small and large). It is important to note that, apart
from the noticeable increase in variability, the overall perfor-
mance of the ion exchange group in terms of exural strength
was better than that of the control group, since the lowest
strength value measured in the rst was higher than the high-
est value obtained for the latter. In addition, Table 2 shows
that the ion-exchange group had a signicantly higher frac-
ture strength at the more clinically relevant failure probability
of 5% (
5%
), considering the 95% condence interval.
The higher stress corrosion susceptibility coefcient (n)
obtained after the ion exchange (Table 2 and Fig. 3) indicates
that this process not only increased the strength of the dental
porcelain studied but also reduced its degradation over time
in the articial saliva environment at 37

C. The ion exchange

material showed an increased resistance against slow crack
growth due to the presence of compressive stresses in the
surface layer. In fact, it is possible to note in the fractographic
analysis (Fig. 6) that critical crack sizes were larger for the con-
trol group especially at the stress rate of 0.01MPa/s, indicating
that inthis group the absence of residual compressive stresses
allowed cracks to grow at a higher rate. The ability of the ion
exchange treatment in reducing slow crack propagation can
also be noted by comparing the values of
f0
(early strength)
and
10
(predicted strength after 10 years) in Table 2. These
results show that the degradation in strength after 10 years
of service was higher for the control group (decreased 47%,
from58.1 to 31.1MPa) as comparedto the ionexchange treated
group (decreased 29%, from 127.9 to 90.4MPa). Such differ-
ence in strength degradation can also be observed in Fig. 3,
in which the curve corresponding to the control group shows
the steeper slope.
Fig. 1 shows that in the low failure probability range, the
lower Weibull modulus (m) of the ion-exchanged porcelain
results in exural strength values that are closer to that of the
control porcelain, decreasing the difference observed between

0
values. The higher stress corrosion susceptibility coef-
cient (n) of the ion-exchange porcelain, however, compensated
this effect partially, since its slower strength degradation
rate resulted in an increase in the difference between the
strength of both groups for any level of fracture probability
(Fig. 4).
The higher strengthdegradationof the control group is also
observed inthe SPTdiagraminFig. 4, since the period between
curves is larger for this group. This graph also gives us the
perspective of what would be the stress to fracture 5% of the
specimens after 10 years of service (Table 3). Such stress is
approximately 100% higher for the treated group, indicating
that the ion exchange leads to a signicant improvement in
the porcelain service lifetime. In order to extrapolate these
results to clinical practice, it is necessary to consider that
times to failure described in the SPT diagram are for static
loading calculated from dynamic fatigue tests [26]. Therefore,
these results may not correlate well with the cyclic loading
pattern of the mastication process. However, it is possible to
estimate, for a certain time of cyclic loading regimen, the cor-
responding time in static loading by adding all the periods
of effective mastication. In this way, for a clinical lifetime of
about 10 years, one can assume that the restoration would be
subjected to average masticatory stresses for only 14% of the
time, which corresponds to a period varying from 38 to 152
days. These periods of time fall within the periods of 1 day
and 1 year of static loading presented in Table 3. Consider-
ing that the mean applied stress in each chewing cycle in the
molar region is approximately 28MPa [37], it is possible to note
that for both periods of 1 day and 1 year (Table 3) the fracture
stresses (at 5%failure probability) of the control group are very
close to the stress of 28MPa described above, while the values
obtained for the treated group indicate a more reliable situa-
tion, since they are at least double the stress of one chewing
cycle in the molar region.
The clinical parameters describedabove canalsobe applied
to the SPT diagram to calculate the failure probability of the
experimental groups taking into consideration a static load-
742 dental materi als 2 5 ( 2 0 0 9 ) 736743
Fig. 8 Number of fracture pieces as a function of the
biaxial exural strength.
ing at 28MPa for a period of 38 or 152 days. In this case, the
estimated failure probabilities of the control group would vary
from 8 to 19%, while no failures would be observed in the
treatedgroup. Suchpredictions shouldbe carefully considered
since the magnitude, duration and stress development in the
oral environment are quite complex. Inthis regard, it shouldbe
taken into account that the cyclic nature of mastication com-
prises long periods without the application of stresses, which
may result in crack healing or crack blunting [38]. Other fac-
tors should also be evaluated suchas the restorationthickness
and shape, defects introduced during processing or adjusting
and the presence of residual stresses.
Fig. 8 was constructed in order to assess if there might be
any clinical concern regarding the number of fracture pieces
of an ion-exchange restoration fractured in the mouth. It is
possible to note that all the specimens in the control group
fractured in only two pieces, while most of the ion exchange
specimens fractured in 3 or 4 pieces. The higher number of
pieces in the ion exchange group is related to the higher frac-
ture energythat is releasedduring crackpropagation. Fromthe
clinical point of view, the number of fracture pieces found in
the present work should not represent a clinical problem. This
statement is limited only to the porcelains strengthened by
the paste method (using short ion exchange treatment), since
glasses strengthened by the conventional extended chemi-
cal strengthening method can fragment in a large number
of small pieces, depending on the residual stress levels intro-
duced during the treatment [36].
5. Conclusion
Based on the results of this study it was possible to con-
clude that the ionexchange treatment using the paste method
improved strength, reduced slow crack growth (increased the
stress corrosion susceptibility coefcient, n) in articial saliva
at 37

C, and reduced strength degradation over time for the

leucite-reinforcedfeldspathic porcelaintested. The signicant
increase in strength and the higher coefcient n compensated
for the noticeable reductioninreliability, as represented by the
decrease in the Weibull modulus after the treatment.
Acknowledgments
The authors would like to thank Dr. Victor Styopkin for pro-
viding the porcelain used in this study. Based on a thesis
submitted to Universidade de So Paulo, in partial fullment
of the requirements for the M.Sc. degree. This research was
supported by Brazilian agencies CAPES, FAPESP and CNPq for
the nancial support of the present research.
r e f e r e nce s
[1] Hayashi M, Tsuchitani Y, Kawamura Y, Miura M, Takeshige F,
Ebisu S. Eight-year clinical evaluation of red ceramic inlays.
Oper Dent 2000;25:47381.
[2] Smales RJ, Etemadi S. Survival of ceramic onlays placed with
and without metal reinforcement. J Prosthet Dent
2004;91:54853.
[3] Cesar PF, Yoshimura HN, Miranda Junior WG, Okada CY.
Correlation between fracture toughness and leucite content
in dental porcelains. J Dent 2005;33:7219.
[4] Odo GY, Nogueira LN, Lepienski CL. Ionic migration effects
on the mechanical properties of glass surfaces. J Non-Crys
Solids 1999;247:2326.
[5] Varshneya AK. Physical properties of ion-exchanged and
melt-processed glasses differ. Glass Researcher 2001;10:217.
[6] Fischer H, Marx R. Suppression of subcritical crack growth in
a leucite-reinforced dental glass by ion exchange. J Biomed
Mater Res A 2003;66:8859.
[7] Bartholomew RF. Ion exchange. 4 EUA: ASM International;
1991.
[8] Seghi RR, Crispin BC, Mito W. The effect of ion exchange on
the exural strenght of feldsphatic porcelains. Int J
Prosthodont 1990;3:1304.
[9] Fischer H, Tinschert J, Marx R. Steigerung der
Beanspruchbarkeit vollkeramischer Brcken durch
Ionenaustaschverfahren Dtsch Zahnarztl Z 1999;54:3214.
[10] Piddock V, Qualtrough AJ, Brough I. An investigation of an
ion strengthening paste for dental porcelains. Int J
Prosthodont 1991;4:1327.
[11] Sinton CW, Lacourse WC, OConnell MJ. Variations in K
+
-Na
+
ion exchange depth in commercial and experimental oat
glass compositions. Mater Res Bull 1999;34:23519.
[12] Cesar PF, Gonzaga CC, Miranda Jr WG, Yoshimura HN. Effect
of ion exchange on hardness and fracture toughness of
dental porcelains. J Biomed Mater Res B Appl Biomater
2007;83:53845.
[13] Ritter JE. Crack propagation in ceramics. 4 Metals Park: OH:
ASM International; 1991.
[14] Wachtman JB. Mechanical properties of ceramics. New York:
John Wiley & Sons; 1996.
[15] Cesar PF, Soki FN, Yoshimura HN, Gonzaga CC, Styopkin V.
Inuence of leucite content on slow crack growth of dental
porcelains. Dent Mater 2008;24:111422.
[16] ASTM. C 1161 Flexural srength of advanced ceramics at
ambient temperature. American Society for Testing
Materials, 2002.
[17] Zijlstra AL, Burggraaf AJ. Fracture phenomena and strenght
properties of chemically and physically strengthened glass.
II. Strength and fracture behavior of chemically
strengthened glass in connection with the stress prole. J
Non-Crys Solids 1969;1:16385.
[18] ASTM Designition. Standard test method for biaxial exure
strength (modulus of rupture) of ceramics substrates.
Philadelphia, PA: American Society for Testing Materials;
F39478 [reapproved 1991].
dental materi als 2 5 ( 2 0 0 9 ) 736743 743
[19] Cate JMT, Duijisters PPE. Alternating demineralization and
remineralization of articial enamel lesions. Caries Res
1982;16:20110.
[20] Shetty DK, Roseneld AR, Mcguire P, Bansal GK, Duckworth
WH. Biaxial exure tests for ceramics. Am Ceram Soc Bull
1980;59:11937.
[21] JIS. Testing methods for elastic modulus of high
performance ceramics. JIS R 1602 1986;216.
[22] Yoshimura HN, Molisani AL, Narita NE, Cesar PF, H. G.
Porosity dependence of elastic constants in aluminum
nitride ceramics. Mater Res 2007;10:12733.
[23] ASTM. C 1368-00 Standard test method for determination of
slow crack growth parameters of advanced ceramics by
constant stress-rate exural testing at ambient temperature.
Annual Book of ASTM 2001;15:19.
[24] Weibull W. A statistical distribution of wide applicability. J
Appl Mechan 1951;18:2937.
[25] ASTM. C1239 Reporting uniaxial strength data and
estimating Weibull distribution parameters for advanced
ceramics. American Society for Testing Materials, 2000.
[26] Davidge RW, McLaren JR, Tappin G.
Strength-probability-time (SPT) relationship in ceramics. J
Mater Sci 1973;8:1699705.
[27] Morena R, Lockwood PE, Fairhurst CW. Fracture toughness of
commercial dental porcelains. Dent Mater 1986;2:
5862.
[28] Orgaz F, Navarro JMF. Prediction of results of strengthening
glass by using the mistting sphere theory. New York:
Plenum Press; 1985.
[29] White SN, Seghi RR. The effect of ion strengthening
time/temperature kinetics on the exural strength of
feldspathic porcelains. Dent Mater 1992;8:3203.
[30] Denry IL, Rosenstiel SF, Holloway JA, Niemiec MS. Enhanced
chemical strengthening of feldspathic dental porcelain. J
Dent Res 1993;72:142933.
[31] Sglavo VM, Green DJ. Flaw insensitive ion-exchanged glass:
II, production and mechanical performance. J Am Ceram Soc
2001;84, 1832-1238.
[32] Fischer H, Marx R. Improvement of strength parameters of a
leucite-reinforced glass ceramic by dual-ion exchange. J
Dent Res 2001;81:3369.
[33] Fischer H, Maier HR, Marx R. Improved reliability of leucite
reinforced glass by ion exchange. Dent Mater 2000;16:1208.
[34] Varner JR. The practical strength of glass. New York: Plenum
Press; 1985.
[35] Green DJ, Tandon R, Sglavo VM. Crack arrest and multiple
cracking in glass through the use of designed residual stress
proles. Science 1999;283:12957.
[36] Glass SJ, Tandon R, Heller D. Characterization of crack
branching and fragmentation patterns for ion-exchanged
glass. In: Ceram Transactions, v. 1999. Hoboken, New Jersey:
The American Ceramic Society & John Wiley & Sons; 2007.
[37] Lohbauer U, Kramer N, Petschelt A, Frankenberger R.
Correlation of in vitro fatigue data and in vivo clinical
performance of a glass ceramic material. Dent Mater
2008;24:3944.
[38] Fairhurst CW, Lockwood PE, Ringle RD, Twiggs SD. Dynamic
fatigue of feldsphatic porcelain. Dent Mater 1993;9:26973.