Int. J. Appl. Ceram. Technol.

, ]] []]] 1–10 (2011)

DOI:10.1111/j.1744-7402.2011.02661.x

Ceramic Product Development and Commercialization

Mechanical and Chemical Properties of Zr and P-Doped

Lithium Disilicate Glass Ceramics in Dental Restorations
Zahra Khalkhali,* Bijan Eftekhari yekta, and Vahak K. Marghussian
Department of Material Science, Ceramic Division, Iran University of Science and Technology,
1684613114, Hengam Street, Tehran, Iran

The Weibull modulus, flexural strength, fracture toughness, Vickers microhardness, and chemical durability of sintered
Li2O–SiO2 glass ceramic specimens doped with P2O5 or ZrO2 were evaluated in accordance with the norm of EN ISO 6872.
Peak crystallization temperatures, crystalline phases, and microstructure were characterized by means of differential thermal
analysis, X-ray diffraction, and scanning electron microscopy methods, respectively. Phase formation induced by the addition
of P2O5 led to precipitation of Li3PO4, which in turn caused more intensive crystallization of Li2SiO3. The high-temperature
crystalline phase Li2Si2O5 was precipitated more intensively in P2O5 containing specimens resulting in an interlocked
microstructure of needle like disilicate crystals. Therefore, the P-doped glass ceramic exhibited the optimum mechanical
and chemical properties (i.e., m 5 15, sf 5 181715 MPa, KIC 5 1.9470.19 MPa m1/2, Hv 5 3.771.1 GPa, chemical
solubility 5 5379 mg/cm2)

Introduction their low mechanical properties such as low resistance to

Recent efforts in dental restorative research man-
aged strongly to eliminate the use of metals and metal
alloys; that is, amalgam, in restorative dentistry.1 As an
alternative to amalgam, the early attempts to place com-
posites in posterior teeth had only limited success due to
*Khalkhali_z@yahoo.com
r 2011 The American Ceramic Society
wear.2 On the other hand, lithium disilicate glass ce-
ramics are suitable for fabricating restorative prosthesis
consisting of dental inlays, onlays, veneers, crowns, and
two to multiunit bridges.1,3–5 In sintering method, there
is a large driving force for surface nucleation. Therefore,
the addition of slight amounts of P2O5, ZrO2, and
TiO2 is required to transform the lithium disilicate-
based glass system from surface to bulk crystallization.6–9
Zheng et al.9 studied the effect of P2O5 content and heat
2 International Journal of Applied Ceramic Technology—Khalkhali, Eftekhari yekta, and Marghussian Vol. ]], No. ]], 2011
treatment on crystallinity and microstructure in a Li2O–
SiO2–ZnO–K2O–CaO glass system. They found that
introducing 1 mol% P2O5 to the base glass system led to
up to 67% degree of crystallization after two-stage heat
treatment and the predominant crystallization growth of
Li2Si2O5 occurred epitaxially along specific planes of
Li2SiO3 crystals with o15% misfit. They also reported
that introducing more than 2 mol% P2O5 to the glass,
hampered both Li2Si2O5 and Li2SiO3 precipitation even
after two stage heat treatment.9 Numerous researches
have so far been conducted on dental glass ceramics pre-
pared by melt quenching method. However, a few in-
vestigations have been done on sintered glasses as dental
restorations in literature. In this work, glasses in Li2O–
SiO2 system doped with Zr or P were prepared by sinte-
ring method to reveal the effect of P2O5 and ZrO2
on chemical and mechanical properties of these glass
ceramics.
Materials and Methods
Glass specimens were prepared using sintering
method with compositions listed in Table I. The mo-
lar ratio of SiO2:Li2O was kept at 1:2.4, according to a
separate study by Höland and colleagues due to the high
mechanical properties of the final product. Standard
reagent grade SiO2, Al2O3, Li2CO3, KNO3, P2O5,
H3BO3, and ZrO2 powders were chosen as raw mate-
rials. 3.41 part by weight P2O5 and ZrO2 were added to
the base glass and formed GP and GBZ, respectively. GB
was considered as the base composition and hence did
not contain any additives. We added 3.41 part by
weight B2O3 as a melting accelerator to GBZ specimens
to compensate for the increase in the viscosity of the
glass due to the replacement of P2O5 by ZrO2. The
100 g batches were melted in a high-alumina crucible in
an electric furnace (Atbin AHT 15, Atbin, Tehran,
Iran), at 13501C for 1 h in air. The melt was poured
into distilled water and formed the glass frit which was
fast-milled in 45 min to reach o45 mm particle size.
Table I. Batch Compositions (Part by Weight) and Theoretical Optical Basicity of the Glasses
SiO 2 Al 2 O 3 Li 2 O K2O
GB 74.24 3.58 15.48 3.29
GBZ 74.24 3.58 15.48 3.29
GP 74.24 3.58 15.48 3.29
Differential thermal analysis (DTA) was performed us-
ing a thermal analyzer (Polymer Laboratories 1640,
Amherst, MA) on 10 mg of every specimen in high-
Al2O3 crucibles with a heating rate of 101C/min in air
to characterize thermal behavior of the glasses. Phase
analysis and microstructure studies were run using X-ray
diffraction (XRD) and scanning electron microscopy
(SEM) methods, respectively. For X-ray diffractometry
a JEOL-JDX 8030 (JEOL, Tokyo, Japan) apparatus
with CuKa radiation and scanning from 51 to 751 was
used and SEM was run by means of a Philips XL30
apparatus (Phillips, Eindhoven, The Netherlands) over
polished specimens and etched in 5 vol% HF solution
for 30 s. The number and relative intensity of the XRD
peaks were used to calculate the crystallinity of glasses.
In this method, crystallinity Xc is measured through the
following equation:
P
Ici
XC ¼ P  100% ð1Þ
Ici þ KIa
where Ia and Ic are the integrated intensity of the am-
orph and crystalline phases, respectively and K is a com-
position-related constant which for lithium disilicate
glass ceramics is equal to 0.963.9 Cylindrical specimens
of 4.5 mm height and 15 mm diameter were pressed
under the pressure of 45 MPa. They were then sintered
in an electric furnace at 8501C for 2 h in air. The bulk
density of the specimens was determined by the Ar-
chimedean method.
Chemical stability was measured using the norm of
EN ISO 6872. For this purpose, 10 specimens of each
composition sintered at 8251C for 2 h, were put in a 4%
acetic acid solution at 801C for 16 h. Then the loss of
mass was reported in (mg/cm2) as a reverse representative
of chemical durability. Microhardness was determined
by means of a Vickers microhardness measuring device
(Micromet of Buehler, Dusseldorf, Germany). Flexural
strength was measured in the three-point-bending test
according to EN ISO 6872 over 25 mm  5 mm 
2 mm specimens in a universal testing machine
P2O5 B2O3 ZrO 2 Lth70.001
— 3.41 — 0.723
— 3.41 3.41 0.720
3.41 — — 0.727
www.ceramics.org/ACT Mechanical and Chemical Properties of Lithium Disilicate Glass Ceramics 3

(Zwick/Roell ZO20, Ulm, Germany) with a span

length of 20 mm and a crosshead speed of 1 mm/min.
Equation (2) was used for this purpose.
M ¼ 3Wl=2bd 2 ð2Þ
where M is the flexural strength in MPa, W is the break-
ing load in newton, l is the test span (20 mm), b and d
are the width and thickness of the specimens, respec-
tively. According to EN ISO 6872, in order to pass the
test at least eight of the 10 specimens shall meet the re-
quirements for flexural strength stated in Table III. If
five or less specimens pass, the material fails. If six or
seven pass, a further 10 specimens shall be tested. Of
these, 10 or 9 shall pass, that is, at least 16 shall pass in
total.
For every trial series, Weibull statistics were per- Fig. 1. DTA curves of the powdered glass frits.
formed over 30 specimens of each composition. Both
the Weibull parameter m and the Weibull characteristic
strength s0 were determined in a ln s_ln (ln 1/(1F)) DTA curve of GP at 6251C and 8251C. Whereas in GB
diagram. The parameter m is determined from the slope and GBZ only one exothermic peak emerged at 6251C
of regression line within the plot using the following and 6501C, respectively. Figure 2 presents XRD pat-
equation: terns of samples after heat treating at peak crystallization
ln ln 1=ð1  F Þ ¼ m ln s þ ðln V  m ln s0 Þ ð3Þ temperatures for 2 h. From Fig. 2 it is seen that the first
exothermic peak in the DTA curves of the samples at
where F is the failure probability, s is the flexural 6251C represents crystallization of lithium metasilicate
strength, V is the specimen volume, and s0 is the Wei- (Li2SiO3) whereas the second one at 8251C in GP rep-
bull characteristic strength which results from the resents that of lithium disilicate (Li2Si2O5). Li2Si2O5
strength at a failure probability of PF 5 0.632 or ln was precipitated in all three specimens after heat treating
(ln 1/(1F)) 5 0.10 at 8251C for 2 h. XRD pattern of GP heat treated at
Fracture toughness can be obtained by either di-
rectly measuring the flaw size or by using the strength
method.11 The latter was used in this work. A Vickers
hardness measuring device (Micromet of Buehler) was
used to indent on 10 specimens of each composition.
To produce the indentations, a Vickers indenter was
used at a load of F 5 4.905 N for 30 s. To evaluate the
fracture toughness, the following equation was used.
 3=4
KIC ¼ ZRV ðE=H Þ1=8 sP 1=3 ð4Þ

where ZRV is a geometrical constant (0.5970.12), E/H

is the modulus-to-hardness ratio, s is the three point
flexural strength, and P is the force applied in
indentation.12

Results Fig. 2. XRD patterns of the three groups of glass specimens heat
treated at peak crystallization temperatures for 2 h. d, lithium
Figure 1 shows the DTA curves of the three pow- disilicate (Li2Si2O5); m, lithium metasilicate (Li2SiO3);
dered glass frits. Two exothermic peaks appeared in the L, Li3PO4.
4 International Journal of Applied Ceramic Technology—Khalkhali, Eftekhari yekta, and Marghussian Vol. ]], No. ]], 2011

6251C for 2 h showed crystallization of a slight amount

of Li3PO4 whereas in GB and GBZ, only Li2SiO3 crys-
tallized. Li3PO4 crystallization peak had an overlap with
Li2SiO3 crystallization peak in the DTA curve of GP
and as aresult only one exothermic peak appeared at
6251C other than that which appeared at 8251C refer-
ring to Li2Si2O5 in this DTA curve.
Figure 3 presents micrographs of specimens after
sintering at 8251C for 2 h. Interconnected needle-like
crystals o5 mm in length precipitated in GB which
changed into plate like aggregates in GBZ with a larger
aspect ratio. Whereas the interconnectivity of the needle
like crystals increased in GP that accompanied by a
slight decrease in particle size compared with that of the
base glass ceramic GB. Because Li2SiO3 and Li3PO4
were dissolved in HF solution while etching the spec-
imens, only Li2Si2O5 crystals are observed in these
micrographs. This was approved via EDAX analysis.
Figure 4 illustrates SEM graphs of crack formation
at points indented by microhardness measurements.
Chemical and mechanical properties of the specimens
heat treated at the peak crystallization temperature
(8251C) for 2 h are summarized in Table II. Note
that in the sintering method, no nucleation heat treat-
ment is required because the fine powdered glass frit
facilitates surface crystallization. The chemical solubility
decreased from GBZ to GB and to GP, respectively.
Microhardness decreased from GP to GBZ and to GB,
respectively. Moderate values of three point flexural
strength, Weibull modulus, and fracture toughness
were obtained for the sintered samples.
Table III listed the mechanical and chemical prop-
erties required by En ISO 6872 according to which
although all the three glass ceramics studied in this
work satisfy the chemical properties, some mechanical
properties are not fulfilled efficiently for every dental
restorative.

Fig. 3. SEM photographs of etched surfaces of the three groups of

Discussion
According to Table I, B2O3 was the constant con-
stituent of the three samples. Generally the coordination
number of glass network forming elements with an ionic
bond is 4. However, in oxide glasses, B2O3 occurs with
two coordination numbers 3 and 4, as a glass network
former. B2O3 acts as a very efficient flux in glasses due to
the weak bonds between [BOn] structural units and
considerably reduces the liquidus temperature of glass.13
lithium disilicate glass ceramic heat treated at the peak
crystallization temperature (8251C) for 2 h.
Therefore, it was added to GBZ to compensate for the
increament of glass viscosity due to the addition of
ZrO2.
Although the peak representative of Li2Si2O5 only
appeared in the DTA curve of GP, it was precipitated in
all three specimens after one-stage heat treatment at
www.ceramics.org/ACT Mechanical and Chemical Properties of Lithium Disilicate Glass Ceramics
Fig. 4. SEM graphs of crack formation at points indented by
microhardness measurements.
8251C for 2 h. This indicates that Li2Si2O5 crystalliza-
tion mechanism is mainly by the surface rather than the
bulk. P2O5 induce phase separation in lithium disilicate
glasses and leads to formation of Li- and Si-rich regions
within the glass matrix.9 Subsequently, Li3PO4 clusters
5
nucleated in Li-rich regions facilitates the heterogeneous
nucleation of Li2SiO3 due to a reduction in surface en-
ergy. Li2SiO3 is a metastable transient phase and leads
to the crystallization of Li2Si2O5 and is favorable from
this point of view.9 Thereupon, it can be concluded that
Li3PO4 crystals acted as a nucleating agent for Li2Si2O5
crystals in GP specimens.
As mentioned above, the main crystallization mech-
anism of lithium disilicate is by the surface. Therefore,
using the fine particle size of o45 m in the sintering
method acted as a driving force for nucleation of
Li2Si2O5.
In glasses, an important feature that affects both
physical and chemical properties is the nonbridging ox-
ygens (NBOs) present in the glass. The so-called theo-
retical optical basicity is a chemical parameter based on
the ionic nature of oxides and provides a measure of
NBOs.14
For a glass composed of oxide constituents the the-
oretical optical basicity Lth is given by the following
relation:
X
Lth ¼ xi Lci ð5Þ
Lc ¼ 1=gc
where xi and Lci are the equivalent fraction and optical
basicity of oxide i, respectively. gc is the basicity mod-
erating parameter indicating the attraction of electrons
for chemical bonding of the cation c15 and is calculated
through the following equation:
gc ¼ 1:36ðxm  0:26Þ ð7Þ
16
where xm is the electronegativity of the metal ion. xm,
gm, and Lc of each constituents of the glasses are pre-
sented in Table IV and Lth for each glass sample is cal-
culated and given in Table I. From this table it is seen
that P2O5 increased Lth of the base glass from 0.723 to
0.727 whereas ZrO2 decreased it to 0.720. In other
words, the number of NBOs decreased in the sequence
of GP, GB, and GBZ. Therefore it was not unexpected
that crystallization in GP improved but reduced in GBZ
with respect to that of GB because of the changes in the
large scale order of the glass network due to the changes
in the number of NBOs.
The chemical solubility decreased from GBZ to GB
and to GP, respectively, which can be attributed to the
degree of crystallization that increases in the above men-
tioned sequence of samples. Another origin of this
might be that Li2SiO3 which is crystallized in GB and
6 International Journal of Applied Ceramic Technology—Khalkhali, Eftekhari yekta, and Marghussian Vol. ]], No. ]], 2011

Table II. Mechanical and Chemical Properties of the Three Glass Ceramics Sintered at 8251C for 2 h
Chemical Flexural Fracture Weibul Bulk
solubility, loss strength toughness modulus, Vickers micro X c density
Material in mass (lg/cm2 ) (MPa) (MPa m 1/2 ) m hardness (GPa) (%) (g/cm3 )
GB 6074 168721 1.6870.27 10.12 2.870.4 46 2.46
GBZ 9075 76716 0.8470.32 4.61 3.471.3 44 2.44
GP 5379 181715 1.9470.19 9.74 3.771.1 57 2.83

GBZ at 8251C is a chemically unstable crystal.1,3,4 GP Vickers indenter is hutted to porosity, greater penetration
contains only Li2Si2O5 crystals with a larger degree of of the indenter leads to a lower apparent hardness. Hard-
crystallization (57%) compared with that of GB (46%) ness increases with the decrease in the grain size according
and GBZ (44%). Therefore, GP showed higher resistance to the Hall–Petch equation,
to solution in acid than GB and GBZ. Moreover, note
that formation of two crystalline phases (Li2Si2O5 and sy ¼ s0 þ ky d 1=2
Li2SiO3) in GB and GBZ, results in lower amount of
residual silica in the glass matrix, leading to a lower re- where sy is hardness, d is the grain size, and s0 and ky are
sistance to solution in acetic acid. Although Li3PO4 is constant for a given material.17 Fine-grained materials
also a low chemical resistant crystal, sintering the glass tend to be harder than coarse-grained ones of the same
ceramic above 8251C allows no residual Li3PO4 in the composition regarding the fact that they are less prone to
glass matrix (Fig. 2) and the sole crystalline phase in GP local shattering of grains.18 On the other hand, SEM
is the chemically durable Li2Si2O5 crystals. studies on crack formation at microhardness indents pre-
As shown in Table II, microhardness decreased from sented in Fig. 4 shows that horizontal and vertical cracks
GP to GBZ and to GB, respectively. The hardness values of initiated at the points of the indent trace in GB, whereas
natural dentine and enamel are in the range of 0.5–0.7 smaller cracks produced at indentation points in GBZ and
and 3.0–3.4 GPa, respectively. Therefore, hardness of re- no cracks formed around the indents in GP. Generally
storative materials must not exceed 3.4 GPa. Otherwise, indentation induced cracks propagate parallel to the di-
they may destroy the front teeth.3 Thus with regard to rection of lithium disilicate crystals more easily than prep-
hardness, the three glass ceramics are suitable to be used as endecular to the crystals orientation.19 Therefore, the high
restorative enamel. The high deviation standard given for hardness obtained for GP is not unexpected due to its
hardness is possibly a result of different phases present in smaller grain size, higher density, more random distribu-
glass ceramics. In hardness measurement experiments, if tion and higher content of lithium disilicate crystals. The
the Vickers indenter is hutted to the harder phase, hard- two latter factors prohibited crack propagation by crack
ness value obtained is higher and vice versa. Thus, prac- deflection mechanism.
ticing macrohardness instead of microhardness in
multiphase materials such as this glass ceramic system Table IV. Electronegativities, Basicity Moderating
provides more reliable results. Hardness is dominantly at- Parameters of Metal Ions, and Bulk Optical Basicities
tributed to the grain size, porosity, and the kind and of Individual Metal Oxides Included in
amount of the phases contained in the specimens. If the Glass Compositions
Oxide xm cm Lc
Table III. Mechanical and Chemical Properties
Required by EN ISO 6872:1998 SiO2 1.8 2.08 0.48
Al2O3 1.5 1.69 1.59
Properties Requirement
Li2O 0.95 0.94 1.07
Flexural strength (MPa), 100 50 (dentine/ K2 O 0.8 0.73 1.36
min (core) enamel ceramic) P2 O 5 2.1 2.50 0.40
Chemical solubility, loss in 2000 100 (dentine/ B2O3 2 2.36 0.42
mass (mg/cm2), max (core) enamel ceramic) ZrO2 1.5 1.69 0.59
www.ceramics.org/ACT Mechanical and Chemical Properties of Lithium Disilicate Glass Ceramics
Table V listed a comparison of crystalline phases,
density, porosity, and hardness of bioactive glasses and
hydroxyapatite powder reported in literature. Glasses
with o60 mol% SiO2, high content of Na2O and CaO,
and slight amounts of P2O5 are considered as bioactive
materials. Because they are capable of developing a bio-
active hydroxyapatite layer at the bone/implant surface
and improve bonding with bone and soft tissues.20–22
Although the glass system studied in this work does not
undergo the bioactive materials class, this comparison
provides a comprehensive scope of structural and me-
chanical properties of these dental glass ceramics. Hoe-
pfner and Case11 conducted an investigation on the
hardness of some 50 hydroxyapatite samples and con-
cluded that hardness decreases exponentially with po-
rosity but no clear grain size dependence of hardness was
observed in their research. Although the microhardness
obtained for lithium disilicate glass ceramics in the pres-
ent work are considerably less than that of bioglasses
studied by Salama et al.,20 it is comparable to those of
tapecast and sintered bioglasses (0.2–5.7 GPa)11 and
hydroxyapatite (0.91–5.42 GPa).21
Researchers reported different flexural strength for
Li2O–SiO2 glass ceramic system. It ranges from 96 MPa
(measured by Della Bonaa et al.23) to a maximum value
of 400740 Mpa.3 As mentioned previously, glass ce-
ramics studied in this work, were synthesized by sinte-
ring the glass frit powder and no stress releasing process
like annealing was applied on the products. Therefore,
moderate values obtained for flexural strength of the
specimens especially GB and GBZ may be a result of the
residual stresses induced during the sintering process.
Nevertheless, the flexural strengths of GB (168 MPa)
and GP (181 MPa) are comparable to that of cortical
bone (100–200 MPa).21 Flexural strength in multiphase
materials is related conversely to the mean free path
between crystals as in the following equation:
Ls ¼ d ð1  Vc Þ=Vc sf a1=Ls ð8Þ
where sf is the flexural strength, Ls is the mean free path
between crystals, d is the grain size of crystals, and Vc is
the crystalline volume percentage. The less the grain size
of the crystals d, the less the mean free path Ls which
subsequently results in the increment of flexural
strength. As demonstrated in Fig. 3, Ls is the least for
GP, which together with the higher content of Li2Si2O5
crystals led to a high strength. Moreover, the effective
role of P2O5 as a nucleating agent, which also induced
phase separation before crystallization in GP resulted in
7
a random distribution of needle-like Li2Si2O5 aggre-
gates in GP. This in turn may have led to the deviation
of cracks into the glass phase because its strength is less
than that of crystal. Crack propagation in the glass phase
was then prohibited because of the interlocking crystal
network surrounding the glass matrix. Therefore, a rel-
atively high flexural strength was obtained in GP. Again
according to Fig. 3, the larger lithium disilicate crystals
in GBZ resulted in easier crack propagation in the glass
matrix parallel to the crystals direction and thus a lower
value of flexural strength was obtained in GBZ with re-
spect to that of the base glass ceramic GB. Therefore,
although GBZ showed an acceptable chemical durabil-
ity, its strength is lower than what is required for core
restoratives. In contrast, GP and GB are suitable for any
restorative applications according to Table III.
Data gained from Eq. 2 are plotted in a diagram
demonstrated in Fig. 5. Weibull characteristic strength
s0 for GP, GB and GBZ was calculated 175.75, 146.29,
and 78.38 MPa, respectively. The Weibull parameter m
reflects the statistical distribution of the fracture strength
values. A low m values indicates an inhomogeneous flaw
distribution and thus, low reliability of the predictive
value.10
To investigate the dominate cause of different Wei-
bull modules for the three specimens, some fractography
experiments must have been performed which is not
included in this study. Nevertheless, as mentioned in
literature, when surface defects control the fracture, m is
less than when volume defects cause the fracture.24 It is
also well known that strength at the inner weakest
flaw determines the overall strength of these brittle
materials.18 It can be concluded that GBZ had more
surface defects than GB and GP, respectively. This may
be attributed to the thermal expansion anisotropy in
asymmetry crystalline phases,25 which increases with the
size of crystals. As can be seen from Fig. 3, the size of
plate-like lithium disilicate crystals in GBZ is larger than
those of needle-like crystals of GB and GP which re-
sulted in larger thermal expansion anisotropy along
crystallographic axis during cooling down the samples
from sintering to room temperature. The minimum
value demanded for Weibull parameter m by literature
is 15. So far m 5 4.6, 7.9, and 6.9 have been reported
for Empress 2 framework, Empress Veneer, and Eris,
respectively.10 Li2O–SiO2 glass ceramic systems with
dental applications are often coated by glazes such as
flouroapatite glass ceramics which hampers subcritical
crack growth as a result of filling surface defects.3
 8

Table V. Comparison of Crystalline Phases, Density, Porosity, and Hardness of Bioactive Glasses and Hydroxyapatite Powder
Reported in Literature
Authors Biomaterials Processing Crystalline phases Properties
Marikani et al.22 P2O5–CaO-Na2O– Melting at 15501C/3 h HA Density 5 2.62–2.71 g/cm3
(0–6 wt%)K2O Hv 5 257.6–335.8
Salama et al.20 Melting followed by
two-stage heat
treatments at
SiO2–MgO–CaO– 7201C/5 h–9251C/10 h Di1FA d 5 2.93 g/cm3, H 5 6.93 GPa
4.4P2O5–1.5CaF2
SiO2–1.3Al2O3–MgO– 7051C/5 h–9251C/10 h FA d 5 2.92 g/cm3, H 5 7.01 GPa
CaO-3.5P2O5–1.2CaF2
SiO2–8.2Al2O3–MgO– 7501C/5 h–9601C/10 h FA1Geh d 5 2.87 g/cm3, H 5 8.06 GPa
CaO–4P2O5–1.5CaF2
Cluppera et al.21 45S5 Bioactive glass Tape casting followed by HA P (cm3/g) H (GPa) F. st. (MPa)
(42 wt%)1toluene a heat treatment at 1.14 0.2 30
(38 wt%)1ethanol 8001C/3 h 0.40 2.5 67
(11 wt%)1polyvinyl 9001C/3 h 0.08 5.5 83
butyral (6 wt%)1phthalic 10001C/3 h 0.02 5.7 62
acid (3 wt%) 10001C/6 h
Hoepfner and Case11 Calcium hydroxyapatite Cold-isostatic press at HA Porosity 5 0.021–0.283 (vol%)
powder 80 MPa Hardness 5 0.91–5.42 GPa
(50 specimens)
HA, hydroxyapatite; Di, diopside; FA, fluorapatite; Geh, gehlenite.
International Journal of Applied Ceramic Technology—Khalkhali, Eftekhari yekta, and Marghussian Vol. ]], No. ]], 2011
www.ceramics.org/ACT Mechanical and Chemical Properties of Lithium Disilicate Glass Ceramics
Fig. 5. Regression lines to determine Weibull module.
Thereupon, coating an appropriate glass on the final
product leads to even higher mechanical properties in-
cluding Weibull module.
Table II shows KIC for the three glass ceramics
measured by using Eq. 4. In a study conducted by
Chantikul et al.12 the ratio of E/H was substituted with
0.88; indeed, because this ratio varies only between
10 and 50 for most ceramics, replacement of
ZRV ðE=H Þ1=8 by an average quantity of ZRV (E/H)1/8 5
0.88 would add no more than 10% to the error in the
KIC evaluation for a material whose elastic/plastic
parameters are totally unknown. As shown in Table
II, KIC decreases from GP to GB and to GBZ, respec-
tively. However, the fracture toughness (0.84–
1.94 MPa m1/2) obtained for the samples are compara-
ble and even more than that of tape cast and sintered
bioactive ceramic investigated by Cluppera et al.21 Frac-
ture toughness as a function of strength is often given by
the following equation:
pffiffiffiffiffi
KIC ¼ sf Y pc ð9Þ
where Y is a geometric constant, sf is the fracture
strength, and c is the flaw size.18 The high degree of
Li2Si2O5 crystallization together with the low Ls in GP
specimens, lead to a high fracture strength sf in this
material. Therefore, the highest KIC obtained for GP is
not unexpected. Nevertheless, fracture toughness is
more related to crack arrest due to the residual stress
fields than to crack propagation.26 In this way, the
thermal expansion anisotropy induced in asymmetry
crystalline phases can increase fracture toughness con-
siderably. Furthermore, the difference between elastic
properties of glass and crystal produces various residual
stress fields during cooling down the samples, which
subsequently result in a significant mismatch between
9
stress concentration within glass and crystals. Therefore,
crack arrest due to the random distribution of localized
stress fields in GP would occur more frequently than
that of the base glass ceramic GB and the ZrO2 con-
taining one GBZ.
Conclusions
Three compositions in Li2O–SiO2 glass ceramic
system were fabricated by sintering powdered glass frit
to determine the effect of P2O5 and ZrO2 on their
chemical and mechanical properties. According to the
results, Li2SiO3 and Li2Si2O5 are the two crystalline
phases precipitated in the three specimens after 2 h heat
treatment at peak crystallization temperatures. P2O5
acted as a nucleating agent for crystallization of
Li2Si2O5 by precipitating Li3PO4 crystals. Therefore,
a uniform and interlocking morphology with 57% crys-
tallization were attained in P2O5 containing samples.
Because of the random distribution of needle-like lith-
ium disilicate crystals in GP, which induced crack devi-
ation into the glass phase and prohibited crack
propagation, it appeared that a high flexural strength
was obtained for GP. Similarly, crack arrest in randomly
distributed residual stress fields due to the special
microstructure of GP led to a relatively high fracture
toughness.
ZrO2 led to a high glass viscosity which deteriorate
both sintering and crystallization. Li2SiO3 the low-
temperature crystalline phase, which contained in GB
and GBZ is a chemically non-durable substance and led
to a lower chemical durability in these two specimens.
Li2Si2O5 the high-temperature crystalline phase, pre-
cipitated in GP more intensively that led to higher
mechanical and chemical properties. Considering the
minimum flexural strength and the maximum chemical
solubility required by dental restoratives (EN ISO
6872), GP and GB are suitable for any dental applica-
tions and GBZ can be used as every restorative material
except for dental cores.
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