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journal homepage: www.intl.elsevierhealth.com/journals/dema

Zirconia toughened mica glass ceramics for dental

restorations

Sivaranjani Gali a,1 , Ravikumar K. b,1 , B.V.S. Murthy a , Bikramjit Basu b,∗
a Department of Prosthodontics, Faculty of Dental Sciences, M. S. Ramaiah University of Applied Sciences,
Bangalore, India
b Materials Research Centre, Laboratory for Biomaterials, Indian Institute of Science, Bangalore, India

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

Article history: Objective. The objective of the present study is to understand the role of yttria stabilized
Received 3 May 2017 zirconia (YSZ) in achieving the desired spectrum of clinically relevant mechanical prop-
Received in revised form erties (hardness, elastic modulus, fracture toughness and brittleness index) and chemical
4 October 2017 solubility of mica glass ceramics.
Accepted 9 January 2018 Methods. The glass–zirconia mixtures with varying amounts of YSZ (0, 5, 10, 15 and 20 wt.%)
Available online xxx were ball milled, compacted and sintered to obtain pellets of glass ceramic-YSZ composites.
Phase analysis was carried out using X-ray diffraction and microstructural characterization
Keywords: with SEM revealed the crystal morphology of the composites. Mechanical properties such as
Mica glass ceramics Vickers hardness, elastic modulus, indentation fracture toughness and chemical solubility
Fluorophlogopite were assessed.
Zirconia reinforcement Results. Phase analysis of sintered pellets of glass ceramic-YSZ composites revealed the
Indentation toughness characteristic peaks of fluorophlogopite (FPP) and tetragonal zirconia. Microstructural
Brittleness index investigation showed plate and lath-like interlocking mica crystals with embedded zir-
Chemical solubility conia. Vickers hardness of 9.2 GPa, elastic modulus of 125 GPa, indentation toughness of
Dental ceramics 3.6 MPa·m1/2 , and chemical solubility of 30 ␮g/cm2 (well below the permissible limit) were
Glass ceramics recorded with mica glass ceramics containing 20 wt.% YSZ.
Dental restorations Significance. An increase in hardness and toughness of the glass ceramic-YSZ composites
Transformation toughening with no compromise on their brittleness index and chemical solubility has been observed.
Such spectrum of properties can be utilised for developing a machinable ceramic for low
stress bearing inlays, onlays and veneers.
© 2018 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

[1]. The present global statistics demonstrate an alarming

1. Introduction need for dental crowns and prosthetic rehabilitation. Accord-
ing to National Commission on Macroeconomics and Health
One of the global goals of oral health is to increase the num-
(NCMH), the incidence of complete edentulism has been
ber of individuals with functional dentition by the year 2020
reported to be 7–69% world-wide, with developing nations,
having edentulism at 11–37% in the age group of 65–75 years
[2,3]. Addressing the above clinical problem of edentulism,
∗
Corresponding author.
E-mail address: bikram@mrc.iisc.ernet.in (B. Basu).
1
These authors contributed equally.
https://doi.org/10.1016/j.dental.2018.01.009
0109-5641/© 2018 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Gali S, et al. Zirconia toughened mica glass ceramics for dental restorations. Dent Mater (2018),
https://doi.org/10.1016/j.dental.2018.01.009
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dental ceramics have been popular as indirect restorative
materials due to their esthetics, biocompatibility and chemi-
cal inertness. An important class of dental ceramics is glass
ceramics with favourable properties such as ease of fabri-
cation, good aesthetics, marginal fit, minimal abrasiveness
with enamel and chemical durability [4–7]. Mica containing
glass ceramics (SiO2 –Al2 O3 –MgO–K2 O–B2 O3 –F) are well-known
materials for dental restorations due to their machinability,
bioactivity and resemblance to tooth colour [8–10]. However,
they are brittle in nature and have poor mechanical proper-
ties [7,11–13]. It is apparent that for optimal performance of a
dental material in load bearing function in vivo, a desired com-
bination of hardness, fracture toughness and flexural strength
is essential.
Zirconia ceramics, despite few limitations have gained a
remarkable interest amongst the metal free ceramic systems,
due to their impressive mechanical properties [14,15]. The lim-
itations of zirconia consist of an apparent moisture related
low temperature degradation in the oral cavity. The associated
moisture related phase transformation of t-ZrO2 to m-ZrO2 in
the substructure of zirconia, results in 30–40% reduction of
its fatigue strength [16–19]. Despite its opacity and the recent
trends towards translucent zirconia ceramics, the success of
cementation using air abrasion and tribochemical bonding
remains a critical issue in zirconia ceramics, with no suffi-
cient clinical evidence [20–27]. Cohesive veneer fractures of
zirconia restorations reported in clinical studies further add
up to its limitations [16,20–24,28]. Such fractures have been
related to the low flexural strength of veneering ceramics
and its vulnerable interface with zirconia [29,30]. The low
thermal conductivity and its associated cooling rates and sub-
surface tensile stresses result in unstable cracks in ZrO2 -based
veneers during firing [31,32]. Further, insufficient support of
the veneer and improper core design in the prosthesis con-
tribute to their unpredictable failure [32–36]. With advances
in adhesive bonding and CAD-CAM technology, we intend to
address the above clinical gap with a mica glass ceramic rein-
forced with yttria stabilised zirconia to increase their hardness
and fracture toughness for possible applications involving
monolithic ceramics for low stress bearing inlays, onlays and
veneers [21,37].
The processing strategies, such as heat treatment tech-
niques and second phase additions to the multi component
glass systems have been attempted to strengthen glass ceram-
ics, each presenting with an array of microstructures. Heat
treatment as a function of time and temperature influenced
the microstructure and in vitro properties of mica based
glasses [38]. The addition of fluoride influenced mechanical
properties, microstructure, cell adhesion and antimicrobial
properties of K2 O–B2 O3 –Al2 O3 –SiO2 –MgO–F glass ceramics
[39–42]. TiO2 as a nucleation agent, demonstrated improved
machinability and water resistance to calcium mica apatite
based glass ceramics [43]. Similarly, addition of lithium,
magnesium, calcium and barium to the fluormica glass com-
positions affected its microstructure and properties [44,7,45].
Zirconia (YSZ) as an additive is a well-known strategy
to enhance the hardness and fracture toughness in glass
ceramic composites [46]. The role of YSZ in enhancing
the toughness properties of ceramic due to the phe-
nomenon of transformation toughening is apparent. The
Please cite this article in press as: Gali S, et al. Zirconia toughened mica glass ceramics for dental restorations. Dent Mater (2018),
https://doi.org/10.1016/j.dental.2018.01.009
improvements in bending strength, fracture toughness and
hardness were observed in mica based glass ceramic
(SiO2 –Al2 O3 –MgO–K2 O–B2 O3 –F–P2 O5 ) with 15 wt.% YSZ and
mica apatite with 10 wt.% YSZ using uniaxial pressing [47,48].
Cold isostatic pressing of mica base glass composition of
(MgF2 –Al2 O3 –B2 O3 –P2 O5 –MgO–SiO2 –K2 O) with 30 wt.% of nano
zirconia resulted in significant increase in bending strength
and fracture toughness [49]. Bioverit glass of mica apatite
with zirconia and 20 wt.% YSZ have moderately enhanced
indentation toughness [50]. ZrO2 –SiO2 glass ceramics of 30,
35 and 40 mol% ZrO2 produced using a sol–gel method
showed sufficient transmittance, elastic modulus, hardness
and indentation fracture toughness [51]. Also, 5 wt.% t-ZrO2
toughened apatite wollastanite glass ceramics are reported to
have better bending strength, fracture toughness and micro-
hardness with increasing temperature and heat treatment
time [52].
Mica glass ceramics of the phologopite type are commer-
cially known under the trademark MACOR. Although there
are strategies to improve the properties of phyllosilicate mica
glass ceramics with zirconia, investigations on YSZ-MACOR
based composites in particular, has not been previously
attempted [45,47,49,51,53]. Herein, we present an approach to
enhance the mechanical properties of mica based glass using
yttria stabilizied zirconia (YSZ) as an additive, a well-known
strategy to increase the fracture toughness through transfor-
mation toughening mechanism in ceramic composites [54]. In
addition, the effect of YSZ on the hardness, elastic modulus,
brittleness index and chemical solubility of the glass ceramic
has been analysed and compared to the commercially avail-
able glass ceramics such as IPS emax Press in the present
study.
2. Materials and methods
2.1. Glass preparation and heat treatment schedule
Precursor powders of base glass composition (47.2 SiO2 –16.7
Al2 O3 –9.5 K2 O–14.5 MgO–8.5 B2 O3 –6.3 F (wt.%)) were ball milled
in an agate jar with ethanol as milling medium at 300 rpm
for 6 h to ensure homogenous mixing [40]. Subsequently, the
mixed powders were preheated at 950 ◦ C for 1 h and melted at
1500 ◦ C for 2 h in a platinum crucible. The glass melt was then
quenched in deionised water to obtain the glass frit. The glass
frit powder was ball milled with varying amounts of 3 mol%
YSZ (0, 5, 10, 15 and 20 wt.% YSZ) (D50 ≈ 50 nm) (TOSOH, Japan).
The glass–zirconia mixtures were compacted in a cylindrical
die (15 mm diameter) at 50 kN using a uniaxial hydraulic press
to obtain green compacts. Heat treatment schedule of sin-
tering the base glass powder for 48 h was optimised based
on the results of the differential scanning calorimetry, Fig.
S1 (Supplementary material) demonstrating glass transition
temperature (Tg ) at 740 ◦ C and crystallisation temperature (Tc )
at 1060 ◦ C.
A two stage heat treatment sequence was followed to den-
sify the glass ceramic–ZrO2 powder compact. In the first stage,
the green compact was heated to 800 ◦ C with a heating rate of
25 ◦ C/min in a muffle furnace (Carbolite, UK) and held at this
temperature for 2 h to relieve thermal stresses and to initiate
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Table 1 – Mechanical properties of mica glass ceramic (G) composites with YSZ (wt.%).
Sample Composition Vickers hardness Elastic modulus Indentation toughness, Brittleness index
designation (n = 5) (GPa) (GPa) KIc (MPa m1/2 ) (␮m−1/2 )
G Glass 2.0 ± 0.3 73 ± 1.0 0.8 ± 0.2 2.5
G-5Z Glass + 5 wt.% YSZ 4.6 ± 0.1a , b 80 ± 0.6a , b 2.4 ± 0.4a 1.9a ,b
G-10Z Glass + 10 wt.% YSZ 9.1 ± 0.7a 82 ± 1.5a , b 2.7 ± 0.07a 3.3a
G-15Z Glass + 15 wt.% YSZ 9.2 ± 0.7a 114 ± 0.05a ,b 3.5 ± 0.42a ,b 2.6a ,b
G-20Z Glass + 20 wt.% YSZ 9.2 ± 0.5a 125 ± 5.0a , b 3.6 ± 0.20a ,b 2.5a ,b
IPS emax.Press Lithium disilicate 9.0 ± 1.0 155 ± 3.4 2.8 ± 0.86 (IF) 3.2
a
Indicates a statistically significant difference with respect to the pure glass.
b
Indicates a statistically significant difference with respect to IPS emax Press with p < 0.05.

nucleation of crystal phases. Further heat treatment was car-
ried out at 1080 ◦ C with a heating rate of 10 ◦ C/min for 48 h to
complete the crystallization and densification. The major rea-
sons for choosing a temperature of 1080 ◦ C are crystallization
of fluorophlogopite phase and to prevent the t → m ZrO2 trans-
formation, which occurs at 1100 ◦ C. The rationale for holding
time of 48 h was to provide an adequate time for crystal-
lization. However, this holding time can be reduced by using
advanced sintering techniques such as hot pressing and spark
plasma sintering, which are usually carried out under pres-
sure and can attain higher heating rates resulting in greater
densification in lesser time.
2.2. Phase assemblage and microstructural
characterisation
The phase analysis of the sintered glass ceramic–YSZ com-
posites was carried out using X-ray diffraction (PANalytical,
Netherlands) with Cu K␣ radiation ( = 1.5406 Å) with a step
size of 0.026◦ . For microstructural analyses, the samples
were polished using standard metallographic techniques to
obtain a mirror finish. Polished surface was etched with 12%
HF for 3 min, washed and desiccated before imaging with
SEM–EDS (FEI, Netherlands) to reveal the crystal morphol-
ogy. In addition, semi quantitative analysis of the amount
of m-ZrO2 transformation after a bend test of each of the
glass ceramic–YSZ composites was determined to assess the
amount of stress induced transformation from diffraction data
by the following relations,
Im1 + Im2
Xm =
Im1 + Im2 + It
1.311Xm
Vm =
1 + 0.311Xm
where Xm indicates the weight fraction and Vm , the volume
fraction of m-ZrO2 , Im1 and Im2 indicate the intensities of mon-
oclinic phase peaks at 2 = 28.2◦ and 31.5◦ and It , the intensity
of tetragonal phase peak at 2 = 30.2◦ .
2.3. Mechanical characterisation
For hardness testing, Vickers indentation test was used to
evaluate the microhardness of the composites. Specimen
discs of 15 mm diameter and 2 mm thickness of each of the
glass ceramic composition shown in Table 1 were prepared.
The sintered specimens were polished with SiC polishing
paper grades 220 to 2000 followed by polishing with diamond
paste (1 ␮m and 0.5 ␮m particle sizes) to obtain mirror finish.
The polished surfaces were indented using a micro hardness
tester (Zwick Roell, Germany) with an indent load of 1 kg to
ensure the absence of any cracking from the indent edges and
with a dwell time of 20 s (ASTM E92) to obtain a clear indent
on the specimen surface. The indent diagonals were mea-
sured using an optical microscope to determine the Vickers
hardness using the formula,
Hv = 1.8554 P/d2 (3)
where P is the indentation load (N) and d is the average diag-
onal length (mm) [55]. Elastic modulus was estimated from
load-displacement data obtained during indentation on an
instrumented hardness tester using the Oliver–Pharr formula
[56],
√
 S
Eff = (4)
A 2ˇ
1 1 − 2 1 − i2
= + (5)
Eeff E Ei
where Eeff is effective Elastic modulus, ␯, E is the Poisson’s ratio
of the sample (0.3) and Elastic modulus of the specimen, ␯i , Ei
is the Poisson ratio of the indenter (diamond, 0.01) and Elastic
modulus of the Indenter (10 GPa).
Fracture toughness was measured using the indentation
cracking method (ASTM STP 678). Indentations were made
by Vickers indenter at a load of 5 kg. The crack lengths were
(1)
measured using a scanning electron microscope and fracture
toughness was calculated using the Anstis equation [57]:
(2)  E 1/2 P
KIC = 0.016 (5)
H c3/2
where P is the indentation load (N), H is hardness (GPa), E is
elastic modulus (GPa) and c, the average crack length (m).
The mechanical properties of the glass ceramic–YSZ com-
posites was compared to the commercially available glass
ceramic (IPS emax Press). One of the main requirements
for glass ceramics used in the field of dental prosthetics is
machinability of the material, in other words, the ability to
‘cut’ the material to a desired shape without resulting in cracks
or failure. This requires a balance in the hardness (resistance
to cutting) and toughness (resistance to failure) of the mate-
rial. In the present study, the machinability of the composites

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Fig. 1 – (a) XRD plot of the heat treated mica glass ceramic samples (G) with varying wt.% of YSZ crystallised at temperature
of 1080 ◦ C for 48 h. (b) Comparison of toughness enhancement (KC ) to transformability (Vm ) in varying wt.% of YSZ addition
to mica glass ceramics (G).

was estimated by the parameter ‘brittleness index’, defined as 2.4. Chemical solubility
the ratio of hardness to fracture toughness of a material [58].
ISO-6872 recommends the evaluation of chemical solubility
Hv
B.I = with 4% glacial acetic acid for 16 h to mimic the effect of
KIC
chemical environment of a dental implant over the course
of it lifetime [59]. In the present study, a thermostatic shak-
where in Hv is Vickers hardness in GPa and KIC in MPa m1/2 .

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ing incubator (N-Biotek, NB-250V) was used to carry out the

experiment with at least ten specimens of glass ceramic–ZrO2
composites. Ten specimens of 12 mm diameter and 4 mm
thickness polished till # 600 grit, ultrasonicated in distilled
water and dried at a temperature of 150 ◦ C for 5 h, weighed to
an accuracy of (0.01 mg) in a digital weighing balance (Mettler
Teledo). The samples were then placed in 25 ml of 4% freshly
reconstituted glacial acetic acid in the shaking incubator at
a temperature of 60 ◦ C at 200 rpm for 16 h. The samples were
washed and dried in the hot air oven at a temperature of 150 ◦ C
for 5 h and weighed again. Chemical solubility was calculated
based on the weight loss measured in the samples per unit
surface area as per the ISO-6872:2008 guidelines.

2.5. Statistical analysis

The statistical analysis was performed by using SPSS-20.0

(IBM, USA) commercial software. Each test was conducted on
atleast 5 specimens of each composition. The data is repre-
sented as mean value with standard deviation as error bars.
Statistical analysis on different samples was carried out using
one-way ANOVA, followed by post-hoc Tukey test. A value of
p < 0.05 was considered as statistically significant.

3. Results

3.1. Phase analysis and microstructural

characteriation
X-ray diffraction data is shown all compositions in Fig. 1(a)
along with the diffraction pattern for the amorphous
base glass powder. The characteristic amorphous peak was
observed in the base glass powder before heat treatment. After
the heat treatment, the amorphous peak was absent and sharp
peaks were observed indicating that the crystallization of glass
ceramic phases has been achieved. Phase analysis of heat
treated samples of glass showed characteristic peaks of major
phase, flourophlogopite (FPP) and minor phases, forsterite and
spinel (Fig. 1a). The major peaks corresponding to YSZ, being
completely crystalline, appear more intense as compared to
the phases of the crystallized glass-ceramic.
Detailed SEM analysis was carried out to study the mor-
phological features such as crystal shape and size in the
glass ceramic–YSZ composites. The representative micro-
graphs showing the crystal morphology in glass ceramic–YSZ
composites is provided in Fig. 2(a) and (b). It is observed
that glass ceramic–YSZ composites exhibit plate and lath
like microstructure with interlocking crystals, characteristic
of mica-based glass ceramics with dispersed zirconia parti-
cles. An average aspect ratio of ≈3 and an average crystal size
of 3.4 ␮m were observed in the microstructure.
3.2. Mechanical property evaluation
The results tabulated in Table 1 show a steady increase in
hardness with the addition of YSZ. The maximum hardness of
9.2 GPa was recorded with G-20Z and G-15Z followed closely by
G-10Z (with 9.2 GPa and 9.1 GPa respectively). Hardness values
were found to be similar to the commercially available lithium
Fig. 2 – (a) SEM micrograph (25 kX) of mica glass (G)
crystallised at 1080 ◦ C for 48 h demonstrating plate and lath
like crystals (white arrows) and (b) SEM micrograph (50 kX)
showing nano-YSZ dispersed (white arrow) in the mica
glass matrix.
disilicate glass ceramics (IPS emax Press) tested under similar
laboratory conditions as shown in Table 2.
The values obtained for indentation fracture toughness
are listed in Table 1. Base glass ceramic exhibits poor frac-
ture toughness (0.8 MPa m1/2 ), similar to the products currently
used in the market. However, an increase in fracture tough-
ness was observed with the addition of YSZ to the base
glass. Importantly, indentation fracture toughness values of
3.6 MPa m1/2 was observed in G-20Z composite, which is bet-
ter than the well-known material with the commercial name
IPS emax for dental restorations. The reason for this increase
in fracture toughness is mainly crack blunting due to transfor-
mation toughening of yttria stabilised zirconia and this aspect
is discussed in more detail later in the article.
3.3. Chemical solubility
In the present study, it was observed that the solubility of the
glass-ceramic–ZrO2 composites decreased with an increase
in ZrO2 content as seen in Fig. 4. More importantly, all the
materials tested fall within the prescribed limit for chemical
solubility of 100 ␮g/cm2 for a body ceramic and 2000 ␮g/cm2 for
a core ceramic as per ISO 6872 guidelines. Morever, the chemi-

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Table 2 – Properties of commercial glass ceramics and earlier developed mica glass ceramic composites with YSZ.
Sample Vickers hardness
(GPa)
IPS CAD(precrystalline) 9.2 ± 0.30
K2 O–B2 O3 –Al2 O3 –SiO2 –MgO–1.08% Fa 8.2 ± 1.5
K2 O–B2 O3 –Al2 O3 –SiO2 –MgO–3.85% Fa 6.4 ± 1.2
Mica apatite with 10 wt.% Y-PSZb 4.4 ± 0.82
Mica with 15 wt.% Y-PSZc 4.3 ± 0.64
Bioverit with monoclinic zirconiad – –
Present work (G-20Z) 9.2 ± 0.57
Human enamele 3.5 ± 0.4
Human dentine ∼1
a
Molla and Basu [41].
b
Montazerian et al. [49].
c
Montazerian et al. [48].
d
Verné et al. [54].
e
Roy and Basu [39].
cal solubility of G-20Z (≈28 ␮g/cm2 ) is well within the limts set
by the ISO guidelines.
4. Discussion
4.1. Microstructure-property correlation
XRD pattern of the base glass reveals a broad, diffuse peak in
the 2 range between 35–45◦ in the base glass. The crystallisa-
tion of amorphous glass can be confirmed by the presence of
sharp peaks after the heat treatment of base glass. The peaks
at the 2 values 26.7◦ , 36◦ and 45.4◦ suggest that the major
crystalline phase is FPP. However, the heat treatment process
has also resulted in the formation of minor crystalline phases,
forsterite and spinel. A small fraction of m-ZrO2 has also
been observed due to the t–m transformation during sinter-
ing (Fig. 1b). The formation of these phases can be attributed
mainly to the long duration of sintering, which can be pre-
vented by making use of advanced sintering techniques which
can achieve densification in much shorter scales.
The formation of plate and lath like crystals in the
microstructure is due the two dimensional anisotropic growth
of FPP crystals as the three layered FPP crystal structure pro-
motes a preferential growth along the (001) basal plane [60].
The dissolution of norbergite at temperatures above 750 ◦ C
and the lower viscosity of glass at crystallization temperature
provides the required ions for the formation of FPP crystals
[60].
The addition of fluorine (6 wt.%) to mica based glass is
known to reduce the viscosity of glass and the nucleation
temperature for crystallisation. Lowering of glass crystalli-
sation/glass transition temperature has also been observed
with increased fluorine content to barium mica glass ceramics
[61,62]. Several studies have reported the influence of fluorine
content on the microstructure and properties of glass ceram-
ics. The precursor of fluorine (NH4 F, MgF2 ) has a critical effect
on the crystallisation of fluorosilicate glass ceramic system
[38]. With ammonium fluoride as source of fluorine in the
presently investigated mica glass ceramics and at sintering
temperature above 1000 ◦ C, FPP becomes the only prevailing
crystal phase in the glass matrix [63]. The holding time of 48 h
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Elastic modulus Flexural strength Fracture toughness
(GPa) (MPa) (MPa m1/2 )
129 ± 1.5 – 1.0 ± 0.12 (IF)
58 ± 2.8 95 ± 14 –
70 ± 2.9 81 ± 7.7 –
– 132 ± 14 1.4 ± 0.16 (SEVNB)
– 132 ± 13.8 1.3 ± 0.07 (SEVNB)
96 1.7 (IF)
125 ± 5.0 – 3.6 ± 0.20 (IF)
72 ± 4.5 – –
– – –
has provided an adequate time for FPP crystal growth which
explains its crystal size of 3.4 ␮m. YSZ was observed to be
non-reactive and dispersed as agglomerates amidst the glass
ceramic matrix.
Microstructural parameters such as aspect ratio, volume
crystallinity and the interlocking nature influence proper-
ties such as hardness and machinability of mica based glass
ceramics. A lower aspect ratio (≈3) of FPP crystals and the
addition of YSZ together has contributed to the enhancement
of hardness of glass ceramic–YSZ composites upto 9.2 GPa
(G-20Z). The corelation between aspect ratio and hardness val-
ues has been discussed elsewhere and our results corroborate
well with previous reports [44,64]. Generally, hardness of glass
ceramics is influenced by the ease of crystal deformation, the
anisotropic nature of mica crystals and reduced effect of the
hard residual glass [64]. In this case, the lower aspect ratio of
the lath and plate like morphology makes crystal deformation
difficult resulting in higher hardness. It is interesting to note
that the addition of YSZ beyond 10 wt.% to mica glass ceram-
ics had no statistically significant effect on the hardness of
the composites (see Table 1). This can be attributed to the fact
that with a homogenous distribution of YSZ in the glass matrix
(such as in 10 wt.%), its effect on the hardness is highest and
further addition does not contribute towards any perceptible
increase in the hardness.
While the addition of YSZ resulted in a marginal increase
in hardness (above 10 wt.%), it plays a major role in enhancing
the toughness of the glass ceramic composite. The fracture
toughness of the composites or in other words, the resis-
tance to crack growth in the glass ceramic–YSZ composites is
enhanced through crack blunting mechanisms due to trans-
formation of t-ZrO2 to m-ZrO2 (larger crystal volume) at the
crack tip, which reduces the driving force for crack propoga-
tion and hence increases the toughness. This interaction
between the crack propogation and YSZ particles is evident
in the micrograph shown in Fig. 3(b), where the crack pass-
ing through a collection of brighter particles (YSZ) can be
observed [14,65]. It was observed that toughness of the com-
posites improved with increasing addition of YSZ with a huge
improvement for G-5Z (2.4 MPa m1/2 ) when compared with the
values for base glass ceramic. Further increase in the amount
YSZ has resulted in an increase in the toughness of the com-
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Fig. 3 – (a) SEM photomicrograph (1 kX) of orthogonal cracks
emanating from the corners of an indentation of G-20Z
with different crack lengths along the X and Y-axes and (b)
SEM image (3 kX) of crack blunting due to transformation
toughening of YSZ in G-20Z glass ceramic.
posites with G-20Z having a fracture toughness of 3.6 MPa m1/2
for 20 wt.% addition of YSZ. This is in sharp contrast to the
effect of YSZ on the hardness property. As fracture toughness
is essentially the amount of energy absorbed by the mate-
rial before undergoing fracture, higher YSZ content increases
the absorbed energy through stress induced phase transfor-
mation from t-ZrO2 to m-ZrO2 and hence results in higher
toughness for G20Z composite. The phenomenon of transfor-
mation toughening has been confirmed in the study through
semi-quantitative analysis of diffraction data of the compos-
ites before and after fracture through a bend test according to
the method suggested by Toraya et al. [66]. The XRD patterns
obtained before and after fracture are given as supporting
material. The effect of transformation of t-ZrO2 in toughening
the composite is depicted in Fig. 1(b) for different compositions
of glass–ZrO2 composites. A steady increase in transformabil-
ity and hence toughness is observed with an increase in the
Please cite this article in press as: Gali S, et al. Zirconia toughened mica glass ceramics for dental restorations. Dent Mater (2018),
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xxx.e7
Fig. 4 – Chemical solubility values of mica glass ceramic (G)
composites with varying wt.% of YSZ, commercial dental
glass ceramics* and permissive limits of ISO 6872
guidelines.
*(Values obtained from product’s scientific documentation).
YSZ content in the glass ceramics. In particular, an increment
of 2.8 MPa m1/2 in toughness with respect to base glass ceramic
due to a transformability of 27% was observed in 20 wt.% YSZ
mica glass ceramic composite, as shown in Fig. 1(b).
Previous studies on mica based glass ceramics reinforced
with zirconia have shown comparatively low fracture tough-
ness (SEVNB) from 0.8 MPa m1/2 to 1.44 MPa m1/2 [53,67]. As
fracture toughness is a clinically relevant parameter that
measures inherent property of a material to resist crack prop-
agation, this result is of utmost significance [68]. The results
of hardness and indentation fracture toughness in G-20Z
are comparable to the commercially available IPS emax.CAD
and IPS emax.Press as shown in Table 2. While there is
no statistically significant difference in the hardness among
G-10Z, G-15Z, G-20Z and available IPS emax Press, the frac-
ture toughness shows a significant difference between G-20Z
(3.6 MPa m1/2 ) and IPS emax Press (2.8 MPa m1/2 ). However, it is
essential to note that results of fracture toughness can vary
depending on the method of testing used and in the present
case, the indentation fracture toughness method is known to
overestimate the crack growth resistance of the material as
compared to a single edge notch beam method, which gives a
more conservative estimate [57,69].
Brittleness index is usually used to assess the machinabil-
ity of a material before attempting any shaping or forming
techniques. A brittleness index of less than 4.3 ␮m−1/2 is
usually required for a material to be machinable [70]. The
brittleness index of glass ceramic–YSZ composites is given in
Table 1. It is observed that all the glass ceramic–YSZ compos-
ites have lesser values of brittleness index and are machinable.
Since there is an improvement in fracture toughness for
glass–YSZ composites along with an increase in hardness, all
the compositions are machinable. Though, the composition
with 5 wt.% YSZ shows the lowest brittleness index (highest
machinability), its hardness and fracture toughness properties
are relatively poor compared to G-15Z and G-20Z. Hence, G-15Z
and G-20Z are expected to be most suitable among the com-
positions for dental restorations with properties marginally
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better than commercially available products. Though machin-
ability is one of the prime advantages of mica glass ceramic
due to inherent nature of weak basal planes between the
silicate chains, the enhancement of fracture toughness and
hardness of glass ceramic–YSZ composites make them more
suited for applications in dental restorations.
4.2. Chemical solubility of glass ceramic–YSZ
composites
The precursor of the presently studied mica glass ceramic
composite is a base glass consisting of oxides of silicon,
alumina, potassium (alkali), magnesium (alkaline earth) and
boron with fluoride. The mechanism of solubility happens
with the selective leaching of alkali ions from the glass matrix
and dissolution of the glass network. However, glasses in crys-
tallized state are more resistant to leaching than in the glass
phase [71]. The presence of alumina and zirconia immobi-
lize the alkali ions in the glass ceramic and hence, reduced
chemical solubility is seen in G-20Z when compared to other
wt.% of YSZ added mica glass ceramics [72]. For an improved
chemical durability, a 7 wt.% of zirconia is required in a mica
glass ceramic system [71]. A formulation of tetra silicic flu-
ormica system containing at least 0.5 wt.% Al2 O3 and 2 wt.%
ZrO2 was recommended for optimal chemical durability [73].
Thus, lower chemical solubility of G-20Z could be attributed
to its partial crystallized state, presence of glass modifiers and
YSZ in its composition.
5. Conclusions
The current choice of glass ceramic materials for ceramic
restorations range from heat pressed leucite (IPS Empress),
lithium disilicate glass ceramics (IPS emax.Press) to felds-
pathic porcelains (VITA Mark II) and machinable IPS
emax.CAD. Our findings show comparable properties of G-20Z
in particular, to the commercially available IPS emax Press
and IPS emax CAD in terms of fracture toughness, hardness
and chemical solubility. A spectrum of properties of zirco-
nia toughened mica based glass ceramic composites can be
explored for metal free ceramic inlays, onlays and veneers.
Acknowledgements
We thank Wellcome Trust DBT India Alliance for funding the
project under Research Training Fellowship with the grant
number IA/RTF/14/1/1014 and Translational Centre on Bio-
materials for Otthopaedic and Dental applications funded by
Department of Biotechnology, Government of India.
Appendix A. Supplementary data
Supplementary data associated with this arti-
cle can be found, in the online version, at
https://doi.org/10.1016/j.dental.2018.01.009.
Please cite this article in press as: Gali S, et al. Zirconia toughened mica glass ceramics for dental restorations. Dent Mater (2018),
https://doi.org/10.1016/j.dental.2018.01.009
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