Future Dental Journal 2 (2016) 55e64

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Future Dental Journal

journal homepage: http://www.journals.elsevier.com/locate/fdj

Zirconia based ceramics, some clinical and biological aspects: Review

Ossama Saleh Abd El-Ghany*, Ashraf Husein Sherief
Department of Fixed Prosthodontics, Faculty of Oral and Dental Medicine, Future University in Egypt FUE, Egypt

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

Article history: Improved material strength, enhanced esthethic and high biocompatibility give Zirconia ceramic a great
Received 22 August 2016 possibility to be used for a wide range of promising clinical applications. This review presents the
Accepted 3 October 2016 different types of zirconia materials available for dental application, the effect of machining procedures
Available online 20 October 2016
on these materials, the esthetic of zirconia ceramics and bonding of the veneering ceramics in addition to
the biologic properties of these new materials.
Keywords:
© 2016 Faculty of Oral & Dental Medicine, Future University. Production and hosting by Elsevier B.V. This
Zirconia ceramics
is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/
Machining
Bonding
4.0/).
Esthetics
Biological aspect
Radioactivity

1. Introduction Zirconium (symbol Zr) is a transition metal element, atomic

The Stone Age and Bronze Age were named for the materials
that dominated these major historical periods. Consequently, the
modern era, which is encountering an ever-increasing assortment
of ceramic materials for industrial or biomedical use, could be
characterized as the “Ceramic Age”. Ceramic materials that
specially developed for medical and dental use are termed bio-
ceramics. Over the last decade, zirconia technology has encouraged
a rapid development of metal free dentistry that may provide high
biocompatibility, enhanced esthetics and improved strength [1].
The name “Zirconium” comes from Arabic word “Zargon” which
means “golden in color” which in turn comes from the two Persian
words Zar (gold) and Gun (color). Zirconium dioxide (ZrO2) was
accidentally discovered by a German chemist his name is Martin
Heinrich Klaproth in 1789 while he was working with certain
procedures that involved the heating of some gems [2]. Subse-
quently, Zirconium dioxide was used as rare pigment for a long
time. In late sixties the progress of research, the use of zirconium as
biomaterials was refined. The first use of zirconium oxide (ZrO2) for
medical purposes was made in 1969 in orthopedic as a new ma-
terial for hip head replacement instead of titanium or alumina
prostheses [3].
* Corresponding author.
E-mail address: osama.abdelghany@fue.edu.eg.com (O.S. Abd El-Ghany).
Peer review under responsibility of Faculty of Oral & Dental Medicine, Future
University.
number 40, atomic weight 91.22, density of 6.49 g/cm3, a melting
point of 2,128 K (1855
C or 3371
F) and a boiling of 4,682 K
(4409
C or 7968
F) and lustrous with exceptional corrosion
resistance. Pure zirconium exists in crystalline form as a white and
ductile metal and in an amorphous form as a blue black powder.
Zirconium is ranked 18th in abundance among the element in
earth's crust, however, this element does not occur in nature in a
pure state but only in conjugation with silicate oxides (ZrO2 XSiO2)
or as a free oxide (ZrO2) [4-7]. Zirconium Dioxide (ZrO2) is a white
crystalline oxide of zirconium found in the minerals baddeleyite
(ZrO2) and zircon (ZrO2).
Zirconium oxide crystals can be categorized into three crystal-
lographic phases: the cubic phase (C) in the form of straight prism
with square side, the tetragonal phase (T) in the form of a straight
prism with rectangular sides, and the monoclinic phase (M) in the
form of a deformed prism with parallelepiped sides. The cubic
phase is stable above 2370
C and with moderate mechanical
properties, the tetragonal phase is stable between 1170
C and
2370
C with improved mechanical properties, and the monoclinic
phase, which is stable at room temperature up to 1170
C, with
lower mechanical properties and may contribute to a reduction of
the ceramic particles cohesion [8-10].
These lattice transformations are martensitic, characterized by
being diffusionless (i.e. involving only coordinated shifts in lattice
positions versus transport of atoms), occurring athermally implying
the need for a temperature change over a range rather than at a
specific temperature and, involving a shape deformation [4].This

http://dx.doi.org/10.1016/j.fdj.2016.10.002
2314-7180/© 2016 Faculty of Oral & Dental Medicine, Future University. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
56 O.S. Abd El-Ghany, A.H. Sherief / Future Dental Journal 2 (2016) 55e64
transformation range is bounded by the martensitic start (Ms) and
martensitic finish temperatures. Volume changes on cooling asso-
ciated with these transformations are very crucial and substantial
so it results in a pure material that is unsuitable for any applications
requiring an intact solid structure. This change is about 2.31% in
case of C/T transformation and approximately 4.5% on cooling
from T to M [5].
1.1. Phase transformation
At ambient pressure, unalloyed zirconia can be found in three
crystallographic forms depending on the temperature. At room
temperature and upon heating up to 1170
C, it is monoclinic. At
temperature between 1170 and 2370
C it is tetragonal and above
2370
C and up to the melting point it is cubic.
Upon cooling, the transformation from the tetragonal (t) phase
to the monoclinic (m) phase is characterized by a substantial in-
crease in volume (about 4.5%), sufficient to lead to catastrophic
failure, sufficient to lead to catastrophic failure. This transformation
begins at 950
C and is reversible [11].
Garvie et al. in their important paper “Ceramic Steel” explained
the best method to use phase transformation of zirconia to improve
the mechanical strength and toughness of this type of ceramics.
They stated that tetragonal phase precipitates that are finely
dispersed within the cubic matrix were able to be transformed into
the monoclinic phase when the constraint exerted on them by the
matrix was relieved by a crack propagated within the matrix. The
stresses resulted from this phase transformation (into a larger size
phase) will act in opposite direction to the stress fields that initiate
and promotes crack propagation. Such mechanism will result in
enhancement in fracture toughness as the energy associated with
crack propagation is dissipated both in both phase transformation
and in overcoming stresses due to the volume expansion.This
process is known as transformation toughening [6].
It was discovered that such strong ceramic could result from
alloying of pure zirconia with lower valance oxides, such as MgO,
La2O3, CaO and Y2O3, and this decreased the amount of strained (m)
phase at room temperature and favored more symmetric (c) and (t)
lattice structures. These (c) and (t) phases are analogous to those in
pure zirconia but have dopant ions substituted on Zr4þ sites and
have a fraction of oxygen sites vacant to retain charge neutrality [7].
2. Different types of zirconia ceramics materials available for
dental applications
2.1. Yttrium tetragonal zirconia polycrystals (3Y-TZP)
Since the late eighties, biomedical grade zirconia usually con-
tains 3mol% yttria (Y2O3) as a stabilizer (3Y-TZP) [8]. 3Y-TZP has
been used to manufacture femoral heads in total hip replacement
prostheses, but its use in orthopedic surgery has been reduced by
more than 90%, mostly due to a series of failures that occurred in
2001 [2]. Also 3Y-TZP is available in dentistry for the fabrication of
dental crowns and fixed partial dentures. It has superior mechan-
ical properties as its flexural strength reaches 900e1200 MPa and
fracture strength about 9e10 MPa(m)1/2 [12e13].
The restorations are processed either by soft machining of
presintered blanks or by hard machining of fully sintered blocks.
The mechanical properties of 3Y-TZP are strongly affected by its
grain size [9]. Above a critical grain size, 3Y-TZP is less stable and
more susceptible to spontaneous t/m transformation (grain sizes
(<1 mm) are associated with a lower transformation rate). In the
same time, below a certain grain size about 0.2 mm, the trans-
formation is not possible, leading to reduced fracture toughness
[10]. Consequently, the sintering conditions (through which the
grain size is controlled) have a strong impact on both stability and
mechanical properties of the final product. Higher sintering tem-
peratures and longer sintering times lead to larger grain sizes [11].
Currently available 3Y-TZP for soft machining of dental restorations
utilizes final sintering temperatures between 1350
C and 1550 C
depending on the manufacturer.
Restorations produced by soft machining are sintered at a later
stage (i.e. following the forming steps), this process prevents the
stress-induced transformation from tetragonal to monoclinic and
leads to a final surface virtually free of monoclinic phase unless
grinding adjustments are needed or sandblasting is performed.
Most manufacturers of 3Y-TZP blanks for dental applications do not
recommend grinding or sandblasting to avoid both the t/m
transformation and the formation of surface flaws that could be
detrimental to the long-term performance, despite the apparent
increase in strength due to the transformation-induced compres-
sive stresses. In contrast, restorations produced by hard machining
have been shown to contain a significant amount of monoclinic
zirconia. This is usually associated with surface microcracks, higher
susceptibility to low temperature degradation (LTD) and lower
reliability [14].
2.2. Glass-infiltrated zirconia-toughened alumina (ZTA)
Another approach to advantageously utilize the stress induced
transformation capability of zirconia is to combine it with an
alumina matrix, leading to a Zirconia-Toughened Alumina (ZTA)
[15]. One commercially available dental product, In-Ceram Zirconia
(VidentTM, Brea, CA), was developed by adding 33 vol% of 12mol% ̊
ceria stabilized zirconia (12Ce-TZP) to In-Ceram Alumina [16]. In-
Ceram Zirconia can be processed by either slip casting or soft
machining. Initial sintering takes place at 1100
C for 2 h, followed
by glass infiltration of this porous ceramic composite.
One of the main advantages of the slip-cast technique is the very
limited amount of shrinkage. However, the amount of porosity is
greater than that of sintered 3Y-TZP and comprises between 8 and
11% [17]. This explains the lower mechanical properties of In-Ceram
Zirconia when compared to 3Y-TZP dental ceramics [12]. On the
other hand Ce-TZP ceramics usually exhibit better thermal stability
and more resistance to low temperature degradation than Y-TZP
under similar aging conditions [18].
In-Ceram Zirconia for soft machining is thought to exhibit better
mechanical properties compared to slip-cast ceramic due to more
consistent processing. Conversely, Guazzato et al. reported a
significantly higher flexural strength for In-Ceram Zirconia pro-
cessed by slip-casting (630 ± 58 MPa) compared to the soft
machined material (476 ± 50 MPa) [19]. Also the fracture toughness
varied between 3.1 and 4.61 MPa(m)1/2 for both materials [20]. The
two materials exhibited similar microstructure characterized by
large alumina grains (6 mm long, 2 mm wide) together with clusters
of small zirconia grains (less than 1 mm in diameter). The crack
patterns were consistently transgranular for ZrO2 and intragranular
for Al2O3. An advancing crack results in the tetragonal to mono-
clinic transformation. The associated increase in volume creates
microcracks in the alumina matrix surrounding the transformed
particle. The toughness is therefore enhanced by microcracking
[21].
2.3. Magnesia partially stabilized zirconia (Mg-PSZ)
Although a considerable amount of research has been focused
on magnesia partially stabilized zirconia (Mg-PSZ) for possible
biomedical applications, this material has not been successful. This
mainly due to many causes as the presence of porosity, the large
grain size (30e60 mm) that can cause wear of the opposing
 O.S. Abd El-Ghany, A.H. Sherief / Future Dental Journal 2 (2016) 55e64
structure, its low stability and low overall mechanical properties
[22]. The microstructure consists of tetragonal precipitates within a
cubic stabilized zirconia matrix. The amount of MgO in the
composition of commercial materials usually ranges between 8 and
10mol%. In addition to a high sintering temperature (between 1680
and 1800
C), the cooling cycle has to be strictly controlled,
particularly in the aging stage with a preferred temperature of
1100
C.2 Precipitation of the transformable t-phase occurs during
this stage, which volume fraction is a critical factor in controlling
the fracture toughness of the material [23].
It is very difficult to obtain Mg-PSZ precursors free of SiO2, so
Magnesium Silicates can form and this decreases the Mg content in
the grains and promote the t/m transformation [24]. This can
result in less stable material with lower mechanical properties.
Denzir-M® (Dentronic AB) is an example of Mg-PSZ ceramic avail-
able for hard machining of dental restorations.
2.4. Zirconia-containing lithium silicate ceramics (Zls)
Lithium silicate-based glass-ceramics were recently introduced
as machinable materials to be used with (Computer aided design-
computer aided manufacture (CAD-CAM) techniques, with
claimed mechanical properties comparable with those of lithium
disilicate glass ceramics. The technology for this new material relies
on the addition of 10 wt% zirconium oxide to lithium silicate glass
compositions. Zirconia crystals act as nucleating agent but remains
in solution in the glassy matrix. A dual microstructure consisting of
very fine lithium metasilicate (Li2SiO3) and lithium disilicate
(Li2Si2O5) crystals is obtained, with a glassy matrix containing zir-
conium oxide in solution [25].
The microstructure is achieved through two stages. The glass-
ceramic in the first pre-crystallized stage contains only lithium
metasilicate crystals and is easy to machine. The final crystalliza-
tion stage, leading to the dual lithium silicate microstructure, is
obtained after a short heat treatment at 840
C for 8 min.
The main difference between ZLS and lithium disilicate glass
ceramics glass ceramics in their final stage of crystallization resides
in the nature of the crystalline phases: lithium metasilicate plus
lithium disilicate for ZLS and lithium disilicate only for lithium
disilicate glass ceramic. The development of zirconia-containing
lithium silicate glass ceramics illustrates the ongoing quest for
ceramic materials that offer adequate translucency combined with
superior mechanical properties. These stable ceramics may offer a
better reliability than zirconia ceramics but may not represent the
endpoint for this quest [25].
According to the manufacturers, these materials offer mechan-
ical properties ranging from 370 to 420 MPa. These values are
comparable with lithium disilicate glass ceramics [26]. The me-
chanical properties are approximately three times higher than
those determined for leucite-reinforced glass ceramics (IPS
Empress, Ivoclar Vivadent, Schaan, Liechtenstein). In vitro testing
revealed a Weibull modulus of 8.9 for this material group which
indicates a uniform and reliable material quality. The improved
strength and reliability are reached by the addition of 8e10 wt% of
zirconium oxide with a mean grit size of approximately 0.5e0.7 mm
[27].
Today, these materials are available as industrially prefabricated
blanks for various CAD/CAM systems (e.g., Cerec, Sirona, Bensheim,
Germany; Artica, KaVo, Leutkirchen, Germany; and Ceramill,
Amann Girrbach, Pforzheim, Germany) in various shades and
translucencies [28]. Rinke et al. stated that ZLS ceramics offer an
excellent combination of high strength and outstanding optical
properties. Thus, these materials are interesting for the fabrication
of monolithic restorations. However, although laboratory studies
showed that ZLS ceramics have a positive combination of
57
properties, the indication should be chosen with strict observation
of the material-specific processing instructions. This attention to
indications and processing instructions is especially important
regarding the necessary minimum wall thickness and required
adhesive luting. Long term clinical studies still needed to verify the
positive results from the few initial clinical experiences available
[29].
2.5. Resin nano-ceramic materials
Lava Ultimate CAD/CAM restorative is a highly cross-linked
polymeric matrix contains a proprietary blend of three fillers: zir-
conia and silica nano particles agglomerated into clusters; indi-
vidually bonded silica nano particles; and individually bonded
zirconia nano particles. The material contains about 80% (by
weight) of this filler blend. The result is a material that has different
properties than feldspathic glass ceramic and composite materials.
This new material offers higher flexural strength and fracture
toughness, which results in long-term durability and maintains a
polish well over the long term.
Lava Ultimate CAD/CAM restorative is easy to mill needs to
polish for a few minutes to achieve an enamel-like luster. The
material is available in eight shades, with both high and low
translucency options, giving dentists the palette necessary to
closely match the esthetics of the patient's dentition. It also allows
for easy adjustments. The material is suitable for use with crowns
(including implant-supported crowns), onlays, inlays and veneers.
The material can be used in challenging areas such as the second
molar, and also blends very well esthetically alongside ceramic
restorations [30].
2.6. Machining of zirconia
CAD/CAM zirconia dental restorations can be produced ac-
cording to two different machining techniques: soft machining of
pre-sintered blanks or hard machining of fully sintered blanks.
2.7. Soft machining of pre-sintered blanks
Since its development, direct ceramic machining of pre-sintered
3Y-TZP has become increasingly popular in dentistry and is now
offered by a growing number of manufacturers. Briefly, the die or a
wax pattern is scanned, an enlarged restoration is designed by
computer software (CAD) and a pre-sintered ceramic blank is
milled by computer aided machining then the restoration is then
sintered at high temperature.
Typically the powder used in the fabrication of the blanks
contains a binder that makes it suitable for pressing that will be
eliminated during the pre-sintering step. The powders consist of
spray-dried agglomerates (about 60 mm in diameter) of much
smaller crystals that are about 40 nm in diameter. The blanks are
manufactured by cold isostatic pressing. The mean pore size of the
compacted powder is very small in the order of 20e30 nm with a
very narrow pore size distribution [31].
The binder is eliminated during a pre-sintering heat treatment.
This step has to be controlled carefully by manufacturers, as If the
heating rate is too fast, the elimination of the binder and associated
burn out products can lead to cracking of the blanks. Slow heating
rates are therefore preferred. The pre-sintering temperature of the
blanks affects the hardness and machinability. These two charac-
teristics act in opposite directions: an adequate hardness is needed
for the handling of the blanks but if the hardness is too high, it
might be detrimental to the machinability. The temperature of the
pre-sintering heat treatment also affects the roughness of the
machined blank. Overall higher pre-sintering temperatures lead to
58 O.S. Abd El-Ghany, A.H. Sherief / Future Dental Journal 2 (2016) 55e64
rougher surfaces. The choice of a proper pre-sintering temperature
is thus critical [31].
Several variations of the milling process exist for example; both
contact scanners and non-contact scanners are available. Overall,
non-contact scanners are characterized by a higher density of data
points and a greater digitizing speed compared to contact scanners.
Sintering of the machined restorations has to be carefully
controlled, typically by using specifically programmed furnaces.
Shrinkage starts at 1000
C and reaches about 25%. Sintering con-
ditions are product-specific. Final sintering temperatures between
1350 and 1550
C with dwell times between 2 and 5 h lead to
densities greater than 99% of the theoretical density. These varia-
tions in sintering conditions are likely to be due to the initial
chemical composition of the 3YTZP powder. For example, small
additions of alumina have been shown to act as a sintering aid,
allowing the use of lower sintering temperatures and times. The
minimum thickness for the copings is 0.5 mm, below which
warpage could occur. The restorations are furnace-cooled to a
temperature below 200
C to minimize residual stresses. As
mentioned earlier, the sintering temperatures and times strongly
influence the grain size [32]. Chevalier et al. [11] also demonstrated
that the amount of cubic phase in 3Y-TZP increases when the sin-
tering temperature reaches 1500
C with a sintering time of 5 h. The
presence of larger cubic grains is detrimental to the resistance of
the ceramic to low temperature aging.
Restorations can be colored after machining by immersion in
solutions of various metal salts such as cerium, bismuth, iron or a
combination thereof [33]. The color develops during the final sin-
tering stage. The concentration of the solution strongly influences
the final shade. Concentrations as low as 0.01mol% are sufficient to
produce a satisfactory coloration. The final sintering temperature
influences the color obtained. Careful respect of the manufacturer's
instructions is therefore important. Coloration with various metal
salts does not appear to affect the crystalline phases or mechanical
properties of the final product. Alternatively, colored zirconia can
be obtained by small additions of various metal oxides to the
starting powder [34]. The restorations are finally veneered with
porcelains of matching coefficient of thermal expansion. The
veneering porcelain is baked at nearly 900
C, with a hold time of
1 min [9]. Representative systems utilizing soft machining of 3Y-
TZP for dental restorations are Cercon® (Dentsply International),
LavaTM (3MTM ESPETM), Procera® zirconia zirconia (Nobel Bio-
careTM), YZ cubes for Cerec InLab® (VidentTM) and IPS e.max®
ZirCAD (Ivoclar Vivadent).
2.8. Hard machining of 3Y-TZP and Mg-PSZ
Y-TZP blocks are prepared by presintering at temperatures
below 1500
C to reach a density of at least 95% of the theoretical
density. The blocks are then processed by hot isostatic pressing at
temperatures between 1400 and 1500
C under high pressure in an
inert gas atmosphere [35,36]. This latter treatment leads to a very
high density in excess of 99% of the theoretical density.
The blocks can then be machined using a specially designed
milling system. Due to the high hardness and low machinability of
fully sintered Y-TZP, the milling system has to be particularly
robust. A study by Blue et al. demonstrated that Y-TZP was signif-
icantly harder to machine than fully sintered alumina with lower
material removal rates [37]. This was confirmed by other re-
searchers who reported that coarse diamond burs were more
efficient for material removal with Y-TZP, while machining with
fine burs led to a more ductile type of damage [38,39]. At least two
systems, Denzir® (Cadesthetics AB) and DCZirkon® (DCS Dental AG)
are available for hard machining of zirconia dental restorations.
2.9. Esthetic aspect of zirconia ceramics:
Zirconia framework is esthetically better accepted than metallic
framework, but it remains too white and opaque. Colored zirconia
framework was introduced to simulate the color of natural teeth. A
traditional ceramic-engineering approach is to add coloring oxides
to zirconia powders prior to blanks pressing. Another approach is
color-doping of powder granules by co-precipitation, leading to
homogeneous color distribution. The need for many shades makes
both of these two approaches financially challenging. A popular
means of coloring zirconia restorations is by infiltration of various
metal salts at low concentrations [40]. However, this technique has
some drawbacks, as a non uniform color due to the possible pres-
ence of porosity gradients [41]. Problems due to limited diffusion
depth of coloring solutions have also been reported, leading to
color variations from one area to another after grinding adjust-
ments. Also, the sintering temperature should be carefully
controlled, since it may influence oxidation state and therefore
color [42].
Y- TZP blocks could be custom - colored where the technique
involves infiltration of the machined restoration at the presintered
stage being brought into a highly porous state with special coloring
solutions to produce work pieces of various shades [40].
These solutions could be applied through immersion of the
restoration in coloring solution for a definite time and concentra-
tion, deposition of the solution by means of spraying process or
through deposition of solutions by means of application in-
struments as brush or swab. After drying and at the initial stage of
heating of the immersed porous presintered zirconia blocks, the
acetic, chloric and nitric ions probably burn out or vaporized and
disappear on the surface of the pores. The metal ions form an oxide
layer on the surface of the pores of zirconia blocks. Theses metal
oxides form a new product with zirconia via solid-solid reaction or
remains as oxides at the boundaries around zirconia around zir-
conia grains in the final sintering stage (1350e1600
C). These
techniques with infiltration with a coloring liquid although were
thought to have theoretically more customization and character-
ization, few drawbacks as lake homogeneity and infiltration of the
surface layers more than the bulk material had been reported [43]
The ability to control the shade of the zirconia core may elimi-
nate the need to veneer the lingual and gingival aspects of the
connectors in difficult situations like limited interocclusal distance
and the required connector dimensions are minimally achieved.
Also, the palatal aspect of anterior crowns and FPDs may be fabri-
cated of the core material only in cases like extensive vertical
overlap and lack of space for lingual veneering porcelain [44,45].
Since the esthetic of value of a ceramic restoration is based on its
ability to be in harmony with the adjacent natural teeth. Many
authors considered the translucency as a key component for suc-
cess of ceramic restorations [46,47]. Zirconia based ceramics have
poor translucency due to their chemical nature, the amount of
crystals, the particles' size, the pores and the sintered density. All of
these factors determine the amount of light that is reflected,
transmitted and absorbed and hence the optical properties of the
ceramic materials [48]. Since Zirconia based ceramics (like Y-TZP)
are polycrystalline materials, most of the light passing through it is
intensely scattered and diffusely reflected leading to its opaque
appearance [49].
Some studies suggested that microcrystals and full densification
could enhance light transmission and optical properties of zirconia
ceramic [50-52]. Jiang et al. found that Y-TZP could gain nearly full
density and 17e18% transmittance if finally sintered at
1450e1500
C [53].
Attempts trying to introduce translucent zirconia had been
through consolidating nano-powder to full density with nano-
 O.S. Abd El-Ghany, A.H. Sherief / Future Dental Journal 2 (2016) 55e64
crystals through the industrial sintering technique such as hot e
isostatic pressing (HIP), millimeter wave, microwave and spark
plasma sintering (SPS) [51-55]. Electric current assisted powder
consolidation techniques have became of the most successful
methods for production of a fully dense ceramic with nano-size
crystals [56].
2.10. Bonding of veneering material to zirconia
Zirconia core is covered by veneering porcelains to realize the
esthetic restoration. The veneering of the zirconia ceramic may be
performed with ceramics using a layering technique, or a press
technique, or combination of these techniques.
It seems that the veneering porcelains are mainly bonded to
zirconia with mechanical interlocking and compressive stress due
to the small difference between the zirconia and the veneering
porcelain in thermal shrinkage by cooling after sintering. Also there
was no evidence for chemical bonding between the zirconia and
the veneering porcelains, SEM observation could not confirm the
presence of reaction layer between the zirconia and the veneering
porcelain. In addition to the difference in coefficient of thermal
expansion many other factors could affect bonding between zir-
conia core and veneering material as poor wetting of the core with
the veneering material, firing shrinkage of the veneering layer,
phase transformation of zirconia crystals at the core e veneer
interface due to thermal and/or mechanical stresses and inherent
flaw formation during processing [57].
Coefficient of thermal expansion of veneering ceramic
(8.8e10.0  106 per
C) which is slightly less than that of zirconia
core (10.0e10.5  106 per
C), this difference leads to compression
within the veneering mass and enhance bonding to zirconia core.
Current studies demonstrated that sandblasting of the core mate-
rial prior to veneer application did not enhance bonding, and even
have negative effect due to alumina particles remain on the surface
[58]. Bonding strengths between zirconia and veneering porcelains
ranged between 26.5 and 31.6 MPa [50].
Chipping or lamination of the veneer material was recorded as
one of the most common complications of zirconia restorations.
Von steyern et al. [59] reported that porcelain chip-off fractures
causes the success rate of Dc zircon all-ceramic fixed partial den-
ture to drop from 100 to 85% after 2 years. Also, Donovan reported
that the fracture rate of the veneering ceramic has ranged from 8 to
50% at one to two years, while the reported rate of veneer fracture
with metal ceramic restorations has been between 4 and 10% after
10 years [60]. The cause of this chipping is not known, and both
core flexure and bond failure have been suggested. Another
possible cause of chipping is the lack of uniform support of the
veneering ceramic by the core. Bonfante et al. [61] stated that their
results suggest that the porcelain to core thickness ratio play a role
on the fracture chip size in anatomically correct molar crowns,
investigations concerning alterations in core geometric design with
thinner and more uniform veneer thickness are warranted.
One of the most frequent technical problem in all studies of
zirconia reconstructions is chipping or cracking of the veneer
ceramic In an investigation using a different prototype zirconia
ceramic, veneer chipping was found in 15.2% of the cases after 35.1
months of follow-up [62]. In another investigation with the same
zirconia ceramic, chipping was found in 13% after 37.2 months [63].
Also, chipping of the veneer was reported to occur in 15% of the
cases after 2 years [64]. A fourth study reported chipping in 25% of
cases after 31.2 months of observation [65]. Finally, a study re-
ported the lowest chipping incidence, 6% after 37months. These
results were attributed to low or moderate bond strength between
zirconia frameworks and veneering ceramics and it can be
concluded that various veneering ceramics available for zirconia
59
possess insufficient mechanical properties [66].
The use of zirconia surface modification techniques to achieve
strong bond between coping and veneering ceramic could improve
the clinical failure rates observed. Application of a silicate inter-
mediate layer, applied on the zirconia surface via a tribochemical
approach or vapour deposition approach that could also enable
conformal silicate surface modification without use of an aggres-
sive physical process, which might result in damage to the coping
surface. The application of a liner, used to modify the color of white
zirconia for esthetics, has shown mixed results in bond strength
when used on veneers [67].
Sandblasting is a popular means. It might be assumed that
sandblasting would enhance the bond strength of cores to
veneering porcelains by increasing surface roughness and
providing undercuts [68,69]. The results of a recent study by Saleh
[70] showed that sandblasting with 110 mm Al2O3 particles effec-
tively increased both surface roughness (Ra) of zirconia samples
and shear bond strength between zirconia and the veneering por-
celain compared with the untreated samples However, another
study by kim et al. reported that bond strength decreased by
sandblasting [71].
Some studies have suggested that sandblasting induces trans-
formation from the tetragonal to the monoclinic phase, thus
affecting bond strength [72]. The coefficient of thermal expansion
of monoclinic zirconia is 7.5  106
/C, and that of tetragonal zir-
conia is 10.8  106
/C. Accordingly, an increase in the difference
in the coefficient of thermal expansion between the TZP framework
and the veneering ceramic leads to a decrease in bond strength
[73]. Heat treatment of the TZP framework for 5 min at approxi-
mately 1000
C prior to commencement of the veneering process is
recommended. Induction of the monoclinic zirconia phase by
sandblasting is reversed by heat treatment [74], with a concomitant
alteration in the coefficient of thermal expansion.
A recent evaluation of the shear bond strength of feldspathic
porcelain to the Katana zirconia framework material concluded
that shear bond strength between these materials was comparable
to the bond between feldspathic porcelain and gold alloy and de-
pends on the strength of the porcelain. The discrepancies in CTE
between veneering porcelains and Katana zirconia significantly
affected the shear bond strength of the porcelain zirconia system
[75].
Based on concepts found in metal ceramic literature and known
physical properties of zirconia, a zirconia collar may be used to
support the veneering porcelain. Extending the zirconia collar to
the interproximal area is useful to limit the amount of veneering
porcelain that might fracture or chip [76].
2.11. Bonding and surface treatments
Several studies investigated different bonding methods as sur-
face roughening, silica coating, silanization and the use of different
bonding agents to zirconia ceramic.
2.12. Surface treatment methods causing micromechanical
interlocking
2.12.1. Sandblasting
Sandblasting is known to form surface roughness and irregu-
larities and increase the surface area, wettability of the ceramic
surface. Also it is used to clean the substrate surfaces, thus allowing
resin cement to flow in to the surface [77,78]. Previous studies have
demonstrated that sandblasting enhances the crown retention
regardless of the cement used. Although sandblasting improves
bonding, its effect on mechanical properties is controversial some
reports supposed mechanical weakening of zirconia [79] due to
60 O.S. Abd El-Ghany, A.H. Sherief / Future Dental Journal 2 (2016) 55e64
phase transformation which can cause fatigue in the material
structure [80]. However, others reported that sandblasting
strengthens the mechanical characteristics of zirconia [81-83].
2.12.2. Hot chemical etching
The action of hot etching solution is basically corrosion e
controlled process where it selectively etches the zirconia ceramic
surface resulting in rough surface and enhances the possibility of
mechanical interlocking with resin cements. The etchant used
modifies the grain boundaries by removing the less arranged high
energy grain boundaries [84e86].
2.12.3. Laser treatment
Absorption of laser energy by zirconia ceramic resulted in a
smooth surface with irregular microcracks [87,88]. Such surface
treatment was investigated and the results were controversial,
some investigations reported that laser treatment did not improve
the mechanical interlocking with resin cement [87], while other
reported that preparation of zirconia ceramic surfaces with CO2
and Er:YAG lasers significantly increased the bond strength, with
the CO2 laser being superior to Er:YAG laser [89].
2.12.4. Nano-structured alumina coating
This method depends on the application of a nano-structured
alumina coating with a high surface area and good wettability to
create a micro-mechanical interlocking. The creation of the nano-
structured layer is achieved by the hydrolysis of aluminum
nitride to form lalamellar (AlOOH) onto the zirconia surface then a
series of heat treatments were performed. The end results was a
discontinuous nano-structured alumina coating (240 mm thickness)
which was found to significantly improve the bond strength to
resin cements [90,91].
2.13. Surface treatment methods causing chemical adhesion
2.13.1. Silane coupling agents
Silane coupling agents are hydrid inorganic-organic synthetic
compounds that are used to enhance the bonding of the resin
composite to glass-based fillers and HF-etchable ceramics or silica
coated metals and oxide ceramics [92]. Zirconia ceramics are not
silica based and thus they present a physico-chemical challenge for
reliable and durable resin bonding [93].
2.13.2. Other coupling agents
A new primer (AZ Primer, Shofu, Kyoto, Japan) containing a
phosphonic acid monomer, 6-MHPA (6-methacryloxyhexyl- phos-
phonoacetate), has been introduced for promoting bonding resin
composite cements to alumina and zirconia ceramics. Kitayama
et al. found that primers containing a phosphonic acid monomer or
a phosphate ester monomer, including 6-MHPA and MDP, were
effective in promoting bonding of resin cements to zirconia
ceramic. Without any primer, the resin cement containing MDP was
found to be effective in bonding to zirconia ceramic [94].
2.13.3. Resins and resin composites
Several studies suggesting the use of a phosphate monomer
containing luting resin for cementation of zirconia restorations. It
provides significantly higher retention of zirconia ceramic crowns
than conventional luting cements, Tanaka et al. [95], Shahin and
Kern [96], Kern and Wegner [97], de Oyagüe et al. [98], reported
that a phosphate monomer-containing luting system is recom-
mended to bond zirconia and surface treatments are not necessary.
Manufacturers have produced new phosphate monomers
designed not only to bond to zirconia. One of the recently devel-
oped phosphate monomers (RelyX Unicem) has a characteristic of
self-etching phosphorylated methacrylates with two phosphate
groups and at least two double bonded carbon atoms and this result
in good bond strength to zirconia in addition to adequate cross-
linking to the resin matrix [99].
2.13.4. Gas fluorination
In an attempt to modify the zirconia to create a more reactive
surface and hence improve the chemical bonding a new method in
which an oxyfluoride conversion layer was created on the surface of
zirconia ceramic and thus increase its reactivity. This method was
investigated by Piascik et al. and found to be effective and they
concluded that oxifluoration conversion layer formed was effective
in bonding to silane coupling agent [100].
2.14. Surface treatment methods causing chemical bonding and
micro-mechanical interlocking
2.14.1. Silica coating
There are several methods to coat zirconia ceramic surfaces with
silica. The aims of this process are to clean the surface, create a
highly retentive surface and the most important is to promote good
bonding to resin cement through silane application.
There are many methods used for silica coating. A thermal silica-
coating system (Silicoater MD system, Heraeus Kulzer, Wehrheim,
Germany) was introduced since early 1980's. It involves sand-
blasting of the zirconia ceramic surface followed by silica-coating.
Then, the surface was coated with silane which formed at
increased temperature silica coating for the substrate in Silicoater
MD apparatus [101].
Tribochemical silica coating utilizes the same principle with a
specifically surface-modified alumina with SiO2 coating on the
surface of the particles. The first tribochemical silica-coating sys-
tem for dental use (Rocatec™ system, 3 M ESPE, Seefeld, Germany),
introduced in 1989. It involves creating chemical bonds by applying
kinetic energy in the form of sandblasting, without additional heat
or light [102,103].
Tribochemical silica-coating using CoJet™ at the dental office is
a widely used now as a conditioning method for both ceramic and
metal alloy. Literature recorded two possible disadvantages; pos-
sibility of subcritical crack propagation within zirconia in case of
thin restorations [104-106], and the potential to remove significant
amount of material which could affect their clinical adaptation
during air abrasion step [107].
Other methods of silica coating include. Silicoater-technology
based on pyrolysis of silanes is used in the PyrosilPen™-technol-
ogy. They are based on a flame from mixture of butane gas and
tetraethoxysilane (TEOS). Tetraethoxysilane decomposes in the
flame to produce ≡Si-O-C≡ type species. Objects subjected for the
flame over a short time (5 s), will be covered by a layer of these
fragments which bond adhesively to the substrate surfaces. This
surface has glass-like properties and be ready for resin bonding
through silane application. So many researchers conducted in the
last few years and proved the efficacy of the process of silica coating
€
for Zirconia e resin bonding. A study by Ozcan and Vallittu [108]
confirmed the effectiveness of silica coating and subsequent
silane treatment on bonding to glass infiltrated zirconia. Also Sahafi
et al. [109], confirmed the same finding by using tribochemical
coating system on bonding to zirconia material. Same findings were
recorded by Ernst et al. [110], Piwowarczyk et al. [111], and Lüthy
et al. [112].
2.14.2. Selective infiltration etching
Selective infiltration etching (SIE) is a novel surface treatment
developed to transform zirconia surface into a retentive one by
promoting the inter-grain nanoporosity. Such porosity will be
 O.S. Abd El-Ghany, A.H. Sherief / Future Dental Journal 2 (2016) 55e64
infiltrated and interlocked by the resin cements. SIE utilizes a
specific glass infiltration agent that is capable of diffusing between
the grains and results in nano-inter-grain porosity. In a recent
study, the effect of three different surface treatments on the bond
strength was investigated: selective infiltration etching, particle
abrasion, and coating with MDP monomer. The initial high bond
strength was observed for the SIE surface treatment. Additionally, it
was the only method capable of maintaining long-term bond
strength values after storing in water for four weeks [113]. It was
recorded by Kitayama et al. that the bond strength could be further
improved with special zirconia primers [93].
2.15. Biological aspects of zirconia ceramics
2.15.1. Biocompatibility of zirconium e based ceramics:
Biocompatibility has been defined as the ability of a material to
perform with an appropriate host response in a specific application.
Biocompatibility is one of the most important advantages of zir-
conium based ceramics. Many In vitro tests were performed using
cell cultures with cells such as fibroblasts, blood cells and osteoblast
cells [114]. Garvie et al. implanted magnesia partially stabilized
zirconia (Mg-PSZ) in paraspinal muscles of rabbits, which were
examined at different intervals of time (1 week, 1 month, 3 months
and 6 months). They reported no significant adverse soft tissue
response to implants, and no degradation of the properties of Mg-
PSZ occurred in contact with these living tissues. There was no
change were detected in the surface phase content, surface
roughness and strength of the implants [115].
Christel et al. studied the effects of zirconia ceramic in vivo.
Yttria stabilized zirconia and alumina cylinders were implanted
into paraspinal muscles of rat. After 1e12 weeks after placement,
no significant difference was observed between the two materials.
They concluded that no cytotoxic effect for zirconia ceramic when
tested both in vitro and in vivo [116]. Josset et al. investigated hu-
man osteoblasts in culture with zirconia and alumina discs. They
found that the osteoblasts showed good adhesion and spreading
properties and the cells preserved their capacity to proliferate and
differentiate into ostogenic pathways [117].
Scarano et al. studied the bond response to zirconia implants
inserted into tibia of white mature rabbits when the implants were
retrieved after 4 weeks. They reported the presence of newly
formed bone and osteoblasts directly on zirconia implants with no
inflammation observed [118].
Uo et al. studied cytotoxicity of dental ceramics cultured with
human gingival fibroblast cells. They used Alamar Blue assay (the
activity of the metabolic reaction of cells) and DNA quantification
(number of cell growth and activity). They concluded that no
cytotoxicity of various ceramics including Denzir (YTZP) [119].
Ichikawa et al. evaluated in vivo tissue reaction and stability of
partially stabilized zirconia ceramic in subcutaneous implantation
test. During the experimental period, zirconia ceramic was
completely encapsulated by a thin fibrous connective tissue with
(less than 80 mm in thickness). No changes of weight and three-
point bending strength of the zirconia samples were detected af-
ter 12 months of implantation. The result of this study suggested
that zirconia ceramic is biocompatible and no degradation of zir-
conia ceramic occurred [120].
Researchers reported that zirconia is not able to generate mu-
tations of the cellular genome [121], in particular, mutant fibro-
blasts found on ZrO2 were fewer than those obtained with the
lowest possible oncogenic dose compatible with survival of the
cells [122]. Moreover, zirconium oxide creates less flogistic reaction
in tissue than other restorative materials such as titanium [123].
This result was also confirmed by a study about peri-implant soft
tissue around zirconia healing caps in compared with that around
61
titanium healing caps. Inflammatory infiltrate, microvessel density,
and vascular endothelial growth factor expression were found to be
higher around the titanium caps than around the ZrO2 ones [124].
Bacterial adhesion, which is an important aspect in order to
maintain zirconia restorations without marginal infiltrations or
periodontal alterations, proved to be satisfactorily with zirconia
restorations. Scarano et al. found a degree of coverage by bacteria of
12.1% on zirconia as compared to 19.3% on titanium [125]. Rimon-
dini et al. confirmed these results with an in vivo study, in which Y-
TZP accumulated fewer bacteria than Titanium in terms of the total
number of bacteria and presence of potential putative pathogens
such as rods [126].
Although Zirconia materials showed excellent tissue reaction,
but in the same time this material has no direct bone bonding
properties or osteoconduction behavior, except it shows a
morphological fixation with the surrounding tissues [127,128].
Strategies for modifying the nature of the material surfaces may
affect cell-material interactions, which in turn influence tissue
development. The results obtained by Wu et al. showed that the
wettability of ZrO2 were noticeably improved by oxygen plasma
treatment that was effective for retaining a stable surface hydro-
philicity. The improved wettability did actively promote the
attachment, proliferation and differentiation of human osteoblast-
like cells [129].
2.15.2. Radioactivity of zirconium based ceramics
Zirconia powder contains small amounts of radionuclides from
the uranium, radium (226 Ra) and thorium (228Th) actinide series.
The separation of these elements is difficult and costly. Two types of
radiation are correlated with zirconia, alpha and gamma. Signifi-
cant amounts of alpha radiation have been observed in zirconia
based ceramics used in the manufacture of implants and due to
their high ionization; the alpha particles destroy cells of hard and
soft tissues but the literature suggests that the radiation level is not
worrisome in zirconia [130].
Great concerns were raised in the early 1990s about the use of
zirconia ceramics for medical and dental applications because of
these radioactive impurities and their effect on human body.
However, after purifying procedures, zirconia powders with low
radioactivity (<100 Gyh1) can be achieved [131]. These values are
below the European radiation limits accepted for human body
external exposure or for local internal exposure of organs and tis-
sues and so near to those of alumina ceramics and Co-Cr alloys for
dental and medical uses. After purifying of zirconia powders, ura-
nium concentration in zirconia powders ranges between 0.001 and
0.007 Bq/g, (max: 1.0 Bq/g according to ISO 6872). Therefore, the
radiation levels of the commercially available zirconia powders
conform to the recommendations of the International Commission
for Radiation Protection (ICRP) and are generally found lower than
the normal ambient radioactivity induced by natural radiations
[131].
Moreover, The mass activity of the current zirconia powders is
much lower than the mass activity of the human bone (20e50 Bq/
kg), which roughly corresponds to a radionuclide content of 1 ppm
(0.0001%) or less which is quite below the values recommended by
the International Standards Organization (ISO 13356) and the
American Society for Testing and Materials Standards (F1873). They
recommended that the mass activity of zirconia powders used for
surgical grade ceramics should be lower than 200 Bq/kg [132].
3. Conclusions
1. Dental applications of zirconia ceramics seem to gain a well-
established place in clinical dentistry today, due to its
62 O.S. Abd El-Ghany, A.H. Sherief / Future Dental Journal 2 (2016) 55e64
exceptional physical and biological properties and the great
enhancement in CAD-CAM technology.
2. A reliable choice of surface treatment and luting cement for
cementation of zirconia contributes toward preventing leakage.
It is recommended to use resin cements because they have been
shown to produce higher bonding to both the zirconia surface
and dentin when compared to conventional cements.
3. Because of the rapid development of both materials and pro-
cessing technologies, application of zirconia-based FPDs can be
seen as promising alternative. However, dentists, researchers
and dental technicians must collaborate to overcome the
esthetic limitation of zirconia materials.
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