Prosthodontics Original Article

ZIRCONIA: PROPERTIES AND APPLICATION — A REVIEW

1
Seyed Asharaf Ali
2
Suma Karthigeyan
3
Mangala Deivanai
­4Ranjana Mani
ABSTRACT

Over the last decade, zirconia has propelled a rapid development of metal-free dentistry with
improved material strength, enhanced esthethic and high biocompatibility for a wide range of prom-
ising clinical applications. It holds a unique place amongst the oxide ceramics due to its excellent
mechanical properties owing to the phase transformation toughening mechanism. Like other side of
the same coin, this mechanism is also responsible for its low temperature degradation which is the
main limiting factor in the extensive use of zirconia.

Zirconia is an inert material and presents reduced bond strength with the conventional ceramic
cementation procedures. Bonding to traditional silica based ceramics is a predicta.

A high percentage of clinical failures of zirconia-based restorations are attributed to debonding

and or fracture of veneering ceramic. This review presents the properties, types of zirconia for dental
application, the manufacturing procedures, the various application and its guidelines, luting of zir-
conia and bonding of the veneering ceramics.

INTRODUCTION capabilities are highly attractive in prosthetic dentistry,

where strength and esthetics are paramount.4
Recently zirconia has emerged as a versatile and
promising material among dental ceramics, due to its PHASES OF ZIRCONIA
excellent mechanical properties owing to the trans-
Zirconia is polymorphic in nature, and displays
formation toughening mechanism. Zirconia (ZrO2) is
different crystal structure at different temperatures
a white crystalline oxide of zirconium.1 Zirconia is a with no change in chemistry. It exists in three crys-
polycrystalline ceramic without a glassy phase and talline forms: monoclinic (m), tetragonal (t) and cubic
exists in several forms. The name ‘zirconium’ comes (c). Pure zirconia has a monoclinic structure at room
from the Arabic word ‘Zargon’ which means ‘golden in temperature, which is stable up to 1170ºC. From 1170ºC
colour’. Zirconia was discovered by the German chemist to 2370ºC, tetragonal zirconia is formed, while cubic
Martin Heinrich Klaproth in 1789.2 zirconia is formed at temperatures above 2370ºC up to
the melting point (2680ºC). Upon cooling spontaneous
Its mechanical properties are very similar to those reversal of transformation occurs.1 The transformation
of metals and its colour similar to tooth colour. Hence is a thermal and diffusionless (“martensitic”).6 Further-
it has been called as ‘Ceramic Steel’ by Garvie.3 The more, the t–m transformation occurs with a volume
expansion of about 4-5% inducing high compressive
mechanical properties of zirconia are the highest ever
stresses in the material.1
reported for any dental ceramic. This may allow the
realization of posterior fixed partial dentures and per- Passerini and Ruff et al, discovered that the
mit a substantial reduction in core thickness. These tetragonal, or even the cubic form could be retained
metastably at room temperatures by alloying zirconia
1
For Correspondence: Professor Prosthodontics, Raja Muthia Dental
College & Hospital, Annamalai University, Chidambaram, Pin with other cubic oxides termed as “stabilizers”.4
Code: 608002. Tamil Nadu, India Email: jsldental@gmail.com
2
Professor and Head of the Department of Prosthodontics STABILIZED ZIRCONIA
3
Lecturer
4
Post Graduate Student. Email: ranjana.mani@yahoo.com
Stabilized zirconia is a mixture of zirconia poly-
Received for Publication: January 30, 2014
Accepted: February 23, 2014 morphs obtained at room temperature, by the addition

Pakistan Oral & Dental Journal Vol 34, No. 1 (March 2014) 178
 Zirconia: Properties And Application — A Review

of stabilizer. With the addition of stabilizing oxides in terials, allowing good cell adhesion and while no local
concentrations less than those required for complete or systemic adverse reactions have been associated
stabilization, zirconia can also be partially stabilized with it.1 Zirconia ceramics have similar cytotoxicity
in a multiphase form, known as partially stabilized to alumina (both lower than tiO2). No oncogenic, or
zirconia (PSZ). It consists of cubic zirconia, as the major mutagenic effects on fibroblasts or blood cells were
phase, and monoclinic and tetragonal zirconia precip- observed. Zirconia implants osseointegrate as well as
itates, as the minor phase. When the whole material titanium ones. Zirconia creates less flogistic reaction in
is constituted by transformable t-zirconia grains it is tissue and lesser bacterial colonization than titanium.
called Tetragonal zirconia polycrystals (TZP). To date, However, particles from the degradation of zirconia
Zirconia stabilized with Y2O3 has the best properties at low temperature (LTD) or from the manufacturing
for dental applications. process can be released, promoting an immune localized
inflammatory reaction.9
Yttrium-Oxide Partially Stabilised Zirconia (Y-PSZ)
is a fully tetragonal fine-grained zirconia ceramic Radioactivity: Zirconia powder contains small
material made of 100% small metastable tetragonal amounts of radionuclides from the uranium-radium
grains (Y-TZP) after the addition of approximately 2 (226Ra) and thorium (228Th) actinide series. However,
to 3 mol% yttrium oxide (Y2O3) as a stabilizing agent.1 after purifying procedures, zirconia powders with low
radioactivity (< 100 Gyh-1) can be achieved which were
PHASE TRANSFORMATION TOUGHENING below the European radiation limits for human body
external exposure of organs and tissues and comparable
When a crack develops on zirconia surface con- to those of alumina ceramics and Co-Cr alloys.1
taining metastable t -ZrO2, it is subjected to a remote
macroscopic tensile stress. This tensile stress concen- Optical Characteristics: Yttria-stabilized zirco-
tration at the crack tip causes the transformation of nia (YSZ) shows high refractive index (2.1 to 2.2), low
metastable t- ZrO2 to the monoclinic crystalline phase. absorption coefficient, and high opacity in the visible and
The consequent volume increase of the crystals, con- infrared spectrum. The increased opacity of zirconia is
strained by the surrounding ones, results in a favorable very useful in esthetically demanding clinical situations
compressive stress which acts on the surfaces of the to mask polychromatic substrates like blackened teeth,
crack, and thus hinders its propagation. Such a mech- pins and metal cores. Because of its opacity, it must
anism has been defined “transformation toughening” be covered with translucent ceramics to yield natural
or “phase transformation toughening”.5,1 tooth-like appearance. Zirconia ceramics posses the
highest amount of relative translucency, comparable
PROPERTIES to that of metal. The use of CAD/CAM has allowed the
construction of a thinner infrastructure (0.5mm), creat-
Mechanical Properties: Mechanical properties of ing more space for the application of a ceramic layer.9
zirconia were proved to be higher than those of all other The high radiopacity of zirconia ceramics, comparable
ceramics for dental use and similar to those of stainless to that of metal alloys, enhance the radiographic eval-
steel. Fracture toughness Zirconia is between 6 and 10 uation of marginal integrity, removal of cement excess
MPa m1/2, which is almost twice as high all that of alu- and recurrent decay.1
minum oxide ceramics. This is due to transformational
toughening, which gives zirconia its unique mechanical AGEING
properties. It has a flexural strength of 900–1200MPa Aging or low temperature degradation is the spon-
and a compression resistance of 2000MPa. An average taneous, slow transformation of the metastable tetrag-
load-bearing capacity of 755N was reported for zirconia onal phase to the more stable monoclinic phase, in the
restorations. Fracture loads ranging between 706N, absence of any mechanical stress, occurring over time
2000N and 4100N were reported; all of the studies at low temperatures. It is exacerbated in the presence
demonstrated that in dental restorations zirconia of water, steam or fluids. LTD is based upon the same
yields higher fracture loads than alumina or lithium mechanism as PTT; that is, it requires the presence of
disilicate.1 t-ZrO2 grains in thermodynamic metastability which
can undergo t-m transformation.
Biocompatibility: Both in vitro and in vivo studies
have confirmed the superior biocompatibility of high The slow transformation of tetragonal crystals to
purity Y-TZP powders. They are chemically inert ma- the stable monoclinic phase starts at the surface in
Pakistan Oral & Dental Journal Vol 34, No. 1 (March 2014) 179
 Zirconia: Properties And Application — A Review

isolated grains by a stress corrosion type mechanism deterioration or destabilization in the presence of saliva,
and later progresses inwards to the bulk of the mate- slowing the growth of subcritical cracks. It exhibits low
rial. The transformation of one grain is accompanied porosity and high density.
by an increase in volume that induces stresses on
the surrounding grains. This causes a surface uplift Partially stabilized zirconia (Mg-PSZ): The stabi-
and microcracks which offers a path for the water to lizer added is MgO in concentrations lower than that
penetrate down into the specimen. Water penetration required for full c-ZrO2 stabilization. In commercial
then exacerbates the process of surface degradation materials the amount of MgO usually ranges between
and the transformation progresses from neighbour to 8 and 10 mol%. The microstructure of Mg-PSZ consists
neighbour. of tetragonal ZrO2 intragranular precipitates within a
matrix of stabilized cubic ZrO2. Due to the difficulty of
Ageing is associated to roughening which will obtaining Mg-PSZ precursors free of SiO2, magnesium
lead to increased wear and microcracking which will silicates can form that lower the Mg content in the
lead to grain pull-out and generation of particle debris grains and promote the t-m transformation. This can
and slow crack growth leading to premature failure. result in lower mechanical properties. This material
Apart from these drawbacks, the zirconia crystals has not been successful due to the presence of porosity,
once already transformed to the m-polymorph cannot associated with a large grain size (30-60µm) that can
exhibit PTT, just like a used match cannot be lit again.7 induce wear, low stability, and overall poor mechanical
This phenomenon can have detrimental effects on the properties, especially when compared to 3Y-TZP.
mechanical properties of zirconia. The main factors
affecting the aging phenomenon are the grain size, the Glass-infiltrated zirconia-toughened alumina
type and the amount of stabilizer and the presence of (ZTA): Zirconia particles are combined with a matrix of
residual stress. Although ageing reduces mechanical alumina forming a structure known as zirconia-tough-
features of zirconia, the decrease falls into clinically ened alumina (ZTA). The zirconia-toughened materials
acceptable values.8 utilize the stress-induced transformation capability
of the dispersed zirconia. In contrast with the other
DIFFERENT TYPES OF ZIRCONIA CERAMICS two classes, stability of the tetragonal phase to room
AVAILABLE FOR DENTAL APPLICATIONS temperature does not primarily involve the use of dop-
ants but is controlled instead by particle size, particle
Although many types of zirconia-containing ceramic morphology and location (intra- or intergranular).4,5
systems are currently available, to date only three types
are used for dental application. These are: MANUFACTURING PROCEDURES

• Yttrium tetragonal zirconia polycrystals (3Y-TZP) CAD/CAM zirconia dental frameworks can be
produced according to two different techniques: “soft
• Magnesium partially stabilized zirconia (Mg-PSZ) machining” of presintered blanks or “hard machining”
and of fully sintered blanks.5

• Zirconia-toughened alumina (ZTA). Soft machining: The soft machining process is the
most diffused manufacturing system for 3Y-TZP, based
ZTA and Mg-PSZ are by-phasic materials with on milling of pre-sintered blanks that are then fully
t- phases as a minor phase; whereas “yttria partially sintered at a final stage. The pre-sintered blanks, at
stabilized tetragonal zirconia polycrystal” (3Y-TZP), is the so-called “green state”, are produced by compacting
a mono-phasic material. zirconia powders along with a binder through a cold,
isostatic pressing process.
3Y-TZP: Yttria partially stabilized tetragonal
zirconia polycrystal (3Y-TZP) is the most popular and The die of the supporting abutments or directly
frequently used form of zirconia commercially avail- the wax patterns of the crown/FPD are scanned. Both
able for dental applications. It consists of an array of contact scanners and non-contact scanners are avail-
transformable t-Zr grains stabilized by the addition able. After scanning, a virtual, enlarged framework is
of 3mol% yttrium-oxide (Y2O3). 3Y-TZP is fabricated designed by sophisticated computer softwares (CAD).
with microstructures containing small grains (0.2 to Then, through a CAM milling procedure, a framework
0.5 mm in diameter) depending on the sintering tem- with enlarged, accurately controlled dimension is
perature, which avoids the phenomenon of structural machined out of the blank. The sinterization of the

Pakistan Oral & Dental Journal Vol 34, No. 1 (March 2014) 180
 Zirconia: Properties And Application — A Review

framework is completed at high temperature. During may allow the fabrication of 0.3 mm thick copings,
sinterization the framework regains its proper dimen- however, reduction of the coping thickness from 0.5 mm
sions as it undergoes a linear volume shrinkage. to 0.3mm can negatively influence the fracture loading
capacity (35% decrease) of zirconia single crowns.10
Hard machining: Fully-sintered 3Y-TZP blocks
are used. They are prepared by presintering at tem- Fixed partial dentures – Exceptional mechanical
peratures below 1500ºC to reach a density of atleast properties of zirconia like high flexural strength and
95% of the theoretical density. The blocks are then fracture resistance allows realization of fabrication of
processed by “hot isostatic pressing” at high tempera- all-ceramic FPDs in both anterior and posterior sites.
tures (1400-1500ºC) under high pressure in an inert For a good long-term prognosis for zirconia FPDs, the
gas atmosphere to produce very hard, dense (99% of the connectors should be properly designed and fabricated.
theoretical density) and homogeneous blocks of fully Connecting surface area of the FPD must be at least
sintered zirconia. The blocks can then be machined 6.25 mm2. For this reason, ceramic FPDs should only
using a specially designed milling system to shape be used when the distance between the interproximal
the framework to the proper, desired form and to the papilla and the marginal ridge is close to 4 mm. In a
right, final dimension. Due to the high hardness and comparison between 3-, 4- and 5-unit zirconia fixed par-
low machinability of fully sintered Y-TZP, the milling tial dentures and minimal connecting surface resulted,
system has to be particularly robust.4,5 respectively, 2.7mm2, 4.0 mm2 and 4.9mm2. Height of
abutment is fundamental to obtain ZrO2 frameworks
APPLICATION AND GUIDELINES FOR with correct shape and dimension in order to ensure
ZIRCONIA IN DENTISTRY mechanical resistance of restoration. Although some
manufacturer allows obtaining also full arch resto-
The spectrum of clinical application of zirconia
rations, 5 units-FPDs are reported to be as maximal
includes the fabrication of veneers, full and partial
possible.3 Maximum tensile stress concentrates on the
coverage crowns, fixed partial dentures, posts and/
gingival surface of the connector and the veneering
or cores, primary double crowns, implants, implant
porcelain may control the failure. Hence the ultimate
abutments and various other dental auxillary compo-
strength can be achieved by omitting porcelain veneer-
nents like cutting burs, surgical drills, extra-coronal
ing in that region.10
attachments and orthodontic brackets.
Zirconia posts – The main advantage of zirconia
Bilayer veneers – the inherent opacity of the zirconia
posts lies in its translucency and tooth-colored shade,
core allows clinical application of high-strength veneer
thereby rendering the material usable with all-ceramic
restoration with better masking ability for the colour
crowns in the anterior region. Zirconia posts are also
management of discoloured teeth. The modified core
indicated for teeth with severe coronal destruction, as
may be fabricated with 0.2 mm to 0.4 mm thickness.10
they offer better strength than composite materials.
Zirconia crowns – Tooth preparation for zirconia Post space preparation principles for zirconia posts
crowns is comparable to those for metal-ceramic resto- are similar to other post systems. Care should be ren-
rations. The abutment should be adequately prepared dered to preserve tooth structure during root canal
to allow enough space for both the substructure and the preparation. Maintenance of both appropriate ferrule
veneering material and the favourable distribution of effect (minimum 2mm in height) and the periphery of
the functional stresses. Preparation in anterior teeth the root canal dentin (minimum 1 mm in width) are
must have a reduction of at least 1.5 mm incisal and 1.0 essential for achieving clinical longevity. Zirconia posts
mm axial on margin with a 4º6º taper; axial reduction can be placed in conjunction with hybrid composites or
in aesthetical areas can be extended up to 1.5 mm. special built-up composites.10 The main disadvantage
Posterior teeth should be prepared with 1.5 mm of oc- of zirconia posts is that its higher rigidity results in
clusal reduction and with 1.0mm of axial reduction on more of root fractures than fracture of posts which is
marginal region with a 4º6º taper. Tooth preparation undesirable. Besides, it is almost impossible to retreat
can be realized with various finishing lines, although teeth restored with zirconia posts as it is very difficult
chamfer and rounded shoulder are recommended.3 After to remove it from the root canal.11
milling, a 0.5 mm-thick uniform zirconia core should be
Zirconia implant – Y-TZP as endosseous dental
fabricated for single posterior crowns. Particularly in
implant material presents enhanced biocompatibility,
the anterior region, strength and esthetic requirements
improved mechanical properties, high radiopacity, and
Pakistan Oral & Dental Journal Vol 34, No. 1 (March 2014) 181
 Zirconia: Properties And Application — A Review

easy handling during abutment preparation. Zirconia Chemical-cured phosphate monomer-containing

ceramic is well-tolerated by bone and soft tissues. Y-TZP resin-based cements, Panavia Ex (10-methacryloy-
implants can successfully osseointegrate under loading loxydecyl-dihydrogenphosphate or MDP) and Panavia
conditions similar to titanium implants. Nevertheless, 21 Ex, exhibited high bond strength. They showed no
clinical and laboratory research data were scarce on safe significant difference in bond strength after artificial
recommendations for a widespread clinical application aging as they formed a water-resistant chemical bond
of Y-TZP implants. with zirconia.
Zirconia abutments – Conventional metal (tita- The addition of a MDP-containing bonding/silane
nium) abutments do shimmer, especially through
coupling agent to enhance bonding of MDP resin ce-
all-ceramic crowns with increased semi-translucency
ments has produced positive results. It was shown that
and, subsequently, through thin peri-implant muco-
particle air-abrasion or tribochemical coating, followed
sa, resulting in a grayish appearance of the entire
restoration. These esthetic problems or the possible by the application of MDP-containing bonding/silane
exposure of the underlying metal abutment can be coupling agent, resulted in increased bond strength
accommodated by the clinical application of zirconia compared to MDP-containing cements alone.
abutments. Y-TZP abutments are available as prefabri-
cated and custom-made. Further customization can be BONDING OF VENEERING MATERIAL TO
achieved by either extra-oral or intra-oral preparation. ZIRCONIA
A pronounced chamfer or a shoulder preparation with
Zirconia copings for crowns or multi-unit frame-
rounded inner line angles are the most recommended
works require application of veneering ceramic, usually
finish lines.10
specialized porcelain, to achieve suitable esthetics. A
LUTING OF ZIRCONIA high percentage of clinical failures of zirconia-based
restorations are attributed to debonding and/or fracture
A major clinical problem associated with use of of veneering ceramic.
zirconia-based components is the difficulty in achieving
suitable adhesion with intended synthetic substrates The bond strength between zirconia and veneer-
or natural tissues. Resin-based composite cements are ing ceramics is influenced by many factors. Bonding
the standard material used in luting a ceramic pros- mechanisms include chemical bonding, mechanical
thetic to tooth structures. The non-silica composition fitting, and shear stress based on the difference in the
of zirconia makes it difficult to bond zirconia to tooth coefficient of thermal expansion between the TZP and
structures using traditional resin composite cements. the veneering ceramics. However no conclusion has
In some instances, high strength ceramic restorations been reached regarding the bonding mechanism itself.
with ideal retention can be placed using conventional Factors influencing the bond strength include surface
cements which rely only on micromechanical retention. roughness, heat treatment of the TZP and the use of
However, a resin bonding is desirable in many clinical liner porcelain.
situations such as short or tapered prepared tooth struc- Since ceramics are extremely susceptible to tensile
ture. Strong resin bonding relies on micromechanical stresses, achieving a slight compressive stress in the
interlocking and adhesive chemical bonding between veneering ceramic is preferred, as in metal-ceramic
the cement and the ceramic surface. (PFM) restorations. For this to occur, the veneering
material must have a thermal expansion coefficient
Retention of zirconia-based ceramic restorations
lower than the core material. Zirconia ceramics have
depends on mechanical roughening of the surface and
coefficients of thermal expansion (CTE) ranging from
chemical bonding with adhesive monomer in special
approximately 9 to 11µm/ m K while specialty porcelains
primers or resin cements. An acidic adhesive monomer
can have CTE values ranging from 7 to 13 µm/ m K.
such as MDP bonds to zirconia-based ceramics. The
phosphate ester group of the acidic monomer results The use of zirconia surface modifiers to achieve
in chemical bonding to metal oxides, zirconia-based strong primary bonding between coping and veneering
ceramics and other ceramics. Therefore it is recom- ceramic could improve the clinical failure rates observed
mended to use self-adhesive or adhesive resin cement to date. Application of a silicate intermediate layer,
containing an adhesive monomer (MDP) or application applied on the zirconia surface via a tribochemical ap-
of ceramic primer containing an acidic adhesive mono- proach has been studied. A vapour deposition approach
mer as pre-treatment before cementation of zirconia. could also enable conformal silicate surface modification
Pakistan Oral & Dental Journal Vol 34, No. 1 (March 2014) 182
 Zirconia: Properties And Application — A Review

without use of an aggressive physical process, which applications for zirconia are being discovered, the future
might result in damage to the coping surface. of this biomaterial appears to be very promising.

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