RESTORATIVE DENTISTRY

Zirconia and its novel compositions:

What do clinicians need to know?
Jan-Frederik Güth, Prof Dr med dent/Bogna Stawarczyk, Priv-Doz Dr rer biol hum, Dipl Ing (FH), MSc/
Daniel Edelhoff, Prof Dr med dent/Anja Liebermann, Priv-Doz Dr med dent, MSc

For several years, there has been a clear trend in the dental mar-
ket towards monolithic tooth-colored restorations. In this con-
text, further developments, particularly in the field of zirconia
ceramics, have led to considerable improvement in the mater-
ials’ optical properties. Modern zirconia materials can be div-
ided into several cohorts, differing from each other with respect
to their optical and mechanical properties. The knowledge
about indications and limitations of each zirconia cohort is es-
sential for a correct clinical application. Clinical long-term ex-
perience for the zirconia of the newest generations is still
scarce and only in-vitro data are available. Despite all advance-
ments, clinical long-term success remains closely linked to the
specific indications, preparation, material selection, know-
ledge, and experience of the dental practitioner and dental
technician, as well as an adequate luting mode and occlusal
concept. Due to the high innovation rate within materials and
CAD/CAM technology in general, clinicians and dental techni-
cians need to be well informed in order to be able to work suc-
cessfully with the various options. (Quintessence Int 2019;50:
512–520; doi: 10.3290/j.qi.a42653); Originally published in Ger-
man in Quintessenz 2018;69(8):878–888)

Key words: all-ceramics, flexural strength, generations, monolithic restorations, translucency, zirconia

Due to their high biocompatibility and esthetic potential, all-
ceramic materials are a suitable alternative to metal-based res-
torations for many indications within restorative dentistry. Apart
from a great number of glass ceramics, the class of dental ceram-
ics also comprises different types of zirconia materials, which are
continuously being enhanced and modified. Due to the great
number of options available – also in the field of monolithic zir-
conia – the selection of a restorative material in everyday clinical
practice has turned into a complex and challenging task.
At the same time, a clear trend towards monolithic restor-
ations can be observed in the dental market. Crucial reasons for
choosing monolithic restorations over frameworks veneered
using a manual layering technique include reduced manufac-
turing expenses, higher reliability (improved Weibull modulus),
and reduced thicknesses, leading to less invasive preparations.
In addition, it is possible to create the morphology in a more
accurate way, avoiding sinter shrinkage of the veneering
ceramic. Besides the facilitation of the computer-aided design
(CAD) process itself, this leads to a design-related reduction of
the related chipping risk. Proper material selection remains
decisive: there are considerable differences in the mechanical
and optical properties of the available zirconia materials for
monolithic clinical use. These differences are dependent on the
material composition and manufacturing procedure. This article
aims to provide assistance for clinicians who would like to cor-
rectly classify and adequately utilize zirconia materials for their
adequate indications – because “zirconia” has become a gen-
eral term for a wide range of novel zirconia-based materials.
Classification of modern zirconia materials
The basic objective of further developing zirconia materials
was to increase their translucency in order to use them in spe-
cific indications for fabrication of monolithic restorations. To

512 QUINTESSENCE INTERNATIONAL | volume 50 • number 7 • July/August 2019


flexural strength
2nd Generation
~ 3 mol% Y2O3
tion in
AL 2O 3
g
~ 0.05 w% Al2O3
1st Generation Reduc positionin
and re
~ 3 mol% Y2O3
~ 0.25 w% Al2O3
Fig 1 Overview of zirconia divided in generations in relation to the chronology the material classes were introduced to the dental market.
Graphic representation based on Stawarczyk et al.9
achieve greater translucency, different strategies for the modi-
fication of the material composition could be pursed:
■ reduction of the number of defects in the material struc-
ture, eg, achieved by addition of a glass phase or a sintering
additive1
■ refinement of the microstructure, so that grain boundaries
will no longer interfere with the light that passes through
■ increase of the grain size to reduce the number of boundaries2
■ creation in the material structure of a cubic phase, which
has isotropic optical properties to avoid double refractions.3
The great number of available options and parameters makes it
difficult to keep track of current developments and to be sure
what type of zirconia material is actually being held in the hands.
Zirconia can theoretically exist in three crystalline forms
depending on the composition and temperature: monoclinic,
tetragonal, and cubic. This results in a wide range of material
options with different mechanical and optical properties. The
production and processing of zirconia also has a decisive impact
on the final properties. Furthermore, incorrect treatment of the
material during the production of a restoration can cause phase
transformations, affecting the mechanical properties in general
and especially the coefficient of thermal expansion.
Zirconia materials can currently be divided into four types
or generations according to their mechanical and optical prop-
erties. Figure 1 provides an overview of the available zirconia
generations. This overview is used to facilitate orientation in
everyday clinical practice.4-9
QUINTESSENCE INTERNATIONAL | volume 50 • number 7 • July/August 2019
Güth et al
1
3rd Generation
~ 5 mol% Y2O3
Y 2O 3 ~ 0.05 w% Al2O3
ase in
Incre
4th Generation up to 53% cubic structure
~ 4 mol% Y2O3
translucency
Y 2O 3 ~ 0.05 w% Al2O3
ase in
Incre
First generation: 3-mol%-yttria-stabilized
tetragonal zirconia polycrystals (3Y-TZP)
3Y-TZP material is partially stabilized in the tetragonal phase,
offers the highest mechanical properties, and was introduced to
the dental market more than 25 years ago. Due to its outstand-
ing biocompatibility and a flexural strength of more than
1,000 MPa, zirconia of the first generation is generally used as a
framework material.10,11 Its mechanical properties enable its use
in minimal wall thicknesses and for multi-unit restorations. How-
ever, due to its high opacity and the resulting compromised
optical appearance, the material is predominantly used as a sup-
porting framework structure. The first generation zirconia is
therefore mainly indicated for the fabrication of frameworks
that will be manually veneered as well as for the production of
hybrid abutments in implant restorations. In-vitro and in-vivo
investigations showed that these zirconia restorations offer a
favorable mechanical stability and high clinical reliability.12-15
According to the S3 guideline “All-ceramic crowns and
bridges,”16 the use of veneered fixed dental prostheses (FDPs)
with up to three units can be recommended for the anterior
and posterior areas whenever sufficient anatomical support of
the glass-ceramic layer is ensured by the framework design.
Clinical data reveal a very good survival rate of 98.2% and a
success rate of 92% after 10 years.17 The knowledge and skills of
the practitioner regarding preparation design and adhesive
cementation of zirconia, however, have a huge impact on the
long-term success.
513
 RESTORATIVE DENTISTRY
2a
Fig 2a Framework made of second generation zirconia with ana-
tomical reduction in regions of the mandibular left second premolar
and first molar (35 and 36). The fixed dental prosthesis anchor at the
mandibular left second molar (tooth 37) has a monolithic design.
2c
Fig 2c Fluorescence behavior of a framework structure made
of second generation zirconia with anatomical reduction in regions
of the mandibular left second premolar and first molar (teeth 35
and 36).
2e
Due to its high opacity, first generation zirconia is contra-
indicated for the fabrication of monolithic restorations. In order
to make the material suitable for monolithic use, the material
structure has been modified in various ways. The main focus
was to improve the optical properties, especially increasing the
translucency.18 The first approach of the material scientists was
to alter the sintering parameters. The final sintering tempera-
514 QUINTESSENCE INTERNATIONAL | volume 50 • number 7 • July/August 2019
2b
Fig 2b Hand-veneered ceramic at mandibular left second premolar
and first molar (teeth 35 and 36). Fixed dental prosthesis anchor at
the mandibular left second molar (tooth 37) did not receive any glass
ceramic layer but was polished and glazed.
2d
Fig 2d Fluorescence behavior after manual veneering of the
anatomically reduced parts in regions of the mandibular left second
premolar and first molar (teeth 35 and 36) compared to the mono-
lithically designed fixed dental prosthesis anchor at the mandibular
left second molar (tooth 37).
Fig 2e Lateral/occlusal view of the adhesively luted zirconia fixed
dental prosthesis, manually veneered in regions mandibular left
second premolar and first molar (teeth 35 and 36), monolithic in
region mandibular left second molar (tooth 37). Laboratory work:
MDT Marc Ramberger.
tures were increased to up to 1,600°C and the holding times
were extended. These measures led to an increase of translu-
cency, but at the same time, to a decrease of flexural strength
with the appearance of structural defects. This strategy finally
resulted in spontaneous fractures and reduced reliability14,19
and did therefore not prevail in the dental market. Instead,
alternative methods were chosen to increase the translucency.

3a
Figs 3a and 3b Three-unit monolithic fixed dental prosthesis made of third generation zirconia. (a) Least possible preparation; (b) adhesively
luted fixed dental prosthesis. Laboratory work: MDT Hans-Jürgen Stecher.
Second generation: 3-mol%-yttria-stabilized
tetragonal zirconia polycrystals (3Y-TZP) with
reduced alumina content
Around 2013, an enhanced version of the 3Y-TZP materials was
presented. The innovation was mainly based on a modification
carried out on the molecular level: the number and size of the
alumina grains (Al2O3) contained in the material structure were
reduced. In addition, the alumina grains were placed at the
boundaries of the zirconia grains, resulting in a higher level of
light transmission and therefore translucency. At the same
time, the in-vitro long-term stability was sufficient, and the flex-
ural strength remained high.12,20 Due to its durable strength
and better optical properties, this type of zirconia is predomi-
nantly used as framework material for one- and multi-unit
FDPs. Partially veneered restorations are also possible, allowing
a defect-oriented preparation on the one hand and an attrac-
tive esthetic appearance on the other (Fig 2).
Third generation: 5-mol%-yttria-stabilized
tetragonal zirconia polycrystals (5Y-TZP)
A further enhancement in the translucency of zirconia was
achieved by an increase of the yttria (Y2O3) content to 5 mol%.
This new type of material was introduced in 2015. It is described
as a fully stabilized zirconia with cubic-tetragonal microstruc-
ture, colloquially named cubic zirconia. The cubic content
amounts to approximately 50%. Because the cubic crystals are
larger than the tetragonal crystals, light that is transmitted
through the restorations passes fewer boundaries and porosi-
ties that might cause refractions. As a consequence, the material
appears more translucent. The greater the amount of cubic crys-
QUINTESSENCE INTERNATIONAL | volume 50 • number 7 • July/August 2019
Güth et al
3b
tals in the material structure, the higher the translucency. An
increase of the amount of cubic crystals has, however, a nega-
tive impact on the mechanical properties such as flexural
strength and fracture toughness. The translucency of the third
zirconia generation is slightly lower than that of lithium (x)sili-
cate, while their flexural strength and fracture toughness are
higher. Consequently, third generation zirconia may be regarded
as a possible alternative to high-strength glass ceramics.18,21
Most manufacturers recommend third generation zirconia
– just like lithium (x)silicate – for the production of single tooth
restorations, and FDPs with up to three units and one pontic
between two crowns in the premolar region. It is, however
advisable to check the material’s instructions for use to obtain
detailed information about the specific indications. In this con-
text, it needs to be mentioned that there is (apart from investi-
gation on their translucency behavior) a lack of clinical and also
in-vitro data for the third generation zirconia. Figure 3 shows a
three-unit FDP made of a third generation zirconia.
4
Fig 4 Transmission of visible light (400 to 700 nm) through four dif-
ferent zirconia layers (from left to right: enamel layer, transition layer 1,
transition layer 2, body layer), shown behind the neutral gray ring of a
multilayered zirconia blank (Katana Zirconia Multi-Layered Disc,
Kuraray Europe). Adopted from Ueda et al.22
515
 RESTORATIVE DENTISTRY
5a
5b
5c
Figs 5a to 5c Zirconia with different compositions, each with shade
and translucency gradient. (a) Katana Zirconia ML; (b) Katana Zirconia
STML; (c) Katana Zirconia UTML. Laboratory work: MDT Josef Schweiger.
Fourth generation: 4-mol%-yttria-stabilized
tetragonal zirconia polycrystals (4Y-TZP)
In order to increase the indication range for monolithic zirconia
restorations, there is an ongoing effort to optimize the material
properties through diverse modifications. In 2017, the fourth
generation of zirconia was introduced. Compared to the third
generation, the yttria content was reduced to 4 mol%, which
led to an enhancement of the mechanical properties with a
combined reduction in its light-optical properties. Depending
on the manufacturer, fourth generation zirconia is indicated for
short-span multi-unit FDPs.
516 QUINTESSENCE INTERNATIONAL | volume 50 • number 7 • July/August 2019
Additional modifications
For different zirconia generations, multilayered or gradient-
shaded zirconia blanks are available. These were developed to
facilitate imitation of the color gradient of natural teeth (Figs 4
and 5).22 In addition, blanks that combine different zirconia
generations (eg, multilayer) have recently been introduced to
obtain the best possible mechanical and optical properties.
These blanks consist, for example, of a body out of fourth gen-
eration zirconia (4Y-TZP) to ensure a slightly increased stability,
and a third generation material (5Y-TZP) with higher translu-
cency is selected for the incisal area for enhanced optical prop-
erties. Also, different combinations and mix forms are available
from different manufacturers. Other zirconia blanks have inte-
grated fluorescent particles (Fig 6).
Another trend is towards an acceleration of the sintering
procedures (speed or super-speed sintering) for speeding up
the manufacturing procedure. Depending on the geometry of
the restoration, sintering may take only approximately 30 min-
utes. However, this is possible, only for materials that are specif-
ically developed for a speed-sintering process. Also, there is still
a lack of sufficient scientific data supporting speed sintering.
Cementation of zirconia restorations
Considering the luting process of zirconia restorations, there
are differences between traditional cementation and adhesive
luting with or without using additional adhesive systems. For
translucent restorations made out of third or fourth generation
zirconia, it is recommended to not use an opaque luting mater-
ial in the visible area for esthetic reasons.
The major criterion for luting material selection is, how-
ever, the preparation design, which should be chosen based
on the guidelines for all-ceramic preparations. For a traditional
cementation using glass-ionomer cement, the prepared tooth
stump should offer an adequate form of retention and resis-
tance.23-25 The results of a clinical study with an observation
period of up to 9 years revealed, for example, that all-ceramic
crowns made of lithium disilicate (IPS e.max Press, Ivoclar
Vivadent) cemented with glass-ionomer cement (Ketac Cem,
3M) showed no increased decementation rate when the pre-
pared tooth presented a convergence angle of 10 degrees
and a minimal stump height of 4 mm.26 A minimal stump
height of 4 mm and a maximum convergence angle of 15 de-
grees may be regarded as clinical reference points in the de-
cision of whether or not a traditional cementation procedure
is possible.27
 Güth et al

6a 6b 6c 6d

Figs 6a to 6d Optical comparison of different zirconia generations. (a) Fixed dental prosthesis (FDP) from maxillary right first premolar to first
molar (tooth 14 to 16) and single crown maxillary right second molar (tooth 17) made of a second generation zirconia in visible light. (b) FDP
from 14 to 16 and single crown 17 made of a second generation zirconia captured with an ultraviolet light source in order to reveal the fluores-
cence behavior of the material. (c) FDP from maxillary left canine to second premolar (tooth 23 to 25) with cantilever on the lateral incisor
(tooth 22; experimental use outside indication range) and crown on the first molar (tooth 26) made of third generation zirconia, which has inte-
grated fluorescent particles (Lava Esthetic, 3M); the same restorations captured under an ultraviolet light source (fluor_eyes, www.finest-dental.de).
Laboratory work: MDT Josef Schweiger.

Cementation is described as a process that establishes a
mechanical connection achieved via mechanical interlocking
on the prepared tooth stump. An accurate fit of the restoration
is essential. As long as the preparation guidelines regarding the
form of retention and resistance are respected, it seems that
even traditional placement methods with traditional cements
do not cause a cumulative occurrence of cases with a loss of
retention.28-30 Current studies running for up to 10 years, how-
ever, have revealed a significant increase of decementations,
especially when FDPs were placed with zinc phosphate cement
in the mandible. Accordingly, the authors recommended to
critically reassess the use of this type of cement.31,32 Prepara-
tions for single crowns presented an average preparation angle
of more than 26 degrees.33 Therefore, it seems to be debatable
if it is possible to respect the given preparation guidelines in
everyday practice. Against this background, adhesive luting
seems to be beneficial. This method is more technique-sensi-
tive and time-consuming than a cementation, but with better
chemical bonding and low solubility compared to traditional
cements. A better marginal integrity is also obtained. In this
context, an adequate pretreatment of the tooth substance and
the inner surface of the restoration is an important precondi-
tion for a reliable result.
Within the class of composite resin cements, a distinction
can be made between luting materials with and without (self-
etch) the use of an adhesive system based on their chemical
composition. When self-etch composite resin cements are
used, a conditioning of the tooth structure is not mandatory.
Whenever enamel is present, an initial selective enamel etching
step will, however, lead to a better bond quality and durable
marginal seal. Due to the presence of acidic and phosphoric
monomers in the formulation, separate conditioning of the
dentin surfaces with primers is not recommended.
Independent of the zirconia generation used, a chemical
bond is established between the restorative material and the
self-etch composite resin cement. Composite resin cements
with additionally used adhesive systems based on dimethacry-
late require separate conditioning with an adhesive system that
contains phosphate. However, if the conventional composite
resin cement contains phosphate monomers like MDP (10-meth-

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 RESTORATIVE DENTISTRY
acryloyloxydecyl dihydrogen phosphate), it is not necessary to
pretreat zirconia with a phosphate-containing adhesive system.
After intraoral try-in, which is usually associated with saliva con-
tamination, the restoration should be cleaned thoroughly. As
zirconia is an oxide ceramic material that is free of glass particles,
etching with hydrofluoric acid does not have the desired effect.
Instead, moderate airborne-particle abrasion is recommended
after the try-in (authors’ recommendation: pressure maximum
1 bar, distance approximately 10 mm, particle size ≤ 50 μm).
Cleaning with phosphoric acid needs to be reconsidered
critically. Although phosphoric acid seems to be much more
effective than cleaning with alcohol,34 a decrease of the bond
strength is observed after artificial aging if phosphoric acid
cleaning was used. This effect can be prevented only by a sub-
sequent cleaning step with alcohol.35-37 The cleaning of zirconia
surfaces with phosphoric acid cannot be recommended if adhe-
sive luting is desired. Whenever the surface is not cleaned suffi-
ciently with alcohol following phosphoric acid treatment, the
phosphate groups in the phosphoric acid might occupy oxide
binding sites. These binding sites are usually available for the
phosphate monomers contained in the self-etch composite
resin cement or the adhesive system to form a chemical bond. A
high airborne particle-abrasion pressure with overly large parti-
cles should be avoided to prevent inducing superfluous surface
damage, stresses, or micro cracks.
With their composition based on acidic monomers being
responsible for bonding to the tooth surface, self-adhesive
composite resin cements do not require a pretreatment of the
zirconia surface. When conventional composite resin cements
are used, a separate conditioning with an adhesive system that
contains a phosphate monomer (eg, MDP monomer) is neces-
sary to facilitate chemical bonding. MDP is a bifunctional
monomer that is able to bond to zirconia with its phosphate
group end and to the resin cement with its methacrylate end.
In order to minimize potential sources of error, it is essential to
strictly adhere to the specific luting protocols recommended
for the adhesive system.
Surface treatment following adjustment
procedures (grinding)
With regard to the protection of the antagonist enamel from
abrasion, the surface of the restoration should be as smooth as
possible. When it comes to monolithic zirconia restorations,
this is particularly important as inadequately polished surfaces
might have extremely sharp edges, which could potentially
harm the antagonist.
518 QUINTESSENCE INTERNATIONAL | volume 50 • number 7 • July/August 2019
For veneered zirconia restorations, surface treatment after
the adjustment of premature contacts is decisive, as problems
with chipping are reported. Chipping is defined as a fracture of
the veneering ceramic, which is often observed for rough, insuf-
ficiently polished surfaces. In order to minimize the chipping
risk, it may be necessary to send the restoration back to the
laboratory after intraoral adjustments. Depending on the size of
the adjusted surface, it is recommended to put the restoration
through a second glaze firing (more than 1 mm2) or to repolish
the area. For polishing, which may also be carried out in the
dental office, different (usually multi-step) polishing systems
are available, consisting of silicone polishers with different grain
sizes. If the polishers are used in the recommended order (from
coarse to fine), good results can be obtained. The ceramic pol-
ishing systems are suitable for veneering ceramic and zirconia.
Monolithic zirconia restorations may also be polished in
white state prior to sintering. As the material is very soft and
the substance can be easily removed, the polishing should be
performed carefully.
Assessment of monolithic zirconia restor-
ations based on the available literature
Basic support in selecting the best suitable dental ceramic
material is provided by the S3 guideline “All-ceramic crowns
and bridges” published in 2014.16 Due to the insufficient amount
of clinical data available and the lack of results from long-term
observation periods, however, modern monolithic restorations
based on zirconia are not included in this guideline. So far, very
little is known about the new zirconia generations and scientific
data are scarce. Yet, the specific properties of these new mater-
ial classes and the numerous unsolved issues for clinical use
catch the interest of users and scientists alike. At the moment, it
is only possible to assess and classify these new monolithic zir-
conia materials based on the available scientific data (mostly
in-vitro data) and the expertise of the authors.
Especially regarding single tooth restorations, tooth-col-
ored monolithic zirconia is in strong competition with other
all-ceramic materials with clinical long-term data. In laboratory
investigations, however, monolithic zirconia restorations show
higher fracture loads than crowns made of alternative ceramics
like lithium disilicate.38 This makes less invasive preparation
designs for monolithic zirconia crowns possible. In laboratory
tests, for example, single crowns with a layer thickness of
0.5 mm showed a sufficient fracture load and in-vitro perfor-
mance independent of the placement method (adhesive luting
1,628 ± 174 N, cementation 1,357 ± 340 N).39
 Güth et al

What plays a decisive role in this context is an adequate form
of retention and resistance required to avoid a loss of retention.
One investigation shows, however, that there is a tendency
towards a too conical preparation (mean convergence angle of
26 degrees in single crown preparations).33 It is essential that
practitioners put a strong focus on an exact preparation, which
might prevent an early loss of retention.26 In addition, the results
point to the fact that in the busy everyday clinical routine, an
adhesive luting protocol might be a useful preventive measure
against possible retention loss.28 In the material selection pro-
cess, when assessing the criterion “minimum possible layer
thickness,” the clinician should always take into account the
level of destruction of the tooth. In this context, it is essential
to check critically if an alternative, even less invasive form of
restoration and preparation (eg, onlay, overlay, veneer, partial
crown) using alternative types of material is feasible.40
Another aspect that should be respected in the context of
material selection is the abrasive wear behavior of the materials
themselves and especially their effect on the antagonist.41 The
clinical data available on this topic are also insufficient to pro-
vide advice for or against using specific materials or material
classes. It is ultimately up to the restorative team to implement
a well-balanced occlusal concept. To ensure the desired results,
it is advisable in this context to strictly adhere to the recom-
mended protocols.
Practitioners should be careful in drawing conclusions from
investigations focusing on specific materials and to transfer
findings to other zirconia generations. This is due to different
amounts of yttria in the formulations and differences in the
aging behavior. Even if initial in-vitro data show promising
results, clinical studies that focus on monolithic zirconia in var-
ious indications need to be initiated. Their results will be able
to provide sufficient clinical evidence for the use of this new
material class.
Conclusion
A decisive improvement of the optical properties of ceramic
materials has been achieved through further developments.
Still, clinical long-term success is strongly linked to the selec-
tion of the correct indication, preparation, and material, the
knowledge and experience of the dental practitioner and tech-
nician, and adequate luting procedure and occlusal concepts.
The high innovation rate in material and CAD/CAM technology
development demands good knowledge of the practitioner for
the optimal and successful use of all available options.

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Jan-Frederik Güth Jan-Frederik Güth Associate Professor, Deputy Director, Depart-

ment of Prosthetic Dentistry, University Hospital, LMU Munich,
Munich, Germany
Bogna Stawarczyk Head of Material Science, Department of
Prosthetic Dentistry, University Hospital, LMU Munich, Munich,
Germany
Daniel Edelhoff Head of Department, Director, Department of
Prosthetic Dentistry, University Hospital, LMU Munich, Munich,
Germany
Anja Liebermann Associate Professor, Department of Prosthetic
Dentistry, University Hospital, LMU Munich, Munich, Germany

Correspondence: Prof Dr Jan-Frederik Güth, Department of Prosthetic Dentistry, University Hospital, LMU Munich, Goethestraße 70,
80336 München, Germany. Email: jan_frederik.gueth@med.uni-muenchen.de

520 QUINTESSENCE INTERNATIONAL | volume 50 • number 7 • July/August 2019