Current Oral Health Reports

https://doi.org/10.1007/s40496-019-00243-4

MODERN PRODUCTION LABORATORY ADVANCES IN DENTAL TECHNOLOGY (M BERGLER AND E

STEGER, SECTION EDITORS)

3D Printing of Zirconia–What is the Future?

J Schweiger 1 & D Bomze 2 & M Schwentenwein 2

# Springer Nature Switzerland AG 2019

Abstract
Purpose of Review Within this review, the current needs of the dental industry will be discussed with special focus on additive
manufacturing (3D printing) of dental restorations. Up to now, subtractive manufacturing methods are state of the art for
production of monolithic restorations. Here, the challenges and opportunities currently existing for 3D printing of crowns and
bridges will be evaluated.
Recent Findings Over the last 10 years, the LCM technology has evolved to the state of the art 3D printing technique for dense
and precise ceramics. A case study will present here the full digital workflow from acquiring the data of the patient to
manufacturing the final restoration.
Summary It can be shown that with the LCM technology, it is possible to manufacture highly accurate parts with exceptional
good surface quality. Furthermore, it can be shown that established techniques for staining and glazing conventionally
manufactured restorations are also perfectly suitable for parts manufactured by means of the LCM technology. Particularly
attractive restorations and outstanding reproduction of the sharp-edged crown margins are possible, together with the exact
reproduction of the occlusal surfaces with sharp and natural replication of the fissures.

Keywords 3D printing . Additive manufacturing . Zirconia . Crown . LCM Technology . Dental restoration

Introduction Ultimately, the introduction of the VITA VMK 68 in 1968 led

One of the primary goals of dentistry has always been to restore
lost tooth substance by restoring teeth as naturally as possible.
As early as 1900’s, the US dentist Charles Henry Lund
invented the jacket crown, the first all-ceramic crown restora-
tion. However, this technical application was very complicated
and associated with many problems, meaning that this crown
variant was esthetically pleasing but exhibited insufficient me-
chanical strength. In order to achieve higher levels of strength,
VITA Zahnfabrik made its first attempt in 1958 to burn dental
ceramic materials onto a Degussa precious metal alloy.
This article is part of the Topical Collection on Modern Production
Laboratory Advances in Dental Technology
* D Bomze
dbomze@lithoz.com
1
Poliklinik für Zahnärztliche Prothetik, Klinikum der
Ludwig-Maximilians-Universität München, Goethestr. 70,
80336 Munich, Germany
2
Lithoz GmbH, Mollardgasse 85a/2/64-69, 1060 Vienna, Austria
to the great breakthrough of metal ceramics [1]. Crowns and
bridges made of metal and ceramics are still the most common
form of restoration in the field of ceramic restorations.
In contrast, tooth-colored materials possess significant ad-
vantages when it comes to producing restorations with a nat-
ural appearance. A large number of new metal-free restoration
possibilities and materials have been developed to meet the
higher esthetic demands of both patients and dentists. Due to
their excellent biocompatibility and outstanding optical prop-
erties, all-ceramic materials are nowadays seen as the material
of choice [2, 3]. All-ceramic restorative materials have signif-
icant advantages over combinations of metal and ceramic ma-
terials, especially when it comes to the task of optical imitation
of the natural tooth [4]. Among the large number of all-
ceramic framework materials, zirconium oxide (ZrO2) has
the best mechanical properties in comparison to all other all-
ceramic materials [5–8] due to its transformation reinforce-
ment. However, clinical setbacks have also been recorded
for all-ceramic restorations based on zirconium oxide frame-
works. The most important problem to mention here is the
chipping of the veneering ceramic. While fractures in zirconi-
um oxide frameworks have been very rarely recorded,

chipping in the veneering area has been frequently reported [9,
10]. One possible approach to avoiding the problem of
chipping is to fabricate fully anatomical monolithic zirconium
oxide crowns and bridges without a veneering layer. The main
clinical advantage of monolithic zirconium oxide restorations
is the significantly reduced material thickness compared with
veneered restorations or other monolithic ceramics such as
silicate ceramics [11, 12•]. By using CAD/CAM technology
(i.e., milling), zirconium oxide can be processed very effi-
ciently and cost-effectively in its pre-sintered state (“white
state”, i.e., the organic binder has already been burnt out)
using subtractive procedures. Compared with manually
veneered zirconium oxide, crown and bridge restorations in
particular, monolithic restorations are much cheaper to fabri-
cate. The classic zirconium oxide with a content of 3 mol%
yttrium oxide (3Y-TZP = yttrium oxide-stabilized-tetragonal-
zirconia-polycrystal) is stabilized at room temperature in the
tetragonal phase. This enables the so-called transformation
reinforcement, which occurs under high mechanical stress
and causes a conversion from the tetragonal to the monoclinic
phase. Due to the 4% increase in volume caused by this con-
version, crack flanks are virtually compressed. This special
feature gives 3Y-TZP very attractive mechanical properties
and makes this oxide ceramic particularly suitable for dental
use. However, 3Y-TZP is very opaque, so applications for
monolithic restorations using this material are associated with
comparatively large esthetic losses. Most dental zirconium
oxide manufacturers have found different approaches to meet
the increased translucency requirements. On the one hand,
light transmission can be increased by either reducing the
concentration of aluminum oxide or increasing the concentra-
tion of yttrium oxide. Examples include zirconium oxides
with 4 or 5 mol% yttrium oxide. With these so-called cubic
zirconium oxides (e.g., 5Y-CZP), more than 50% of the zir-
conium oxide is in the cubic phase, which does not allow for
transformation reinforcement ,and thus, leads to a reduction in
crack toughness. The material therefore becomes more brittle.
The latest development in the field of translucent zirconium
oxides is the so-called “Gradient Technology” (GT). In addi-
tion to a color gradient (basal highly chromatic, less chroma to
incisal), a material-specific gradient is also incorporated into
the milling blank. The high-strength raw material 3Y-TZP and
the highly translucent raw material 5Y-TZP are combined in a
special way and facilitate a continuous, layer-free color and
translucent gradient [13].
Since zirconium oxides can be milled very well when they
have not been sintered yet, but have low inherent strength in this
state, the marginal areas need to be augmented in CAD. This
prevents the edges from breaking out during subtractive machin-
ing. However, these results in a considerable amount of post-
processing work being needed in these marginal areas. Since the
crown margin, in addition to the occlusal surface, is a very im-
portant area of crown and bridge restoration, post-processing
Curr Oral Health Rep
must be carried out very carefully under the stereomicroscope,
which takes a considerable amount of time. Rotating instruments
that are used in milling can only produce very tapered fissure
geometries. The fissures of the occlusal surfaces also require
post-processing as rotating instruments can only reproduce the
classic, tapered fissure geometry to a limited extent.
Additive manufacturing methods offer significant advan-
tages here, as these methods can perfectly reproduce pointed
inner geometries. The latest developments in the field of 3D
printing ceramics demonstrate the enormous potential of this
technology. In particular, the additive fabrication of restora-
tions made from zirconium oxide allows for the production of
geometries whose shapes are almost identical to the final ge-
ometries, and thus, no longer require major post-processing.
Fine crown margins and perfectly shaped occlusal surfaces
that were previously impossible to fabricate can now already
be manufactured using the existing technology. Although im-
provements in translucency and coloring are certainly still
necessary, 3D printing also offers advantages in these areas,
as individualized and personalized colorings can be realized
with individual color gradients being conceivable due to the
layered structure created using this technology.
LCM Technology
Additive manufacturing (also known as 3D printing) process-
es which utilize photopolymerization prove themselves to be a
very effective type of technology for the production of highly
complex components, interest in which is rapidly growing in
the field of medical device manufacturing. Using
Lithography-based Ceramic Manufacturing (LCM) technolo-
gy allows for the use of a large variety of ceramic materials in
manufacturing, including alumina, zirconia, tricalcium phos-
phate (TCP), and hydroxyapatite (HA) in any shape.
The LCM process is based on the selective curing of photo-
sensitive ceramic suspensions (i.e., slurries), whereby particular-
ly high-filling degrees and packing densities of ceramic particles
in green bodies are achieved. This is necessary in order to yield
defect-free and dense ceramic parts. The construction process
follows a layer-by-layer principle; the CAD file is virtually di-
vided into very thin layers, which are then lithographically pro-
duced and bonded one after the other. The organic matrix is
cross-linked with the spatially resolved exposure of the suspen-
sion, resulting in a composite of a polymer network and ceramic
particles (DLP process). The polymer network serves as a binder
between the ceramic particles, and thus, the formulation can be
shaped. Figure 1 shows schematically the generation of the layer
information based on the CAD model, whereas Fig. 2 shows the
operation principle along with a schematic view of the process
chamber of the 3D printer.
The print run results in a composite of polymerized binder
with dispersed ceramic particles within, which subsequently
undergoes a cleansing process to remove any excess or
Curr Oral Health Rep
Fig. 1 CAD model is sliced into
two-dimensional virtual images
(layers). Each of these layers are
projected on a photosensitive
formulation which solidifies by
means of photopolymerization
(depicted as white area). Areas of
the formulation which are not
exposed to light remain in their
liquid state (depicted in gray) and
can be removed after the printing
process
uncured raw material (slurry). This is carried out using a di-
rected compressed air stream and appropriate cleaning sol-
vents. Finally, the part needs to undergo thermal post-
processing in order to give the component its final properties.
Best Practice Example
A mandibular molar crown was used to illustrate the current
state-of-the-art technology available in 3D printing zirconium
oxide for dental applications. It was produced in a fully digital
workflow—from the data generation to the production of the
part. In this case, this means that the impression of the pa-
tient’s tooth was taken digitally using a 3D intraoral camera,
with the crown then being designed using CAD software and
finally fabricated using Lithoz’s LCM technology.
3D Intraoral Scan
The three-dimensional recording of the patient’s tooth was per-
formed using the 3Shape TRIOS intraoral scanner. The physical
fundamental for the 3D acquisition is the confocal laser beam
principle. Common scanning procedures are based on triangu-
lation, meaning some areas cannot be detected due to
Fig. 2 Schematic view of the process chamber of a CeraFab 7500 Dental
3D printer from Lithoz (Vienna, Austria). The parts are manufactured
using a bottom-up approach, being pulled out of the vat while still
being attached to the building platform. The structuring is done by a
blue-light LED via a Digital Micromirror Device (DMD) chip and a
sophisticated optical system
shadowing effects. Here, the confocal laser beam principle of-
fers enormous advantages, especially when scanning interdental
spaces. Thus, structures in the mouth can be perfectly captured.
The system can also capture the color of the teeth and gums.
The additional information about the color of the real teeth
enables a perfect reproduction of the color appearance of the
full-ceramic crown during the subsequent additive
manufacturing process.
CAD Generation
For the digital design of the crown, various CAD programs are
available. In our case, the most convenient method is to stay in
the 3Shape workflow and design the crown with the 3Shape
Dental Designer (Copenhagen, DNK). Alternatively, it is also
possible to export the scanned data in STL format. Other CAD
software, such as the Zirkonzahn modeling software (Gais, I),
are specialized in working with dental STL data.
At the end of the design process, the STL file of the fin-
ished crown is obtained, which is then transferred to the
Lithoz system for additive fabrication.
3D Printing of the Crown
In order to allow the generated CAD structures to be printed,
suitable support structures are required. These facilitate the
connection of the freeform surface of the restoration to the
building platform of the 3D printer. In the case presented here,
the support generation was carried out with the 3Data Expert®
from the company Deskartes (Espoo, Finland). The CAD
models, together with the generated support structures, are
loaded into the data preparation software of the CeraFab
7500 Dental 3D printer, where the orientation of the part on
the building platform and suitable printing parameters are se-
lected as indicated in Fig. 3.
LithaCon 3Y 230 (3 mol% yttria-stabilized zirconia, 3Y-
TZP) was used as the raw material for manufacturing the
crowns. The print run took 7 h for 20 crowns, resulting in a
printing time of 21 min per crown. After the printing process,
the parts are in their green state. These “green bodies” consist of

Fig. 3 Example of a single crown (gray) on the virtual building platform (yellow). The toothed structure between the molar crown and the virtual
building platform is the support structure
a cross-linked organic binder system and zirconia particles are
dispersed within the formulation. Any excess uncured slurry is
removed as the parts are cleansed before being transferred to
thermal post-processing (i.e., debinding and sintering). This
cleansing step is carried out using a direct stream of compressed
air from an airbrush pistol in the CeraCleaning Station Ultra
(Lithoz, Vienna, Austria) and the commercial cleaning medium
LithaSol 20 (Lithoz, Vienna, Austria).
Staining and Sintering of the Crown
Thermal post-processing converts the composite green bodies to
the final sintered ceramic crowns. This is done by removing any
remaining organic material through pyrolysis at an elevated tem-
perature of up to 1000 °C. This step is called debinding and takes
a period of several hours. This results in a so-called “white”
body, which is a pure ceramic material and no longer contain
any binder. Furthermore, sinter bridges have already been
formed in this stage, meaning the part can be manually handled.
Restorations can be easily and individually colored using
coloring liquids in the white state. Three methods are possible:
& Dipping the crown in the coloring liquid solutions
& Individual painting of the crown with a brush and coloring
liquid
& A combination of both the aforementioned methods
During the course of the development, the third variant
proved to be ideal. The basic coloring is carried out by im-
mersion, with the individual adaptation then being carried out
after this immersion process using various intensive coloring
liquids, especially in the crown margin area and in the incisal/
Curr Oral Health Rep
occlusal surface area. After the staining process, it is important
that the crowns have been properly and fully dried before the
final sintering process.
The sintering process in this case was carried out at 1600 °C.
The heating rate was 8 °C/min, with a dwell time of 2 h at the
final temperature. The cooling rate thereafter was 8 °C/min
down to 500 °C. Finally, the part was left to cool down at a
room temperature.
Staining and Glazing
In order to finalize the crown restorations, stain and glaze firing
are carried out. These are done at a temperature of 770 °C. In
this case, IPS e.max Ceram stains and glaze have been used.
Evaluation of the Final Result
For the additive production of the crown using Lithoz’s LCM
process, a 3Y-TZP material (3 mol% Y 2O3) was used.
Normally, such high-strength zirconium oxide is used for the
fabrication of crown and bridge frameworks which are manu-
ally veneered with a silicate ceramic material. As that was not
the focus of this study, the translucency of restorations produced
appears rather low. Nevertheless, it proves that the LCM process
is suitable for producing parts which possess attractive esthetic
properties for fully anatomical crowns (Fig. 4).
One particular attractive quality of restorations created using
this method is the outstanding reproduction of the sharp-edged
crown margins, as well as the exact reproduction of the occlusal
surfaces with sharp and natural replication of the fissures.
This factor is especially important as augmentation of the
crown margin is usually always necessary during subtractive
Curr Oral Health Rep
Fig. 4 The 3 processing steps of the Lithoz LCM crowns from 3Y-TZP
are the following: left, green body; middle, white body; and right, finished
crown after the stain/glaze firing
processing, meaning occlusal fissures are always replicated in a
rounded manner due to the finite diameter of the rotating tools.
Additive manufacturing proves to be very advantageous here.
Conclusion and Outlook
Additive manufacturing processes have the essential advan-
tage that the properties of parts can be influenced during the
construction process. This positively affects both the mechan-
ical and esthetic properties of a component. In subtractive
processes, on the other hand, these characteristics are already
determined in the production of the milling blank. This facil-
itates enormous freedom in 3D printing during the design
process. When applied to the additive production of ceramic
dental prostheses, completely new approaches to the nature-
identical production of dental prostheses and replacement of
teeth will be possible in the future.
Digital scanning of the three-dimensional tooth layering
using NIR (near infrared) technology together with tooth
structure databases forms the base of this technology [14•,
15, 16•]. NIR technology uses long wave light in the infrared
range to scan teeth. This allows for the penetration of the tooth
enamel and is reflected at the border of the DEJ (dentin enamel
junction). Consequently, it will be possible in the future to
scan the individual layers of the tooth and to store them in
tooth structure databases.
Additive technologies, such as the LCM process, are the
ideal manufacturing methods to achieve this goal. Gradient
technologies can be individually adapted to the restoration
geometries and offer unprecedented creative freedom in
three-dimensional spaces, which is not possible when using
conventional technologies.
Compliance with Ethical Standards
Conflict of Interest The authors declare that they have no conflicts of
interest.
Human and Animal Rights This article does not contain any studies
with human or animal subjects performed by any of the authors.
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