d e n t a l m a t e r i a l s 3 6 ( 2 0 2 0 ) 442–455

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Suitability of 3D printed pieces of nanocrystalline

zirconia for dental applications

A.C. Branco a,b , R. Silva a , T. Santos c , H. Jorge d , A.R. Rodrigues b ,

R. Fernandes b , S. Bandarra e , I. Barahona e , A.P.A. Matos e , K. Lorenz f ,
M. Polido e , R. Colaço g , A.P. Serro a,e,∗ , C.G. Figueiredo-Pina b,e,h
a CQE, Instituto Superior Técnico, Universidade de Lisboa, Lisboa, Portugal
b CDP2T, Escola Superior de Tecnologia de Setúbal, Instituto Politécnico de Setúbal, Setúbal, Portugal
c HiTEC, Porto Salvo, Portugal
d Centro Tecnológico da Cerâmica e do Vidro (CTCV), Coimbra, Portugal
e CiiEM, Instituto Universitário Egas Moniz, Monte de Caparica, Portugal
f INESC-MN, IPFN, Instituto Superior Técnico, Universidade de Lisboa, Bobadela, Portugal
g IDMEC e Departamento de Engenharia Mecânica, Instituto Superior Técnico, Universidade de Lisboa, Lisboa,

Portugal
h CeFEMA, Instituto Superior Técnico, Universidade de Lisboa, Lisboa, Portugal

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

Article history: Objectives. The main goal of this work is to evaluate the suitability of nanostructured zirconia
Accepted 14 January 2020 pieces obtained by robocasting additive manufacturing (AM), for dental applications.
Methods. The density, crystalline structure, morphology/porosity, surface roughness, hard-
ness, toughness, wettability and biocompatibility of the produced samples were compared
Keywords: with those of samples obtained by conventional subtractive manufacturing (SM) of a similar
3D printing/additive manufacturing commercial zirconia material. Chewing simulation studies were carried out against dental
Robocasting human cusps in artificial saliva. The wear of the material was quantified and the wear
Dental material mechanisms investigated, as well as the influence of glaze coating.
Zirconia Results. AM samples, that revealed to be biocompatible, are slightly less dense and more
Wear porous than SM samples, showing lower hardness, toughness and wettability than SM sam-
ples. After chewing tests, no wear was found both on AM and SM samples. However, the
dental wear was significantly lower when AM samples were used as counterbody. Concern-
ing the glazed samples, both coated surfaces and dental cusps suffered wear, being the
cusps’ wear higher than that found for unglazed samples. More, cusps tested against AM
coated samples suffered less wear comparatively to those opposed to SM coated samples.
Significance. Overall, the results presented in this paper show that AM processed nanostruc-
tured zirconia can be used in dental restorations, with important advantages from the point
of view of processing and tribological performance. Moreover, the option for glaze finishing
should be carefully considered both in SM and AM processed specimens.
© 2020 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.

∗
Corresponding author at: CQE, Instituto Superior Técnico, Universidade de Lisboa, Lisboa, Portugal.
E-mail address: anapaula.serro@tecnico.ulisboa.pt (A.P. Serro).
https://doi.org/10.1016/j.dental.2020.01.006
0109-5641/© 2020 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.

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 d e n t a l m a t e r i a l s 3 6 ( 2 0 2 0 ) 442–455
1. Introduction
Synthetic dental materials are used to repair/replace missing
tooth tissue, allowing re-establishing masticatory, phonetic
and aesthetic functions. Among them, ceramics play an
important role, since they are highly compatible with oral
environment, present good chemical resistance and suitable
mechanical and optical properties to mimic the natural teeth
[1–3]. Zirconia is the most used ceramic for dental crown
replacement [4,5]. It presents high strength, toughness, hard-
ness, and resistance to wear and corrosion, being easily
machinable in the pre-sintered state [4].
Nowadays, the processing of zirconia dental structures
is generally based on CAD/CAM of compact or pre-sintered
core materials. Subtractive manufacturing (SM) is currently
used to produce these types of structures by removing sur-
plus material from ceramic blocs in milling units. However,
this methodology impairs the production of parts with intri-
cate internal details, because the millings units have severe
constraints to the angulations [6]. More, the production of
complex pieces leads to a more time-consuming and expen-
sive cost of fabrication [6]. Additionally, this method involves
a large amount of wasted raw material. To overcome the
drawbacks of SM. To overcome the drawbacks of SM, a new
type of technologies based on additive manufacturing (AM)
(also referred as 3D printing) is emerging as a tool with great
potential to build up long term dental structures [7]. In the
dental field, AM techniques are considered promising and a
valuable tool to ensure mass customization, with higher effi-
ciency, repeatability and reproducibility [6]. They also allow
lower production costs comparatively to SM, a faster produc-
tion of customized dental pieces with complex details (e.g.
intricate internal geometries and arbitrary angles [6]), since
they involve less manufacturing steps. Moreover, they reduce
energy consumption and material waste since the amount of
material needed is only what is required to build the part,
and eliminates the use of conventional manufacturing tools
[7]. AM also allows the production of structured composite
materials by combining different materials to improve the
mechanical and tribological properties [6].
Recently, some studies focused on the production of
zirconia pieces using different AM techniques (e.g. Vat
polymerization/stereolithography [8–10] and material extru-
sion/jetting [11–16]) and investigated properties as density,
porosity, surface roughness, microstructure, dimensional
accuracy, morphology and mechanical behaviour. Such prop-
erties depend on the ceramic paste composition (e.g. solid
content, solid particles size, addition of dispersants and
binders) and printing conditions (e.g. nozzle size, deposition
velocity and temperature). It was found that it is possible to
produce dense 3D components (relative densities 96.9–99.3
% [14,13]) with mechanical properties close to milled zirco-
nia (flexural strength 943−1154 MPa [6,13], fracture toughness
6.4–6.7 MPa·m1/2 [13,6] and hardness 13.9 GPa [10]) and high
dimensional stability [9,10,17]. However, none of the above-
mentioned works studied the tribological behaviour of the
produced materials. To be used in dental crown replace-
ment/restoration, zirconia must be resistant to the stress
induced during mastication without suffering significant
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443
wear. Additionally, they also shall prevent the abnormal wear
of the antagonist natural tooth surfaces [18], since the loss
of dental material may affect negatively the chewing ability,
dental sensitivity and aesthetics.
In order to improve restorations aesthetic properties
(e.g. colour, brightness and translucency), zirconia dental
pieces are usually manually coated with feldspathic ceramics
[6,20,21] which differ in composition and microstructure, but
fulfil stablished standards concerning mechanical properties
(e.g. minimum flexural strength 50 MPa [19]). However, both
clinical practice and in-vitro testing show a typical failure pat-
tern of such coatings, which involves chipping, delamination,
wear and fracture [6,22–25].
The aim of the present work is to evaluate the potential
of the additive manufacturing (AM) method robocasting to
produce nanostructured zirconia pieces suitable for dental
applications. This technique involves the extrusion and layer-
by-layer deposition of a ceramic paste according to a digital
3D model [24]. As far as the authors know this is the first time
that a in-depth characterization of robocasting AM processed
zirconia pieces for dental applications is made. The bench-
mark are zirconia samples processed by classical subtractive
manufacturing processes (SM) typically used in dental appli-
cations. Microstructural and surface characterization of both
type of samples, as well as of their wettability and mechani-
cal and tribological properties was performed. The influence of
glazing was also accessed. Finally, the biocompatibility of both
types of pieces relatively to fibroblast cells was evaluated.
2. Materials and methods
2.1. Materials
Yttria (3% mol) -stabilized zirconia powder Zpex from Tosoh
was used to produce the paste to manufacture AM samples.
Besides, organic corn syrup (La Finestra Sul Cielo), d(-)-fructose
EPR Ph. Eur. (Labkem) and Zusoplast C92 (Zschimmer and
Schwarz) which were used as plasticizers and stabilizers, and
Dolapix CE 64 (Zschimmer and Schwarz) as dispersant. Sam-
ples washing solution was prepared with Extran (Merck). In the
case of SM samples, yttria (3% mol) -stabilized zirconia blocks
Ice Zirkon Translucent from Zirkonzahn were used.
A glaze ceramic paste (IPS e.max Ceram Glaze Paste 3 g)
from Ivoclar Vivadent [25] was used to coat the zirconia sam-
ples.
Dental cusps were isolated from 8 human permanent
healthy molars which were visually inspected to ensure the
absence of caries, damages or fillers/sealants. Informed con-
sents were obtained prior to teeth extraction. Chloramine-T
trihydrate (VWR, ≥98%) and a fluoride free toothpaste (Col-
gate) were used for teeth cleaning. A thermosetting phenol
formaldehyde resin (Bakelite, Vertex Castapress) was used to
immobilize the cusps for wear simulation tests.
Artificial saliva (pH 6.9–7.0), which was used as lubricant in
the chewing simulation tests, was prepared using the follow-
ing reagents (all purchased from Sigma-Aldrich) [26]: sodium
sulphide nonahydrate (Na2 S•9H2 O, 0.005 g/L), sodium chlo-
ride (NaCl, 0.4 g/L), potassium chloride (KCl, 0.4 g/L), sodium
phosphate monobasic dihydrate (NaH2 PO4 •2H2 O, 0.69 g/L),
444 d e n t a l m a t e r i a l s 3 6 ( 2 0 2 0 ) 442–455
urea (NH2 CONH2 , 1 g/L), sodium phosphate dibasic (Na2 HPO4 ,
0.8 g/L), calcium chloride (CaCl2 , 0.2 g/L). Distilled and deion-
ized (DD) water, obtained from a Millipore system, was used
to prepare both artificial saliva and the ceramic paste for AM.
All chemicals and reagents used in cytotoxicity assays
were of highest purity grade and sterile. Dulbecco’s Modified
Eagle Medium (DMEM), bovine calf serum, amphotericin B,
sodium pyruvate, l-glutamine, phosphate-buffered saline
(PBS; 10 mM, pH 7.4), trypsin from bovine pancreas, thia-
zolyl blue tetrazolium bromide (MTT) were purchased from
Sigma Aldrich. Penicillin–streptomycin solution (10,000 U
penicillin and 10 mg streptomycin per millilitre in 0.9% NaCl)
was obtained from Gibco. The dimethylsulfoxide (DMSO)
and Triton-X100 were obtained from Merck. Glutaraldehyde
(Merck), cacodylate buffer (AppliChem Panreac), t-butanol
(Merck) and ethanol (Chem-lab) were used to prepare the
samples with cells for scanning electron microscopy (SEM)
analysis.
2.2. Methods
2.2.1. Dental samples preparation
The extracted teeth were washed with water and disinfected
by immersion in 1% chloramine -T trihydrate solution, at 4 ◦ C,
for one week. Then, the specimens were brushed with tooth-
paste to remove the bacterial plaque and food scraps. Each
tooth was cut in 4 parts, so that 4 cusps could be isolated and
used for the wear tests in the chewing simulator. Cusps were
stored in DD water at 4 ◦ C, until use, to avoid dehydration.
2.2.2. Zirconia samples production
Two methods were used to obtain the zirconia samples: sub-
tractive manufacturing (SM) and additive manufacturing (AM).
Commercial yttria-stabilized zirconia blocks were milled to
produce SM samples (15 × 15 × 4 mm3 , except for biocompati-
bility tests where cubes with 4 × 4 × 4 mm3 were used), using
a Zirkonzahn M5 milling unit. After the milling process, the
samples were cleaned using dry compressed air and were sin-
tered in an oven (Zirkonofen 700 Ultra-Vakuum). The sintering
cycle consisted of a heating step of 3 h, a plateau of 2 h at
1500 ◦ C and finally a cooling step of 3 h.
AM samples were produced by robocasting using a paste
with the following composition: 350 g of ZrO2 , 75.6 g of water,
8.75 g of corn syrup, 10.5 g of fructose, 0.84 g of Zusoplast
C92 and 0.105 g of Dolapix CE 64. 3D CAD models of plates
(15 × 15 × 4 mm3 , except for biocompatibility tests where, as
for SM, cubes with 4 × 4 × 4 mm3 were used) were obtained
through the 123D Design software. Cura software was used to
generate the GCODE code to set the printer (Delta WASP 2040
with Ceramic Extruder kit). The samples were printed at room
temperature using the following parameters: 60 mm/s, noz-
zle size 0.4 mm, printed layer height 0.2 mm. After printing,
the green samples were air dried overnight and then grinded
with a P-600 SiC sandpaper to remove surface features asso-
ciated to layer-by-layer deposition. Samples were submitted
to a sintering cycle which included a pre-heating till 400 ◦ C
at a rate of ≈0.6 ◦ C/min, a debinding plateau at 400 ◦ C for 1 h,
a second heating step till 1500 ◦ C at a rate of ≈0.9 ◦ C/min, a
plateau at 1500 ◦ C during 2 h and finally a cooling step at a
rate of ≈5 ◦ C/min. After sintering, AM samples were polished
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until diamond paste 3 ␮m in order to obtain an average surface
roughness (Ra ) similar to SM samples.
Both AM and SM samples were washed for 5 min in an ultra-
sonic bath with a 15% Extran aqueous solution and then with
DD water for 10 min, dried with nitrogen gas, submitted to
vacuum overnight and finally stored in a desiccator.
Part of the AM and SM samples were manually coated with
a ceramic glaze paste. After glazing, the samples were ovened
at 930 ◦ C during 30 min.
2.2.3. Samples characterization
2.2.3.1. Microstructure and topography
Grazing incidence X-ray diffraction (GIXRD) was performed
using a Bruker D8 Discover diffractometer with K␣1,2 radia-
tion (wavelength 1.54 A◦ ), a Göbel mirror and a 0.6 mm slit in
the primary beam and a Soller slit and scintillation detector
in the secondary beam, at 40 kV and 40 mA. The scanning was
performed with a step size of 0.02◦ , a fixed incidence angle (␣)
of 1◦ and dwell time of 15 s in the range between 2␪ = 25–70◦ .
Zirconia samples (SM and AM) were analysed before and after
glazing. The software Match! was used to visualize the diffrac-
togram of each sample. The crystallites size was estimated
using the Debye-Scherrer equation [27]:
K
t= (1)
Bcos B
where t is the size of the crystalline domains, K is a dimen-
sionless shape factor (default value of 0.9),  is the X-ray
wavelength, B is the line broadening at half of the maximum
intensity, and B is the Bragg angle.
Topographical images of AM and SM samples were
obtained using an atomic force microscope (AFM) Nanosurf
Easyscan 2. Images of 10 × 10 ␮m2 were obtained in contact
mode, at room temperature, using a silicon probe with an
applied force of 25 nN and at a scan rate of 1 Hz. The average
surface roughness of the samples was determined at different
scales using two methods: Sa , based on the whole area of the
previously referred AFM images; and Ra , based on surface 2D
profiles obtained using a surface roughness tester (SRT, Mitu-
toyo 178-923-2A/SJ-201 SurfTest model). In the last, sample
lengths of 1.75 mm, with a cut-off of 0.25 mm were scanned.
Four samples of each type were analysed (three scans/sample).
Samples surface and cross-cut morphology was analysed
by scanning electron microscopy (SEM). To obtain the cross-cut
images, samples were cut with a diamond disc and polished
up to 3 ␮m. Images were obtained using the JEOL scanning
electron microscope (JSM-7001F) with a voltage of 15 kV and a
vacuum of ∼ 8 × 10−4 Pa. Energy dispersive spectroscopy (EDS)
was used to identify the chemical elements present in the
samples. The samples were previously sputter-coated with a
thin film of Au/Pd.
2.2.3.2. Density and porosity
Density measurements were performed through the
Archimedes method. The measurements were done on a
AND GR-200 balance, which includes the proper density
determination kit. Five samples of each type were used.
 d e n t a l m a t e r i a l s 3 6 ( 2 0 2 0 ) 442–455
The porosity of samples surface and cross-cut sections was
estimated from the analysis of five SEM images for each sam-
ple using the ImageJ software.
2.2.3.3. Wettability
Water contact angles were determined through the sessile
drop method. Measurements were performed at room tem-
perature on previously dried samples (vacuum, 24 h), using a
goniometer Ramé-Hart 100-07-00 with a video camera (JAI CV-
A50) coupled to a microscope (WildM3Z). Microdrops of DD
water were generated on the surface samples with a micro-
metric syringe inside a testing chamber saturated with water,
to avoid evaporation. For each drop, images were taken at pre-
established times during 10 min. The acquisition and analysis
of the images was performed using the ADSA-P software
(Axisymmetric Drop Shape Analysis-Profile [28]. At least ten
drops were done on each material.
2.2.3.4. Hardness and toughness
The microdurometer HSV-30 Shimadzu was used to measure
Vickers hardness on the surface and on the cross-cut section
of AM and SM samples. For comparison purposes, measure-
ments were also performed on glaze surface. A load of 294.21 N
with a dwell time of 15 s was applied on the samples surface.
Four samples of each type were analysed. For each sample,
five indentations were performed in different locations. The
indentations on the samples induced the formation of cracks
whose length was measured from SEM images using the
ImageJ software. Fracture toughness was estimated through
the equation [29,30]:
P
KIC = 0.0726 ×
c3/2
where KIC is the indentation fracture toughness, P (N) is the
indentation load and c (m) is the length of the most severe
produced crack in each indentation mark.
2.2.3.5. Tribological behaviour
The zirconia samples (unglazed and glazed) were tested
against dental cusps in artificial saliva, using a chewing sim-
ulator (CS-4.2 SD Mechatronik), in order to mimic the natural
mastication movement. The tests were carried out during 4
days (360,000 chewing cycles, corresponding to approximately
1.5 year of human mastication [31]) at room temperature,
using a setup as the one defined in [5]. The operational
parameters were set as: vertical speed 40 mm/s, horizontal
Fig. 1 – Overlapping of the cusps’ 3D profiles before (grey) and after (orange) wear testing.
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445
speed 20 mm/s, vertical movement 2 mm, horizontal move-
ment 0.7 mm and frequency ∼1 Hz. A vertical load of 50 N,
within the range of the typical masticatory loads observed
in vivo [32–35], was used. For each sample type, eight tests were
performed.
In order to estimate the dental wear rate, 3D scans of each
cusp were obtained before and after simulation tests using
a 3D scanner (Scanner SGOO – Zirkonzahn, Fig. 1). The dental
material volumetric loss was determined from the variation of
the cusps’ volume using the Autodesk Netfabb Standard 2018
software (Fig. 1). For each cusp, three measurements were per-
formed. The wear rate was calculated dividing the loss volume
by the product of the sliding distance by the applied load. The
wear mechanisms of the cusps’ surface were analysed by SEM
as described above. The cusps were pre-coated with a thin film
of Au/Pd.
The wear volume of the zirconia samples (unglazed and
glazed) was determined from 2D profiles of the wear tracks,
obtained using the surface roughness tester referred above.
For each track, the worn volume was estimated by multiplying
the track length by the average of the cross-sectional worn
areas determined by numerical integration of the 2D profiles
(3 per track). The worn surfaces were also characterized by
SEM-EDS.
2.2.3.6. Biocompatibility studies
The biocompatibility studies of AM unglazed samples were
conducted using NIH 3T3 fibroblast cells 93061524 obtained
from Health Protection Agency Culture Collections and sup-
plied by Sigma. SM unglazed samples and glaze coating were
also tested for comparison purposes.
(2)
2.2.3.6.1. Cell culture
The cells were cultured in DMEM supplemented with
10% bovine calf serum, 2.5 ␮g/ml amphotericin B, 1 mM
sodium pyruvate, 2 mM l-glutamine, 100 U/mL penicillin and
0.1 mg/mL streptomycin. The cells were routinely cultured in
25 cm3 culture flasks and kept at 37 ◦ C in a humidified atmo-
sphere of 5% CO2 [36]. Only cells from the 5th to the 8th
passage were used, avoiding changes in their genetic back-
ground.
2.2.3.6.2. Cytotoxicity tests
A cell viability determination was carried out with leached
solutions from AM and SM unglazed cubic pieces with approx-
imately 64 mm3 . Cubes coated with glaze were also used in
446 d e n t a l m a t e r i a l s 3 6 ( 2 0 2 0 ) 442–455
the test. The pieces were exposed for 12 h to UV radiation to
reduce biological contamination. After this process, each cubic
piece was incubated in 2 mL of cell culture medium for 1 and
7 days at 37 ◦ C in a humidified atmosphere of 5% CO2 and 95%
air. At the end of incubation, the extracts were immediately
used for in vitro cytotoxic assays, in which 1 × 104 fibroblast
cells were seeded per well in 96-well plates and incubated
24 h at 37 ◦ C under 5% CO2 , to allow cell adhesion and prolif-
eration. Then, cells were exposed to the leached solutions for
24 h and their cytotoxicity was determined using MTT assay
[37,38]. Briefly, MTT solution (0.5 mg/mL in culture medium,
Sigma) was added to the cells and incubated for 2 h at 37 ◦ C,
5% CO2 . The formed blue formazan crystals were dissolved
in DMSO and the absorbance readings were taken using a
Bio-Rad Model 680 Microplate Reader, at 595 nm. As positive
control 0.1% Triton-X100 was used.
The percentage of viable cells (with functional mitochon-
drial activity) was determined by comparing the values of
optical density of treated cells versus untreated cells (control
set to 100% viability). Eight replicate cultures were included in
each experimental point per independent assay.
2.2.3.6.3. Attachment assays
3T3 fibroblasts (2.5 × 104 cells/well) were seeded directly upon
the surface of AM and SM unglazed surfaces, as well as on
glaze, placed in wells of 48-well culture plates. As control, cells
were incubated in 48-well plate without any piece. After 72 h
incubation at 37 ◦ C under 5% CO2 , the culture medium was
removed and the wells washed gently with PBS to remove
non-adherent cells. The pieces were removed from original
wells and placed in empty wells. Adherent cells on the control
wells and on pieces were trypsinized and harvested for MTT
assay. The MTT assay was done as described. Since the opti-
cal density (OD) is proportional to the number of viable cells,
the number of adherent cells is given as the mean ± SD of OD
obtained for normalized surface area (cm2 ).
Fig. 2 – GIXRD spectra of AM and SM zirconia samples, and glaze coating. Peaks characteristic of the tetragonal (t) and
monoclinic (m) phases are marked [40].
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2.2.3.6.4. SEM analysis
Cells were seeded on AM and SM pieces surfaces and on glaze
samples placed in 24-well culture plate at a density of 0.5 × 104
cells per well for 7 days. At the end of incubation, AM and
SM samples were removed and fixed for 24 h at 4 ◦ C with 3%
glutaraldehyde in cacodylate buffer 0.1 M, pH 7.3. After fix-
ing, the pieces were washed with cacodylate buffered solution
for at least 2 h. Dehydration with sequential alcohol washes
(50, 75, 95%, and absolute solutions) was performed. Further
dehydration was performed with the t-butanol freeze-drying
method [39]. In brief, the samples were passed from ethanol
to t-butanol at 40 ◦ C, stored at 4 ◦ C during 1 h and dried under
vacuum for 2 h. The disks were then put on SEM stubs, rotary
coated with a gold layer in a JEE-4X vacuum and observed
using a JEOL JSM-5400.
2.2.4. Statistical analysis
Statistical analysis was carried out using the using the IBM
SPSS Statistics software (Version 19). Shapiro-Wilk test was
performed to evaluate normality of the results. The compar-
isons of two independent samples in respect to quantitative
variables, which follow normal distributions were performed
through t-test for independent samples. Contrarily, Mann-
Whitney non-parametric test was chosen when normality was
not verified. The comparison of three normally distributed
independent samples was performed through ANOVA (one-
way analysis of variance). Kruskal-Wallis non-parametric test
was applied when normality of at least one group was
not observed. The level of significance chosen was always
0.05. Concerning the sample size, it was estimated to obtain
average values with a maximum error of 6% and a confi-
dence level of 95%. For cusps wear, due to the variability of
the dental samples, the admissible maximum error was of
10%.
 d e n t a l m a t e r i a l s 3 6 ( 2 0 2 0 ) 442–455 447

AFM images (Fig. 3) of both AM and SM ceramic sur-

Table 1 – Application of the Debye-Scherrer equation to
the zirconia peaks of AM and SM samples. faces show a granular morphology with grain size range
≈500–700 nm. For the glaze surfaces was observed a uniform
Sample Phase 2 cos () B (rad) t (nm)
surface without features. Unglazed samples present a similar
AM Tetragonal 30 0.966 0.009 16 surface roughness (Sa , Table 2, p = 0.058). The same tendency
Monoclinic – – – –
was observed for the linear roughness (Ra , Table 2) determined
SM Tetragonal 30 0.966 0.005 29
through contact profilometry (p = 0.911). The glaze coating led
Monoclinic 28 0.970 0.007 20
a smoother surface, with significantly lower roughness values
(Table 2, p < 0.008 for Sa and p < 0.009 for Ra ).
SEM images reveal the existence of pores both on the sur-
3. Results face and bulk of AM samples (Fig. 4). The average size of
the surface pores is 31 ± 8 ␮m, being the maximum pore size
3.1. Samples characterization 50.3 ␮m. For the bulk, an average value of 24 ± 7 ␮m was found,
with maximum pore size 37.8 ␮m. The porosity of the AM
GIXRD diffractograms of AM and SM zirconia samples, as well samples surface is 3.9%, while for the bulk is 1.2% (Table 2).
as of the glaze coating are presented in Fig. 2. AM and SM Contrarily to AM samples, SM samples did not present any
samples show similar diffraction patterns, with peaks corre- sign of pores both on surface and bulk. The application of a
sponding to the presence of both tetragonal (t) and monoclinic glaze layer (thickness ≈53 ␮m, see Fig. 4) leads to a homoge-
(m) phases. However, while in the AM processed samples neous surface on both samples. According to the EDS analysis,
the presence of the low temperature phase (monoclinic) is the glaze coating is feldspathic, containing different ratios
residual, in the SM samples the proportion of this phase is of aluminium (3.1 at%), silicon (29.4 at%), calcium (0.7 at%),
significant. The application of the Debye-Scherrer equation to potassium (3.5 at%) and sodium (5.4 at%).
the peaks of the tetragonal and monoclinic phases allowed Despite the significant differences in the porosity
estimating the crystallites size of the samples (Table 1). For (p < 0.001), AM and SM zirconia samples present close
AM samples, the size of the tetragonal nanocrystallites is values of density (∼6 g/cm3 , Table 2), although statistically
16 nm. For SM, the peaks correspondent to the monoclinic different (p = 0.027).
and tetragonal phases give rise to values of 20 nm and 29 nm, Concerning wettability, AM samples present a lower water
respectively. Concerning glaze coating, a pattern characteristic contact angle than SM samples (Table 2, p < 0.001). The glaze
of a fully amorphous structure was observed in the diffrac- coating led to lower values (p = 0.007).
togram.

Fig. 3 – AFM images of the AM and SM zirconia samples surfaces and of the glaze coating.

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448 d e n t a l m a t e r i a l s 3 6 ( 2 0 2 0 ) 442–455

Table 2 – Resume of the properties of the zirconia samples produced by AM and SM and of the glaze.
AM SM Glaze
Average roughness - Sa (nm) 121 ± 5 126 ± 6 1.0 ± 0.1
Linear roughness - Ra (nm) 241 ± 16 243 ± 9 173 ± 17
Superficial porosity (%) 3.9 ± 1.7 0.10 ± 0.03 ∼0
Cross-cut porosity (%) 1.2 ± 0.1 ∼0 –
Density (g/cm3 ) 5.9 ± 0.1 6.06 ± 0.02 2.05 ± 0.08
o
Water contact angle ( ) 54 ± 3 62 ± 2 33 ± 3
Phases essentially tetragonal tetragonal+monoclinic amorphous
Nanocrystallites sizea (nm) 16 20-29 –
Grain size (nm) ≈500–700 ≈500-700 –
a
As presented in Table 1.

Fig. 5 shows the hardness and toughness of the zirconia
samples measured over the surface and cross-cut section, as
well as over the glaze surface. It was found that hardness
does not vary with the measurement direction in both AM and
SM samples (p = 0.162 and p = 0.315, respectively). AM samples
present a lower hardness (p < 0.001, for both surface and cross-
cut analysis) than SM samples. Regarding the glaze coating, its
hardness is significantly lower than those found for unglazed
samples (p < 0.001). With respect to toughness, AM and SM
samples present a slightly lower toughness in the cross-cut
section (p = 0.023 and p < 0.001, respectively). In addition, it was
observed that the toughness of the AM samples in both direc-
tions is lower than that found for SM samples (p < 0.001 for
surface and cross-cut). The glaze toughness is lower than that
observed for the zirconia samples (p < 0.001).

Fig. 4 – SEM images of the surface and cross-cut of AM samples, SM samples and glaze coating.

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 d e n t a l m a t e r i a l s 3 6 ( 2 0 2 0 ) 442–455 449

Fig. 5 – Surface and cross-cut hardness (a) and toughness (b) of AM samples, SM samples and glaze coating.

Fig. 6 – Wear rate of cusps and AM and SM unglazed/glazed samples.

3.2. Tribological behaviour
Fig. 6 presents the cusps and prosthetic materials’ wear rate
after the chewing simulation tests. AM unglazed samples
induce a cusps’ wear rate about 3.4 times lower than SM
unglazed samples (p = 0.002). The application of the coating
leads to an increase of the wear rate in both cases (p < 0.001 for
AM samples and p = 0.034 for SM samples). However, the dif-
ferences between the two types (p < 0.001) of samples become
lower (SM glazed wear rate 1.6 higher than AM glazed wear
rate). Concerning the AM and SM unglazed zirconia samples,
wear after chewing simulation tests is neglectable (Fig. 6). Con-
trarily, glazed samples present measurable wear rate, similar
for both type of samples (Fig. 6, p = 0.552).
SEM analysis of the cusps tested against AM unglazed sam-
ples show some surface delamination and adhered dental
particles (Fig. 7, marked with *) mainly composed by Ca and P,
as identified by EDS. Cusps tested against SM unglazed sam-
ples shows a smooth wear surface, without features. With
regard to the tests against AM and SM glazed zirconia, it is
possible to observe that both cusps present scratches, delam-
ination and adhered dental and glaze particles (Fig. 7, marked
with * and , respectively), as demonstrated by the EDS anal-
ysis.
SEM analysis show extensive regions of adhered material
on AM and SM surfaces. EDS analysis shows that the adherent
material (Fig. 8, marked with *) is rich in Ca and P, suggesting
that it arises from the dental cusps’ counterface. However, it
can be observed that, while the dental adherent material in
AM samples is mainly adherent on surface defects (pores), for
SM samples it is spread randomly throughout all the surface.
In what concerns the AM and SM glazed zirconia surfaces,
it can be observed that after the chewing simulation tests,
some parts of the glaze suffered wear, leaving zones of zirconia
exposed (Fig. 8, marked with ). Areas where the glaze coat-
ing did not suffer wear are marked with  in Fig. 8. Adhered
worn particles from the cusps are visible on both AM and SM
glazed zirconia samples (Fig. 8, marked with *).
3.3. Biocompatibility
Cytotoxicity tests of the leached solutions from AM and SM
unglazed samples, as well as from glaze led to the results pre-
sented in Fig. 9. No significant differences were found in the
viability of fibroblasts (p = 0.097 for 1 day and p = 0.254 for 7
days). The samples showed no cytotoxicity for fibroblast cells,
according to the ISO 10993-5 guideline cytotoxic threshold [37],
i.e. in the set of tests carried out, cell viability does not reach
values below 70%. The viability of fibroblasts slightly decreases
from 1 to 7 days of exposure to the extract solutions (≈28.1%
for AM, ≈19.4% for SM and ≈2.5% for glaze), but this decrease is
not statistically significant when compared to the untreated

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450 d e n t a l m a t e r i a l s 3 6 ( 2 0 2 0 ) 442–455

Fig. 7 – SEM images of the cusps surface tested against AM and SM unglazed/glazed zirconia samples after wear testing (*
Dental particles;  Glaze).

control cells (p = 0.225 for AM, p = 0.096 for SM and p = 0.136
for glaze). As positive control of toxicity, it was used Triton
X-100 that decreases fibroblasts viability to ≈16.0 % (data not
showed).
The number of attached cells on AM and SM surfaces and
on glaze, after 3 days of incubation, is presented in Fig. 10.
Although cell attachment on both zirconia unglazed samples
and on well culture plate was similar (p = 0.106), the aver-
age number of attached cells on AM samples was slightly
higher than on SM samples. Glazed samples show a signif-
icant decrease in the number of attached cells relatively to
control (p = 0.024).
SEM observations (Fig. 11) were performed to study the
cellular attachment and morphology. It was found that the
cells had an irregular and elongated shape with long filopo-
dia attached to the AM and SM substrates. Concerning glaze,
the cells present the same morphology but there are several
regions without cells indicating that glaze surface is less sus-
ceptible to cell adhesion (Fig. 10).
4. Discussion
In order to evaluate the applicability of an AM technology (robo-
casting) to produce reliable ceramic dental structures made of
zirconia, samples obtained by this technique were character-
ized and submitted to tribological tests against dental cusps
and compared with commercial zirconia samples obtained by

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 d e n t a l m a t e r i a l s 3 6 ( 2 0 2 0 ) 442–455 451

Fig. 8 – SEM images of the AM and SM unglazed/glazed zirconia samples surface after wear testing (* Dental particles;
Zirconia;  Glaze).

subtractive manufacturing (SM). The effect of glazing, a sur-
face finishing used for aesthetic reasons, was also accessed.
The mechanical properties of ceramic materials are
strongly affected by characteristics like density and porosity,
which depend mainly on the raw material (e.g. purity, powder
particles granulometric distribution) and on the manufac-
turing procedure (e.g. technique, operational parameters).
AM samples present a density close to SM samples (Table 2),
correspondent to 98.3% of the theoretical density of fully
dense zirconia (≥6 g/cm3 [41]). Its relative density is close to
that found by Peng et al. [42], who also used robocasting to
produce dense yttria-stabilized zirconia structures (94.5–97.8
%). Concerning porosity, contrarily to SM, where it is residual,
AM samples present pores (Fig. 4). Their random distribution
indicates that they are not related to a bad interlayer binding,
but probably are due to air bubbles trapped in the paste. In
fact, no features associated to eventual interlayear delami-
nation could be observed. An higher porosity results in lower
fracture toughness, as was observed when comparing AM
and SM samples (Fig. 5b). However, the attended value for the
robocasted samples (3.9 ± 0.2 MPa m1/2 ) is within the expected
values for zirconia based ceramics (1−8 MPa .m1/2 [43]). AM
samples microhardness is lower than that observed for SM
(Fig. 5a) and does not depend on the measurement direction.
This probably results from their higher porosity, since their
microstructure does not present significant differences. In
fact, AFM images show that both AM and SM samples present
grains with ≈500−700 nm, which correspond to secondary

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452 d e n t a l m a t e r i a l s 3 6 ( 2 0 2 0 ) 442–455

Fig. 9 – Cytotoxicity of leached solutions from AM and SM unglazed zirconia samples and from glaze coating.

Fig. 10 – Cell attachment on AM and SM unglazed zirconia samples and on glaze coating.

Fig. 11 – SEM images of cultured fibroblast cells in AM, SM and glazed surfaces.

grains composed by smaller primary grains (nanocrystallites
of the tetragonal and monoclinic phases). GIXRD analysis
show that both tetragonal and monoclinic phases are present
in AM and SM samples, being the primary grain sizes of the
same order of magnitude (between 16 and 29 nm). However,
the fracture toughness was lower for the cross-cut section
in both AM and SM samples. For AM, the difference is minor
and may result from small deffects that were created during
the layers deposition. For SM, the anisotropy in toughness
is typical of the unidirecional dry pressing forming method
[44].
Concerning the surface roughness, analogous values were
obtained both for Sa , determined by AFM, and Ra , measured at
a higher scale by profilometry. Ra values fall within the range
observed by other authors for human enamel (200−310 nm
[45]).
Wettable surfaces are generally considered favourable for
dental applications, since they impair the plaque retention
[46]. Since both AM and SM surfaces are hydrophilic, this
shall contribute to avoid microorganisms’ adhesion. How-
ever, the higher surface porosity of AM samples may have an
opposite effect. In fact, it is known that irregularities and/or
pores on the surface usually promote microorganisms adhe-
sion [47–49]. Further studies are needed to clarify the adhesion
behaviour of microorganisms to the produced ceramic mate-
rials.
Biocompatibility of zirconia ceramic dental devices is an
important topic from a clinical point of view, since these pieces

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 d e n t a l m a t e r i a l s 3 6 ( 2 0 2 0 ) 442–455
are designed to be used permanently in oral cavity. Although
generally zirconia is recognized for its high biocompatibility
[3,50,51], some authors refer that it may cause side effects like
immunoallergy [52]. Also, the manufacturing process may add
contaminants and/or change the materials structure, factors
that may affect the behaviour of soft-tissue cells, such as gingi-
val fibroblasts. In this study, it was observed that the extracts
of AM zirconia pieces, as well as of SM and glazed ones, do
not induce toxicity after different incubation periods in cul-
ture media (Fig. 9). Concerning the number of attached cells
(Fig. 10) and their morphology (Fig. 11), AM and SM samples
did not differ significantly. The presence of filopodia suggests
a high degree of adhesion between the cells and the tested
materials. Thus, the results allow concluding that AM samples
present similar biocompatibility to zirconia pieces produced
by SM. The cells on the glaze have the same morphology which
confirms with the non-toxicity of the glaze. However, it seems
that the glaze decreases the cells adherence since the number
of adherent cells is lower when compared with AM and SM
samples. It shall be stressed that cell-adhesion is a desirable
process, since it allows the formation of an effective biological
soft tissue seal that prevents the build-up of plaque. Con-
cerning this issue, unglazed zirconia samples present a better
performance than glazed samples. This behaviour of zirconia
based materials was already reported by other authors [43,53].
The coating of the zirconia samples with glaze originated
a surface without pores (Fig. 4), with a low fracture toughness
(Fig. 5b) which can be due not only to the chemical character-
istics of the material but also to its amorphous nature (Fig. 2).
The coating hardness is 3–3.5 times lower than that found for
the underlying ceramic substrates, being similar to the val-
ues reported for enamel [54]. The absence of pores, together
with the vitreous nature of the coating leads to a significant
decrease of the surface roughness relatively to the AM and SM
surfaces.
Concerning the tribological behaviour of the zirco-
nia/dental cusp pair, no material loss was detected for both
AM and SM zirconia samples. This is in agreement with other
works, where dental cusps were also tested against zirconia
surfaces [5,19,55], and may be attributed to the high tough-
ness of zirconia that avoids microcracking wear mechanisms
on its surface and consequent hard third body particle for-
mation. Such high toughness also explains the absence of
zirconia fracture due to the impact of the cusps during the
chewing simulation tests. Even though there are concerns
about the zirconia ageing in wet and warm environment
[56,57], which triggers the tetragonal to monoclinic transfor-
mation leading to grains’ volume expansion and appearance
of intra-granular cracks followed by the grain pull out, no
evidences of such process were observed by SEM. SEM obser-
vation, together with EDS analysis only demonstrated the
presence of transferred dental material on both AM and SM
surfaces, probably due to the zirconia asperities interlock-
ing with the dental debris. Regarding to cusps wear, it was
observed that its wear rate was much higher when tests were
carried out with SM samples. It should be noted that zirco-
nia is much harder than enamel (359 HV [54]). On the other
hand, no features associated to zirconia third body particles
were observed. Thus, it can be inferred that the dental wear
mainly results from the prosthetic material asperities abra-
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453
sive action on the cusps (two-body abrasion). The asperities
of the harder SM surface shall penetrate deeper into the den-
tal cusps counterface, removing a higher amount of dental
material than the AM surface. On the other hand, the higher
hydrophobicity of SM samples shall impair the lubrication
of the contacting surfaces, thus enhancing the wear of the
counterfaces.
Glazing the zirconia samples is a common procedure per-
formed to improve the restorations aesthetic appearance. The
obtained results show that it leads to a significant increase of
the prosthetic and dental material wear rate. Similar results
were found by other authors [5,19,55] in in vitro tribological
studies. Also clinical studies demonstrated that chipping of
the veneer in the occlusal-proximal contact areas occurs fre-
quently [51,58,59]. Our results indicate that the wear of the
prosthetic material does not depend on the manufacturing
process of the underlying zirconia (Fig. 6). SEM analysis of
the glazed AM and SM samples worn areas (Fig. 5) and the
corresponding dental cusps counterfaces (Fig. 7) suggest the
occurrence of similar wear mechanisms in both cases. Due to
the low toughness of the coating, wear mechanisms associ-
ated with its fragile fracture might occur, leading to release
of three-body particles. These particles induced abrasion on
the cusps surface (Fig. 7) leading to an increased wear of the
dental material compared to that observed in the absence of
glaze (three-body abrasion). In certain areas, the amount of
glaze loss is so high, that zirconia became exposed (Fig. 5).
The higher wear rate observed for SM glazed samples rela-
tively to AM glazed samples (Fig. 6) can be attributed to the
higher hardness of the exposed zirconia of SM samples, as
previously explained for unglazed samples.
5. Conclusions
In the present work, zirconia samples obtained by robocast-
ing (AM) were characterized and compared with samples of
commercial zirconia processed by a traditional subtractive
manufacturing method, aiming their use for dental prosthesis.
It was found that AM samples are non-toxic, present a
nanocrystalline structure, are slightly less dense and more
porous than SM samples. Hardness and toughness of AM
samples are lower. However, the obtained values fall within
the range of zirconia dental ceramics. AM samples are more
hydrophilic, which may be atributed to its higher porosity.
Concerning their tribological behaviour, both AM and SM sam-
ples do not suffer wear. However, AM samples induce a lower
wear on the antagonist dental cusps, in chewing simulation
tests, which can be related to their lower hardness and higher
hydrophilicity.
The application of a glaze coating on both types of mate-
rials resulted in a dramatic increase of the antagonist cusps
wear rate. This shall be due to its low toughness that induces
wear mechanisms associated to fragile fracture and conse-
quent three-body abrasive wear. Therefore, glazing must be
avoided in the occlusal interfaces to prevent abnormal wear
of the antagonist materials. The obtained results show that
the glaze wear rate is similar for both the AM and SM sam-
ples and does not depend on the manufacturing process of
the underlying zirconia.
454 d e n t a l m a t e r i a l s 3 6 ( 2 0 2 0 ) 442–455
Overall, this study demonstrates that robocasting can be
used for the production of zirconia pieces suitable for dental
applications: it allows obtaining biologically safe materi-
als with adequate mechanical and tribological properties.
However, additional studies (e.g. ageing, chemical resistance)
are needed for a more complete evaluation.
Acknowledgements
To Fundação para a Ciência e a Tecnologia (FCT) for fund-
ing through projects 3D-DentalPrint (02/SAICT/2016/023940)
and the unit projects UIDB/00100/2020, UIDB/04585/2020,
UID/CTM/04540/2020 and UIDB/50022/2020 (LAETA) from CQE,
CiiEM, CeFEMA and IDMEC respectively. A.C. Branco acknowl-
edges to FCT the PhD grant SFRH/BD/145423/2019.
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