Dental Materials 39 (2023) 625–633

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Dental Materials
journal homepage: www.elsevier.com/locate/dental

Impact of post printing cleaning methods on geometry, transmission,

roughness parameters, and flexural strength of 3D-printed zirconia ]]
]]]]]]
]]

A. Liebermanna, , A. Schultheisa, F. Fabera, P. Rammelsbergb, S. Ruesb, F.S. Schwindlingb,c

⁎

a
Department of Prosthetic Dentistry, University of Cologne, Faculty of Medicine and University Hospital Cologne, Cologne, Germany
b
Department of Prosthetic Dentistry, Heidelberg University Hospital, Heidelberg, Germany
c
Department of Prosthetic Dentistry, Medical University Innsbruck, Innsbruck, Austria

A R T I C L E I N F O A B S T R A C T

Keywords: Objective: To analyze the impact of different post printing cleaning methods on geometry, transmission,
3D printing roughness parameters, and flexural strength of additively manufactured zirconia.
Zirconia Methods: Disc-shaped specimens (N = 100) were 3D-printed from 3 mol%-yttria-stabilized zirconia (material:
Post printing cleaning LithaCon 3Y 210; printer: CeraFab 7500, Lithoz) and were cleaned with five different methods (n = 20): (A) 25 s
Transmission
of airbrushing with the dedicated cleaning solution (LithaSol 30®, Lithoz) and 1-week storage in a drying oven
Roughness parameter
(40 °C); (B) 25 s airbrushing (LithaSol 30®) without drying oven; (C) 30 s ultrasonic bath (US) filled with
Flexural strength
Lithasol30®; (D) 300 s US filled with LithaSol 30®; (E) 30 s US filled with LithaSol 30® followed by 40 s of
airbrushing (LithaSol 30®). After cleaning, the samples were sintered. Geometry, transmission, roughness (Ra,
Rz), characteristic strengths (σ0), and Weibull moduli (m) were analyzed. Statistical analyses were performed
using Kolmogorov-Smirnov-, t-, Kruskal-Wallis-, and Mann-Whitney-U-tests (α < 0.05).
Results: Short US (C) resulted in the thickest and widest samples. Highest transmission was found for US
combined with airbrushing (E, p ≤ 0.004), followed by D and B (same range, p = 0.070). Roughness was lowest
for US combined with airbrushing (E, p ≤ 0.039), followed by A and B (same range, p = 0.172). A (σ0 =
1030 MPa, m = 8.2), B (σ0 = 1165 MPa, m = 9.8), and E (σ0 = 1146 MPa, m = 8.3) were significantly stronger
(p < 0.001) and substantially more reliable than C (σ0 = 480 MPa, m = 1.9) and D (σ0 = 486 MPa, m = 2.1).
Significance: For 3D-printed zirconia, cleaning strategy selection is important. Airbrushing (B) and short US
combined with airbrushing (E) were most favorable regarding transmission, roughness, and strength. Ultrasonic
cleaning alone was ineffective (short duration) or detrimental (long duration). Strategy E could be particularly
promising for hollow or porous structures.

1. Introduction erate more complex structures and to show a lower material

For decades, tooth-colored restorations have already been produced
subtractively as part of the digital CAD/CAM (computer-aided design/
computer-aided manufacturing) workflow, whereby the restorations
are milled or machined from a material block or disc. For some years
now, additive manufacturing by means of 3D printing has increasingly
been the focus of research and application for the production of tooth-
colored materials. To date, resins are predominantly used to produce
provisional restorations, although more and more materials for defini­
tive use are becoming available on the dental market [1–3]. The ad­
ditive manufacturing method has the advantage of being able to gen­
consumption than when using subtractive manufacturing [4].
Additive manufacturing has been further developed so that zirconia
can also be 3D-printed [3]. To additively manufacture zirconia, the most
frequently described methods are stereolithography, digital light pro­
cessing, selective laser sintering, selective laser melting, ink-jet printing,
fused deposition modeling, direct energy deposition, sheet lamination,
and binder jetting [4]. Lithography-based Ceramic Manufacturing (LCM)
is a stereolithographic method. Objects are 3D-printed layer by layer in a
bottom-up set-up from a printable slurry of zirconia powder and a resin
matrix [5]. The printer selectively exposes the zirconia-resin-slurry to
light at 460 nm wavelength to initiate solidification [6]. The photoactive

⁎
Correspondence to: Kerpener Strasse 32, 50931 Cologne, Germany.
E-mail address: Anja.Liebermann@uk-koeln.de (A. Liebermann).

https://doi.org/10.1016/j.dental.2023.05.005
Received 2 January 2023; Received in revised form 12 April 2023; Accepted 2 May 2023
0109-5641/© 2023 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.
A. Liebermann, A. Schultheis, F. Faber et al.
slurry ingredients consist of photoinitiators, inert dyes and inhibitors.
The photoinitiators form free radicals upon uptake of a UV photon and
initialize the chemical reaction [7]. The resulting “green bodies” are
subsequently fired in furnaces. Firing comprises (i) removal of the acrylic
binder (“debinding”) and (ii) sintering the zirconia to full density.
Compared to milled material, additively manufactured zirconia restora­
tions have been reported to show similar microstructure, biocompat­
ibility, flexural strength, and dimensional stability [8–10], but are not
currently approved as a material in patients [4,11].
For subtractively manufactured zirconia, the optical, mechanical,
and surface parameters are influenced by post-processing, such as
grinding, polishing, glazing, and heat treatment [12,13]. For additively
manufactured polymer-based materials, the cleaning methods after
printing have an impact on wear, biocompatibility, and mechanical
properties [14–18]. It was demonstrated, that cleaning protocols of 3D-
printed polymers vary widely in terms of length, mode (ultrasonic,
centrifugal, etc.), and solution (isopropanol, ethanol, etc.) [14–18].
Each manufacturer specifies different cleaning protocols for its specific
material [18]. The recommended cleaning protocols do not necessarily
achieve satisfactory results in terms of mechanical properties [14].
Most manufacturers recommend isopropanol as a suitable material for
cleaning polymer-based 3D-printed objects, which is why isopropanol is
considered the gold standard for cleaning [16,17].
For 3D-printed zirconia, it can be assumed that post-printing
cleaning affects the material properties. In the green state, a layer of
uncured resin is attached to the object surface and has to be removed
[7]. Thorough removal of this layer is important to achieve a high
geometric accuracy [14–16,19]. In addition, incomplete removal of
uncured material can affect subsequent firing by inducing crack for­
mation [7]. The cracking is caused by strains arising from the thermal
polymerization of residual monomer while heating [20]. For the 3D-
printed zirconia used in this investigation, the manufacturer deems
isopropanol to be too aggressive which may lead to unwished delami­
nations of cured layers during the cleaning process.
When aiming at the assessment of cleaning strategies on 3D-printed
zirconia objects, object dimensions (thickness and diameter), material
strength, optical properties and surface roughness appear valuable.
Flexural strength testing can accurately predict how well a ceramic
material can withstand mechanical stress in a clinical setting. Three
different test methods are approved to examine a ceramic material
[21]: the 3-point, 4-point, and biaxial flexural strength tests. Optical
properties are often analyzed by using a spectrophotometer to measure
the transmission and color values of a tooth-colored material. To test
surface properties, microscopes can be used to view the surface topo­
graphy and thus - or by means of profilometry - measure surface
roughness and roughness depth.
To the best of our knowledge, there is no available literature on the
impact of different post printing cleaning methods on optical, me­
chanical, and surface parameters of additively manufactured zirconia.
Furthermore, it has not been conclusively clarified which post-proces­
sing method is best suited for 3D-printed ceramics. Therefore, this
question is the basis of the present investigation.
The null hypotheses stated that different methods of post processing
cleaning have no impact on the geometry, transmission, roughness
parameters, and biaxial flexural strength.
Table 1
Overview of materials used including material, company, Lot. No., and composition.
Material Company Lot. No. Composition
LithaCon 3Y 210 Lithoz, Vienna, AB0722063 Light-curing resin matrix, 3 mol% yttrium stabilized zirconia (3-TZP): ceramic powder and additives;
Austria polymer content approx. 60 vol%
LithaSol 30®-Spray Lithoz, Vienna, EC0022060 Isopropanol + other components, exact composition unknown
Austria
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Dental Materials 39 (2023) 625–633
2. Materials and methods
2.1. Specimen fabrication
For testing, disc-shaped specimens (N = 100) were fabricated using
LCM technology. A printable 3 mol%-yttria-stabilized zirconia (3Y-TZP)
slurry (LithaCon 3Y 210, Lithoz, Vienna, Austria) was used. Disc di­
mensions were 1.2 × 12.4 mm (dimensions after sintering). The spe­
cimens were first designed (Design X Geomagic, 3D Systems, Rock Hill,
South Carolina, USA), and the resulting STL files were divided layer by
layer into the individual print layers. These layers corresponded to the
individual layers in which the printer cured the ceramic suspension and
created the green body (layer thickness = 25 µm). The suspension
(LithaCon 3Y 210®) consisted of light-polymerizing resin matrix, 3Y-
TZP ceramic powder and additives with a polymer content of ap­
proximately 60 vol%. All materials used are listed in Table 1.
The specimens were fabricated using one 3D printer (CeraFab 7500,
Lithoz, Vienna, Austria) with the following settings: DLP intensity =
55 mW/cm2; DLP energy = 70 mJ/cm2. The size of the build platform
was 76 mm × 43 mm. The maximum building height of the device was
170 mm. The specimens were nested perpendicularly to the build
platform. During the additive process, the printer pulls an automated
rake through the suspension to generate an even distribution of the
individual material components and to reduce sedimentation of the
ceramic particles.
2.2. Post printing cleaning
After 3D printing, the specimens were detached from the build
platform using a scalpel, and the support structures were removed. The
specimens were divided into five post printing cleaning (PPC) methods
(A-E) (N = 20):
1. PPC method A (control group): Cleaning using 25 s of airbrushing
with the dedicated cleaning solution (LithaSol 30® spray, Lithoz,
Vienna, Austria) and storage of one week in a 40 °C drying oven (U
26, Memmert, Schwabach, Germany) according to manufacturer's
instructions.
2. PPC method B: Cleaning by means of 25 s of airbrushing with
LithaSol 30® spray, without subsequent storage in the drying oven.
3. PPC method C: Cleaning by ultrasonic activation (Sonorex RK255,
BANDELIN electronic, Berlin, Germany) at a frequency of 35 kHz for
30 s. To this end, the samples were immersed into a glass filled with
LithaSol 30®, which was put into the ultrasonic bath.
4. PPC method D: Cleaning by ultrasonic activation (Sonorex RK255,
BANDELIN electronic, Berlin, Germany) at a frequency of 35 kHz for
300 s, while immersed into a glass filled with LithaSol 30®.
5. PPC method E: Cleaning by ultrasonic activation (Sonorex RK255,
BANDELIN electronic, Berlin, Germany) at a frequency of 35 kHz in
a glass with LithaSol 30® for 30 s. The samples were subsequently
airbrushed for 40 s with LithaSol 30®.
All post-processing procedures were performed at a constant air
humidity of 40 %. For application of the LithaSol 30® spray, a specially
manufactured cleaning station (CeraCleaning Station Ultra, Lithoz,
A. Liebermann, A. Schultheis, F. Faber et al. Dental Materials 39 (2023) 625–633

Table 2 2.3.3. Surface parameters - surface roughness (Ra) and roughness depth
Sintering protocol of additive manufactured zirconia used. (Rz)
Start temperature End temperature Heating rate Time
Microscopic overview images of the specimens were performed
[°C] [°C] [°C/min] [hh:mm] using a 3D digital microscope (VHX 5000, KEYENCE Corporation,
Osaka, Japan).
40 120 0.20 08:00 Surface roughness, on the other hand, was recorded digitally ac­
120 120 – 04:00
120 130 0.30 00:33
cording to DIN EN ISO 4287 with a 3D laser scanning microscope (VK-
130 130 – 02:00 X3100, KEYENCE Corporation, Osaka, Japan) using VK recording
130 140 0.45 00:22 module software (KEYENCE Corporation, Osaka, Japan; measuring
140 140 – 01:30 range: 4000 µm × 543.12 µm; used optics: CF IC EPI Plan ELWD 20x;
140 170 0.45 01:06
resolution: 505 nm; method: Sparrow-Criterion). Seven individual
170 170 – 02:00
170 200 0.50 01:00 images were acquired side by side at 20× magnification. These in­
200 200 – 04:00 dividual images were then combined by the software to form a pa­
200 250 0.56 01:30 noramic image. Subsequently, the images were evaluated in analysis
250 250 – 02:00 software (VK-X3000 MultiFileAnalyzer, KEYENCE Corporation, Osaka,
250 350 0.56 03:00
Japan). Three horizontal analysis lines perpendicular to the printing
350 600 1.00 04:10
600 1250 1.67 06:29 direction were drawn by means of a panoramic image and Ra and Rz
1250 1450 3.51 00:57 values were determined over these three lines. The surface condition is
1450 1450 – 02:00 represented by determining the arithmetic mean roughness Ra and
1450 25 4.07 05:00
maximum profile depth Rz.

Vienna, Austria) was used. This station allowed for air-brushing the 2.3.4. Biaxial flexural strength (BFS)
objects with the spray at five bar pressure and at a distance of 15 mm. The BFS was measured according to DIN EN ISO standard
When ultrasonic cleaning was performed, all specimens were 6872:2015 using a universal testing device (Z005, ZwickRoell, Ulm,
cleaned simultaneously to ensure a uniform time interval between re­ Germany) with a preload of 0.1 MPa. The load was applied by a cy­
moval from the building platform and cleaning in the ultrasonic bath. lindrical piston (plunger diameter: 1.2 mm) at a radius of 0.6 mm with a
This time interval, as well as the time interval between cleaning and cross-head speed of 1 mm/min. The specimens were positioned on three
debinding/sintering, was two hours in each case. There was only one balls (ball diameter: 3 mm, support radius: r1 = 5 mm). Polyethylene
exception: The interval between cleaning and transfer to the furnace foils were positioned both between the plunger and the specimen and
was extended to one week for method A. between the specimen and the balls (polyethylene foil thickness:
After cleaning and prior to firing, the specimens were air-dried, 50 µm). The die distance at start position was 1 mm. The force was
without any further drying methods such as additional compressed air. applied at the center of the specimens. The test was terminated at
For drying, all groups except group A, were stored on cellulose cloths. failure of the material by breakage of the specimen. The force cut-off
Group A was stored in polymer trays and dried in a drying oven. There threshold was reached at 50 % Fmax (maximum force). Simultaneously,
was no final curing as it is the case for 3D-printed objects made of the results were stored in software (testXpert®III version 1.4,
resins. Debinding, as well as sintering, was performed after the various ZwickRoell, Ulm, Germany).
cleaning methods for all specimens in a sintering furnace (HTCT 08/16, The biaxial flexural strengths in MPa were calculated using the
Nabertherm, Lilienthal, Germany) according to sintering protocol following formula:
(Table 2). No polishing of the surfaces was performed after sintering. (X Y)
= 0.2387 P
b2 (2)
2.3. Parameters analyzed with σ: maximum tensile stress in the center [MPa] and P: total force
[N] at fracture, and
2.3.1. Geometry 2 2
To investigate the dimensional accuracy, the thickness and the r2 (1 ) r2
X = (1 + ) ln +
diameter of the specimens were measured with a digital micrometer r3 2 r3 (3)
(MDC-Lite, Mitutoyo, Kawasaki, Japan). The thickness was determined
2 2
for three times at four measurement points. The diameter was recorded Y = (1 + ) 1 + ln
r1
+ (1 v)
r1
in two directions, again with three measurement repetitions each. The r3 r3 (4)
weight of the samples was documented using a high-precision balance
(MC1 Analytic AC 120 S, Sartorius AG, Goettingen, Germany). with ν: Poisson's ratio, r1: radius of the support circle [mm], r2: radius of
the loaded area [mm], r3: radius of the specimen [mm], and b: thickness
of the specimen [mm].
2.3.2. Transmission
The transmission was determined for all specimens using a UV-Vis 2.3.5. SEM analysis
spectrophotometer (Lambda 365+, PerkinElmer, Waltham, USA). The Qualitative analysis of the surface of the different groups for green
intensity of the light I0 and that of the light I radiated through the body and sintered state was performed by scanning electron microscopy
specimen between 400 and 700 nm were measured with a white (SEM; Amray 1610T, Bedford, MA, USA) after sputter coating (Agar
background and detected in the integrating sphere. The transmission T Sputter Coater, Agar Scientific LTD, Essex, Great Britain).
describes the wave intensity before the object and the wave intensity
after passing the object. It is defined as the quotient of both intensities: 2.3.6. Statistical analysis
Data were analyzed using SPSS 28 Statistics software (IBM, Armonk,
T = I/I0 (1)
New York, USA) at a significance level of p = 0.05. Normal distribution
(I: intensity of light as baseline without a specimen between 400 and was analyzed using Kolmogorov Smirnov test. For descriptive statistics,
700 nm; I0: light radiated through the specimen between 400 and mean values and standard deviations were calculated for the analyzed
700 nm). parametric parameters as well as median, minimum, maximum and

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Table 3
Descriptive statistics of geometry results including diameter, weight, and thickness of specimens with min (minimum), median, max (maximum), IQR (interquartile
range), mean and SD (standard deviation).

Cleaning Method/Parameter Min Median Max IQR Mean SD

Diameter [mm]
A 12.06 12.09a 12.14 0.025 – –
B 12.07 12.09a 12.13 0.023 – –
C 12.08 12.11b 12.13 0.020 – –
D 12.10 12.13b 12.15 0.025 – –
E 12.06 12.09a 12.18 0.020 – –
Weight [mm]
A – – – – 0.861b 0.003
B – – – – 0.858a 0.004
C – – – – 0.872c 0.004
D – – – – 0.869c 0.004
E – – – – 0.858a,b 0.004
Thickness [mm]
A – – – – 1.27b,c 0.005
B – – – – 1.27a,b 0.005
C – – – – 1.31d 0.018
D – – – – 1.28c 0.006
E – – – – 1.26a 0.008
abcd
superscript letters indicate significant differences between the groups tested.

interquartile range for non-parametric parameters. Statistical differ­
ences were calculated using t-test, Kruskal Wallis, and Mann-Whitney U
test. Characteristic strength with Weibull modulus m and Pearson cor­
relation was additionally analyzed.
3. Results
3.1. Geometry
3.3. Surface parameter – Ra and Rz
The Ra values of cleaning group E could be analyzed as significantly
lowest values (p ≤ 0.039), followed by groups A and B, which were in
the same value range (p = 0.172). The Ra values of cleaning group C
had the significantly highest values (p ≤ 0.025), followed by group D,
which also differed from groups A, B, and E (p < 0.001) (Table 5,
Fig. 1). For Rz, similar results were found (Table 5).

Mean thickness was similar (maximum mean difference: 20 µm) for the
groups A, B, D, and E. Group C was significantly thicker (about 40 µm mean
difference, p ≤ 0.009). For the parameter weight, similar results were
found. The mean weight was comparable for the groups A, B, and E. Group
C samples were significantly heavier (p ≤ 0.001), but not significantly
heavier than group D. For specimen diameter, the significantly lowest mean
values were measured for the groups A, B, and E (p ≤ 0.006). No differ­
ences were detected between these groups (p ≥ 0.357). For groups C and D,
the significantly highest diameter values could be measured (p ≤ 0.001),
showing no differences between C and D (p = 0.088) (Table 3).
3.4. Biaxial flexural strength (BFS)
Cleaning groups C and D showed the significantly lowest mean
strengths (p < 0.001), with both groups in the same range of values (p
= 0.760). Groups A, B, and E showed the significantly highest values
(p < 0.001) and were also in the same range of values (p ≥ 0.062).
Characteristic strengths and Weibull moduli are presented in Table 6
and Fig. 2.
3.5. SEM analysis

3.2. Transmission The SEM images revealed that significant surface deposits are visible
after the PPC procedure (green body and sintered state) of group C,
Within the transmission analysis, the significantly lowest transmis­ followed by group D. No deposits are visible in group E, which showed
sion values (p ≤ 0.010) could be analyzed for cleaning group A, fol­ the most homogeneous surface (Figs. 3 and 4).
lowed by groups B and C, which were within a value range (p = 0.496).
The significantly highest transmission values could be measured for Table 5
group E (p ≤ 0.004), followed by group D, whereas group D and group Descriptive statistics of surface parameters roughness and roughness depth with
B were in a value range (p = 0.070) (Table 4). However, since trans­ min (minimum), median, max (maximum), IQR (interquartile range) of sintered
mission of all groups ranged between 24.31 % and 24.67 %, differences stage.
between the groups were rather small. Cleaning Method/Parameter Min Median Max IQR

Table 4 Ra [µm]
Descriptive statistics of transmission values with mean and SD (standard de­ A 0.274 0.457b 0.805 0.139
viation). B 0.267 0.402b 0.752 0.151
C 0.379 0.738d 2.806 0.418
Cleaning Method/Parameter Mean SD D 0.346 0.586c 1.390 0.219
E 0.246 0.357a 0.797 0.066
Transmission [%] Rz [µm]
A 24.31a 0.07 A 2.094 3.32b 7.479 1.543
B 24.47b,c 0.08 B 2.268 3.23a,b 5.477 1.064
C 24.43b 0.13 C 2.672 5.56d 14.104 3.337
D 24.54c 0.05 D 2.834 4,66c 10.103 1.929
E 24.67d 0.06 E 1.965 2,75a 7.632 0.931
abcd abcd
superscript letters indicate significant differences between the groups superscript letters indicate significant differences between the groups
tested. tested.

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Fig. 1. Ra surface parameters (surface analysis) of all post printing cleaning protocol groups in sintered state.

Table 6
Descriptive statistics of biaxial flexural strength with min (minimum), median, max (maximum), IQR (interquartile range), as well as characteristic strength, and
Weibull modulus.

Cleaning Method/Parameter Min Median Max IQR Characteristic strength Weibull modulus

Biaxial flexural strength [MPa]

A 703.4 973.1b 1236.8 230.6 1029.9 8.22
B 771.9 1132.6b 1289.0 195.2 1165.4 9.77
C 141.4 308.7a 996.5 402.6 480.3 1.88
D 175.0 316.8a 1265.0 257.6 486.0 2.08
E 770.9 1093.4b 1392.6 214.4 1145.8 8.27
abcd
superscript letters indicate significant differences between the groups tested.

3.6. Correlations 4. Discussion

Data met Pearson correlation conditions. In the correlation calcu­
lations between the transmission and the thickness, a weak negative
correlation could be analyzed (Pearson correlation: −0.232). No
statement could be made for the roughness parameters (Pearson cor­
relation: −0.176).
The present investigation analyzed the effect of different PPC pro­
tocols on the geometry, transmission, roughness parameters, and
biaxial flexural strength of 3D-printed zirconia discs. For all outcome
parameters, significant effects were found. Therefore, the null hypoth­
esis could be rejected.

Fig. 2. Weibull analysis of all post printing cleaning protocol groups.

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Fig. 3. SEM images of all post printing cleaning protocol groups with 200x magnification (sintered state).

3D printing is projected to replace many traditional, subtractive
manufacturing methods in the mid-term future [22]. To guarantee
successful application in restorative dentistry, 3D-printed objects must
be geometrically accurate, strong and esthetical. On closer examination
of additively manufactured zirconia for dental applications, however,
fit and material quality have been discussed controversially: When it
comes to fit, Revilla-León et al. found clinically unacceptable marginal
and internal crown discrepancies at premolar crowns made from 3D-
printed zirconia [23,24]. In contrast, Lerner and co-workers concluded
that specifically LCM technology was able to guarantee the production
of precise zirconia crowns [25]. When it comes to material quality,
there are reports on a poorer reliability and processing defects with
strength relations measured with X-ray tomography [26,27], possibly
caused by internal voids and superficial delaminations. The present

Fig. 4. SEM images of all post printing cleaning protocol groups with 200x magnification (green body state).

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Fig. 5. Ra surface parameters (surface analysis) of all post printing cleaning protocol groups in green body state.

investigation contributes to the field of zirconia 3D printing by ad­ Nevertheless, ultrasonic activation must be applied carefully. A
dressing one potential source of such problems: inadequate cleaning, an short pulse of ultrasonic activation alone, as performed in group C, was
aspect which has not been addressed in detail before. ineffective. Remnants of unpolymerized slurry sticked to the objects
For the additive manufacturing process, post processing procedures (see Figs. 1, 3–5). The roughness consequently increased. In addition,
are necessary to clean the 3D-printed objects. This post processing is not unpolymerized slurry can cause stress during uncontrolled poly­
necessary after the subtractive manufacturing of zirconia restorations merization in the furnace [20]. In combination with an uneven force
or objects. The term post processing or post printing cleaning (PPC) is transmission during mechanical testing (by the uneven surface), the
often used as a synonym for the surface processing of the 3D-printed lowest strength values were found in group C.
objects. As already suspected in the introduction, this process showed a Longer-term ultrasonic activation (in group D) was overly ag­
significant impact on the measured parameters in the present in­ gressive and induced superficial damage to the objects, visible in in­
vestigation. Furthermore, it should not be underestimated that, apart ferior biaxial flexural strength as well as significant increase in rough­
from the various cleaning protocols, post-processing is performed ness parameter as compared to airbrush and combined methods.
manually and therefore tends to be error-prone [16]. The effect on the Microscopic images of the specimens in group C as well as group D
different parameters will be discussed in the following sections. showed marginal edge cracking in sintered stage, while no cracks were
Each cleaning strategy tested in this investigation had been applied visible in green body state (Fig. 6).
during our previous two years of LCM-zirconia fabrication as well as These results led to the conclusion that cleaning is most effective for
preclinical use and therefore correspond to the experience and further group B and E. In future processing, even shorter ultrasonic pulses
development of the 3D printer with the exception of the "Heidelberg" combined with air brushing seem promising – especially for hollow or
method. This PPC was included as a combination of the previous ex­ porous structures.
perience. All PPC were additionally developed together with the man­ In general, standard tests were performed to test the effect of the
ufacturing company Lithoz and should be tested for their efficacy. strategies. With regard to the geometry, a partially significant impact of
In principle, they can be divided into using airbrushing only, using the PPC procedures on the diameter, the weight and the thickness of the
ultrasonic activation only, and the combination of both. All strategies specimens was shown. Volumetric changes have already been described
relied exclusively on a special cleaning liquid (LithaSol 30®), which has
been developed for 3D-printed zirconia. This specific liquid contains
isopropanol to effectively dissolve the layer of excess slurry.
Simultaneously, additional undisclosed ingredients are added to pre­
vent delamination of the 3D-printed structures themselves. Green body
cleaning must, in essence, balance two aspects: on the one hand, the
slurry removal and on the other hand protection of the object.
The findings of the present investigation need to be discussed.
Different effects were seen in the individual cleaning groups: Group A
(airbrushing and heating oven) presented an effective cleaning strategy.
As storage at 40 °C for one week, however, did not bring any additional
benefits, it could be waived. Group B (airbrush only) and E (short ul­
trasonic pulse and subsequent airbrushing) can both be recommended
instead. The parameters material strength and surface roughness pre­
sented best results. Specimens´ thickness and weight was lowest in
group E, while transmission showed highest values. It is also ques­
tionable whether the ultrasonic bath can be omitted altogether, since
the results of B and E are in the same range. For this purpose, further
investigations must be carried out to see whether ultrasonic activation
brings advantages in cleaning power with hollow or porous test speci­ Fig. 6. Specimen overview of sintered state with visible marginal crack for­
mens. mation.

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A. Liebermann, A. Schultheis, F. Faber et al.
in the literature for additive manufactured zirconia, where the variation
was not due to different post processing, but to the porosity of the
material (0 %, 20 %, and 40 %). The best manufacturing accuracy was
found with the 40 % material [24]. The geometrical differences as well
as the surface roughness may also had an influence on other tested
parameters such as transmission, which represents a limitation of the
present investigation.
There were also significant differences within the transmission values,
with all values ranging from 24 % to 25 %, showing comparable trans­
mission to other conventionally milled zirconia, but always depending on
the thickness and the specific spectrophotometer used. The values, how­
ever, seem to be lower than the transmission values of the silicate ceramics
and thus can be compared with the results in literature [28,29].
For intraoral use, the roughness parameters also play a major role,
as they correlate with plaque accumulation. The roughness values
should be below 0.2 µm intraorally in order to counteract this accu­
mulation [30]. In the present investigation, all roughness parameters
were above the required values, but this could be attributed to the lack
of polishing of the specimens. Thus, comparisons are not meaningful.
The parameters of the present investigation should present which sur­
face exhibited the smoothest surface after the different PPC procedures
following the sintering process. These surfaces also show the least re­
sidues of the slurry and at the same time the best analyzed values of the
various parameters. At this point, a limitation of the used laser scanning
microscope measurement should be mentioned. The measuring range is
select by random on the surface of the specimen. Therefore, not all
possibly different profile areas can be displayed on the surface in total.
The measuring range is quite small and the selection can significantly
influence the measured values.
In addition, the roughness was also measured in three exemplary
green bodies (Ra: 0.339–1.394) and was hardly different from the
roughness of the sintered specimens and were therefore not included in
the final analysis, but only by means of SEM images.
Strength testing was performed in agreement with ISO 6872, using
the established pin-on-three-balls biaxial bending test. The disc-shaped
geometry of the specimens in biaxial flexural strength has a more rea­
listic surface to volume ratio. Thus, the disks simulate the geometry and
mechanical behaviors of the clinical restorations much better than the
bars of the 3-point and 4-point measurements [31]. As soon as an area
of the material weakened by defects is loaded during the measurement,
this can lead to premature fracture of the specimen and lower mea­
surement results [32]. This would not measure the actual intrinsic force
of the material, but the force at which the material fails due to surface
defects [32]. Compared to the 3-point and 4-point measurement, the
biaxial flexural strength test shows the highest measurement results for
ceramic materials, as well as for polymers [32,33].
There was one deviation from the ISO norm: No superficial polishing
was performed prior to loading. This could have led to two con­
sequences: First, the lack of polishing increased the surface roughness,
resulting in an unequal force transmission from pin to disc. This might
have decreased the strength values measured here. Second, superficial
defects to the discs (by handling defects) were not removed by pol­
ishing. This might have decreased material strength even further. Taken
together, polishing would certainly have increased material strength
throughout all groups. However, the effects of the respective cleaning
protocols would have been removed by polishing, therefore we decided
against polishing. Although polishing was avoided, the flexural strength
values retrieved in groups B and E were still comparable with those of
subtractively manufactured 3Y-TZP zirconia and were above 1100 MPa
[34,35]. Taken together, mean material strength of properly cleaned
and carefully fired 3D-printed zirconia is comparable to milled zirconia,
indicating its high potential for clinical use [26].
Weibull parameters were additionally calculated. The Weibull
method is the most common method in dentistry to statistically analyze
the variability of mechanical properties of ceramic materials [33]. This
method provides information about the reliability of the tested material
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Dental Materials 39 (2023) 625–633
[36]. The present results showed the highest reliability for the PPC
group B, followed by A and E. Still the reliability of milled material was
repeatedly found to be superior to that of 3D-printed zirconia [9,26].
This might be due to internal voids and pores in the 3D-printed material
compared to the industrially pre-fabricated blanks for milling. In future,
technological advances could further improve the material quality of
3D-printed zirconia.
In addition, sets of green bodies were investigated after cleaning.
The investigation of the green bodies should help to clarify the cause of
the cracking in groups C and D. It was noticeable that the green bodies
of each group showed no cracks. This leads to the assumption that the
cracks of groups C and D occur after sintering. Group E showed no
cracks both before and after sintering. Accordingly, the cracking cannot
be attributed to the ultrasonic activation, but is more likely a con­
sequence of the excessive surface tension due to the unproperly re­
moved residues. These residues were visible by microscope as puddles
at which significant height differences were measured by profilometry
(Figs. 1, 3–5).
Several study limitations need to be addressed. Only disc-shaped
objects were tested, no hollow or porous specimens. For these geome­
tries, cleaning becomes even more challenging and the use of ultrasonic
baths might become more relevant. Only limited statements can be
made, whether repeated short ultrasonic pulses might be helpful or
detrimental to such structures. Firing is a major factor in the zirconia
3D printing workflow. Only one standard program was applied here. It
would therefore be interesting to analyze the influence of the firing
parameter in combination with cleaning strategies in further in­
vestigations. It could be that a longer firing process led to fewer pro­
blems even with critical cleaning methods. Lastly, only one operator
performed the cleaning process for all samples. Inter-operator differ­
ences were not investigated, but should be addressed in follow-up in­
vestigations, as PPC is prone to execution errors.
5. Conclusion
Within the limitation of the present in vitro investigation, the fol­
lowing conclusions could be drawn:
1. PPC procedures B and E were most favorable with regard to the
parameter tested and can be recommended.
2. Short ultrasonic activation is ineffective, led to worst results, and
must be flanked by additional cleaning.
3. Longer ultrasonic pulses are detrimental to the object structure.
Acknowledgement
This study was supported by the Dietmar Hopp Foundation,
Germany, grant number 1DH1911472.
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