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RESEARCH AND EDUCATION

In vitro study on the influence of postpolymerization and


aging on the Martens parameters of 3D-printed
occlusal devices
Marcel Reymus, Dr med denta and Bogna Stawarczyk, Prof Dr Dipl-Ing (FH), MScb

Occlusal devices are used in ABSTRACT


dentistry to protect the teeth of
Statement of problem. Additive manufacturing has been proposed for the fabrication of occlusal
patients with habits including devices. However, information about the mechanical properties of additively manufactured devices
bruxism or tooth grinding from is lacking.
excessive occlusal wear and
Purpose. The purpose of this in vitro study was to evaluate the influence of the postpolymerization
forces1 and have been advo-
unit and artificial aging on the Martens hardness (HM) and indentation modulus (EIT) of different
cated for alleviating the 3D-printed materials in comparison with a conventionally milled material.
symptoms of temporoman-
dibular disorder.2 Additionally, Material and methods. Thirty disks (20 mm in diameter and 5 mm in thickness) were additively
manufactured (D20 II, Rapidshape & Form 2) for each 3D-printed material (NextDent Splint,
they can be used to test a new
Formlabs Dental LT Clear, and Freeprint Splint). As a control, 10 disks of the same thickness were
occlusal dimension in patients cut from a conventionally milled material (Temp Premium). Each specimen was measured for HM
requiring extensive prosthetic and EIT (ZHU 0,2) after fabrication. The specimens were stored in water at 37  C and measured
treatment.3 Traditionally, again after 2 and 4 weeks. The data were analyzed statistically by using the Kruskal-Wallis,
occlusal devices have been Mann-Whitney U, and Wilcoxon tests (adjusted by Bonferroni correction a=.05/27=.002).
manufactured by either vac- Results. The highest influence on HM parameters was shown by artificial aging (partial eta squared:
uum thermoforming, sprin- HM: hP2=0.840, EIT: hP2=0.855, P<.001), followed by the material (HM: hP2=0.690 EIT: hP2=0.845,
4
kling acrylic resin, or a P<.001) and the postpolymerization unit (HM: hP2=0.649, EIT: hP2=0.778, P<.001). Initial HM values
5 ,6 ranged from 147 ±8.11 N/mm2 for Formlabs postpolymerized in Otoflash to 89.5 ±8.55 N/mm2
combination of both. With
the advent of computer-aided for Detax postpolymerized in the Labolight unit. EIT values ranged from 3.92 ±0.061 kN/mm2 for
design and computer-aided Formlabs postpolymerized in Otoflash to 2.48 ±0.212 kN/mm2 for Detax postpolymerized in the
Labolight unit. In general, HM and EIT values decreased after water storage, whereas the values
manufacturing in dentistry,7 a remained unchanged for the control group.
digital approach to fabricating
occlusal devices has been Conclusions. HM parameters of additively manufactured occlusal devices depend on
postpolymerization strategy. Otoflash and Printbox result in higher HM and EIT values. The 3D-
introduced with a 3-step work-
printed materials are more prone to artificial aging than the control group, which brings into
flow: data acquisition, data question their long-term service. (J Prosthet Dent 2020;-:---)
processing, and manufacturing.
The patient’s data can either be acquired with an intraoral of the occlusal device8,9 and enables straightforward
scanner or indirectly with a conventional impression, later reprocessing of the file if the device needs replacement.
digitalized by using a laboratory scanner. Based on these The computer-aided manufacturing process can
data, the occlusal device can be digitally designed. This either be subtractive by using milling procedures or ad-
allows a more precise and efficient manufacturing process ditive by using 3D printing technology. The subtractive

a
Resident, Department of Conservative Dentistry and Periodontology, University Hospital, LMU Munich, Munich, Germany.
b
Professor, Department of Prosthetic Dentistry, University Hospital, LMU Munich, Munich, Germany.

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material’s behavior must be investigated after artificial


Clinical Implications aging.23,24 In general, the hardness values of resin-based
A correct postpolymerization strategy of additively materials is reduced after artificial aging,25,26 which is
mostly explained by water uptake. However, one study
manufactured occlusal devices is mandatory to
investigating direct restorative materials reported a rise in
achieve adequate mechanical properties. However,
hardness values after aging.27 Indentation tests
such fabricated devices might show inferior clinical
contribute to the understanding of a material’s defor-
performance in terms of service time than milled
mation28 and have been used to characterize mechanical
ones.
properties.29,30 The indentation modulus (EIT) is compa-
rable with the Young modulus and can be determined
simultaneously in a single measurement.17 Occlusal de-
method uses a blank of prefabricated material out of vices must possess some elastic behavior. If too brittle,
which the desired object is milled. This process wastes they will be susceptible to fracture during function. A
material,10 which is especially true for occlusal devices. previous study reported a decrease in flexural strength
Additive manufacturing (AM) builds up the object layer and flexural modulus after 14 days of water storage.31
by layer. Only the support structure, which stabilizes the The purpose of this in vitro study was to investigate
object during the manufacturing process, is discarded. the impact of the postpolymerization unit and artificial
AM is relatively new to dentistry and consists of different aging on the HM and EIT of different 3D-printed mate-
technologies,11 including resin processing devices and rials. The null hypothesis was that no differences would
metal and ceramic sintering devices. The use of AM to be found among the different materials, the different
produce an occlusal device was first described in 201312 postpolymerization units, or the aging levels regarding
and used stereolithography (SLA). SLA or digital light HM and EIT.
processing (DLP) are currently the most popular tech-
nologies for the manufacture of occlusal devices. Both
MATERIAL AND METHODS
technologies work with liquid resin that is either poly-
merized immediately with a laser (SLA) or on a large area The 3D-printed materials tested and the milled control
with a beam (DLP).13 Postpolymerization of the objects is (TP; Temp Premium, Zirkonzahn) are presented in
essential because the photosensitive resin is not Table 1. Thirty disks (20 mm in diameter and 5 mm in
completely polymerized during the printing process.14 thickness) of each of the 3D-printed materials were
However, manufacturers make their own recommenda- additively manufactured by using a DLP printer (D20II;
tions for a polymerization unit, making it difficult to re- Rapidshape) for NextDent Ortho (ND) and Freeprint
view the advantages and disadvantages of the different Splint (DX) and an SLA printer (Form 2; Formlabs) for
technologies. Formlabs Dental LT Clear (FL). For the control group, 10
Regardless of the manufacturing process, the material disks (N=120) of the same thickness were cut from pre-
used for an occlusal device must meet the mechanical re- fabricated blanks. The 3D-printed specimens were
quirements that enable its clinical use. Occlusal devices cleaned for 5 minutes in 96% ethanol (Otto Fischar
must resist occlusal forces of up to 770 N15 and the impact GmbH) in an ultrasonic bath (Sonorex Super RK1022;
of tooth grinding and clenching.16 Hardness is one mea- Bandelin) and subsequently postpolymerized. The post-
sure of evaluating the material’s ability to withstand such polymerization units tested are presented in Table 2. For
stress and resist scratching. Indentation measurements are each 3D-print material, 10 specimens were each post-
efficient in investigating surface properties which, in turn, polymerized in the 3 different units; no specimen was left
can be directly correlated with their morphology and unpolymerized. Subsequently, the specimens were
deformation behavior.17 Traditionally, Knoop or Vickers embedded in autopolymerizing acrylic resin (Scandi
hardness has been used, but they have disadvantages Quick A and B; ScanDia) and semiautomatically polished
including a dependence on test load, dwell times, and the (Tegramin-20; Struers) with consecutive silicon carbide
operator.18 Martens hardness (HM) has been proposed as papers up to P2000 under water cooling.
an improved test for dental materials.19 It is especially The HM and EIT of all specimens was measured
suitable for determining the elastic-plastic mechanical immediately after fabrication. Subsequently, all speci-
properties of one material.20 Such behavior is important for mens were stored in distilled water at 37  C in an incu-
occlusal devices; this is why Martens parameters were bator (HeraCell 150; Heraeus) and measured again after
investigated in the present study. One recent study also 14 and after 28 days. For each measurement, every
used hardness measurements to compare different mate- specimen was tested at 3 different locations (N=1080
rials for the manufacturing of occlusal devices.21 measurements). The parameters of HM were determined
Polymer networks react strongly in a wet environ- by using a universal testing machine (ZHU 0,2; Zwick).
ment22; therefore, for clinically relevant testing, the For this purpose, the specimens were loaded with a

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Table 1. Summary of materials, composition, manufacturers, and lot numbers


Materials Brands 3D Printer Composition Manufacturer Lot No.
3D-printed materials NextDent Ortho Clear [ND] D20II, Rapidshape Methacrylates NextDent XK044N01
Formlabs Dental LT Clear [FL] Form 2, Formlabs Methacrylates Formlabs FLDLCL01
Freeprint Splint [DX] D20II Rapidshape Methacrylates Detax 03709
Control Group Temp Premium [TP] Polymethylmethacrylates Zirkonzahn 9223

Table 2. Summary of postpolymerization units with corresponding technology, duration, wavelength, and manufacturers
Brands Technology Duration Wavelength Manufacturers
LC-3DPrint Box Ultraviolet light 30 min Range 315-550 nm, peaks at approximately 360 and 435 nm NextDent
Otoflash G171 Flashlight, nitrogen 2 processes of 2000 flashes Range 300-700 nm, peaks at approximately 480 and 530 nm NK Optik
atmosphere
Labolight DUO Light-emitting diode 2 processes of 3 min Range 380-510 nm, peaks at approximately 395 and 475 nm GC Europe

Vickers diamond indenter (a=136 degrees) with a force of Table 3. Mean and standard deviation of Martens hardness (HM in
9.8 N for 10 seconds. The minimum indenter depth was N/mm2) for materials for fabrication of occlusal devices, measured
always greater than 5 mm. HM and EIT were calculated directly after fabrication and after water storage in days (d)
Postpolymerization
with software (testX-pert V12.3 Master; Zwick) according Units ND FL DX TP
to the ISO specification32: Printbox
Initial 142 ±6.21c,ii 130 ±7.22b,ii 97.0 ±8.21a,ii 114 ±6.7
F
HM = ; 14 d 78.0 ±12.6a,iii 77.4 ±10.7a,ii 73.7 ±8.18a,iii 111 ±6.76
As ðhÞ
28 d 75.9 ±13.6b,i 64.8 ±8.92a,ii 74.6 ±4.64b,iii 112 ±6.34
Otoflash
where HM is in N/mm2, F (test force) in N, As (h)
Initial 140 ±4.30b,ii 147 ±8.11c,iii 99.5 ±2.41a,ii d
(surface area of the indenter at distance h from the tip) in
14 d 73.5 ±9.13b,ii 95.6 ±4.10c,iii 58.5 ±4.32a,ii d
mm2, h (indentation depth under applied test force) in
28 d 112.7 ±11.8b,ii 119 ±1.50c,iii 51.5 ±3.56a,ii d
mm, and Labolight
  −1 pffiffiffiffi Initial 109 ±4.66b,i 120 ±6.96c,i 89.5 ±8.55a,i
  1 1−v 2i p
d
EIT = 1 − v s ×
2
− with Er = pffiffiffiffiffiffi ;
a,i b,i
14 d 39.4 ±4.00 50.7 ±8.07 61.3 ±7.69c,i d
Er Ei 2C Ap 28 d 74.6 ±4.64b,i 81.4 ±10.9c,i 38.1 ±5.89a,i d

DX, Freeprint Splint; FL, Formlabs Dental LT Clear; ND, NextDent Ortho Clear; TP, Temp
where EIT (elastic modulus of the indenter) is in N/mm2, Premium. a,b,c describe significant differences between materials within one aging level
C (compliance of the contact), vs (Poisson ratio of the test and one polymerization unit. i,ii,iii describe significant differences between polymerization
units within one aging level and one material.
piece), and vi (Poisson ratio of the indenter) with vs=0.433
and vi=0.3.
For each measurement, the corresponding load- combinations of the 3 independent parameters (aging,
displacement curve was recorded. material, and postpolymerization unit) was also signifi-
The data were analyzed descriptively and globally by cant (P<.001, HM: hP2=0.473; EIT: hP2=0.402). Therefore,
using univariate analysis, and the Kolmogorov-Smirnov the data were analyzed separately according to the test
test was used to test the normal distribution. The sta- hypothesis.
tistical differences among the test groups were calculated In specimens postpolymerized by using Printbox, ND
by using nonparametric tests, including the Kruskal- reported the highest initial Martens parameters, followed
Wallis, Mann-Whitney U, and Wilcoxon tests by using by FL (P<.001). The lowest values were observed for DX
statistical software (IBM SPSS Statistics, v25; IBM Corp) (P<.001). After 28 days of water storage, however, DX
(adjusted by Bonferroni correction, a=.05/27=.002). presented the highest values with ND, whereas FL re-
ported the lowest (P<.001). For specimens post-
RESULTS
polymerized by using Otoflash, FL reported the highest
Descriptive statistics are represented in Tables 3 and 4 Martens parameters, regardless of the aging level, fol-
and in Figures 1 and 2. According to the univariate an- lowed by ND (P<.001) and DX (P<.001).
alyses, the highest influence on HM parameters was In specimens postpolymerized by using Labolight, FL
shown by artificial aging (partial eta squared: HM: reported the highest initial Martens parameters (P<.001),
hP2=0.840, EIT: hP2=0.855, P<.001), followed by material followed by ND, whereas DX presented the lowest values
(HM: hP2=0.690 EIT: hP2=0.845, P<.001) and post- (P<.001). After 14 days of water storage, however, DX
polymerization unit (HM: hP2=0.649, EIT: hP2=0.778, reported higher HM values than FL (P<.001) and ND
P<.001). The interaction effect of the trinary (P<.001).

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Table 4. Mean and standard deviation of indentation modulus (EIT in long-term mechanical stress such as tooth clenching. In
kN/mm2) for materials for fabrication of occlusal devices, measured contrast, additively manufactured occlusal devices might
directly after fabrication and after water storage in days (d) lose some precision of the functionally adjusted occlusal
Postpolymerization
Units ND FL DX TP
surface over time.
Printbox
The area between the loading and uploading curve
Initial 3.90 ±0.111c,iii 3.58 ±0.008b,ii 2.70 ±0.151a,ii 3.0 ±0.050 illustrates the permanent damage (Wp=1-hIT) that seems
14 d 2.66 ±0.228c,iii 2.50 ±0.232b,ii 2.01 ±0.195a,iii 2.90 ±0.001 to be dependent on the postpolymerization unit (Fig. 4).
28 d 2.49 ±0.293b,ii 2.15 ±0.210a,ii 2.19 ±0.096a,iii 2.90 ±0.046 After 2 weeks of water storage, TP revealed the lowest
Otoflash permanent damage and thus the highest elastic capacity.
Initial 3.82 ±0.089b,ii 3.92 ±0.061c,iii 2.78 ±0.041a,ii d DX postpolymerized in LC-3DPrint Box or Otoflash
14 d 2.53 ±0.167b,ii 2.94 ±0.081c,iii 1.77 ±0.103a,ii d G171 reported a similar property of permanent damage,
28 d 3.21 ±0.354b,iii 3.47 ±0.319c,iii 1.54 ±0.093a,ii d whereas after postpolymerization in Labolight DUO
Labolight (LL), it seemed to be the highest. Therefore, the choice of
Initial 3.23 ±0.092b,i 3.27 ±0.079c,i 2.48 ±0.212a,i d postpolymerization unit affects the desired viscoelastic
b,i b,i
14 d 1.60 ±0.079 1.64 ±0.138 1.56 ±0.199a,i d
behavior of the material and thus the deformation of the
28 d 2.19 ±0.096b,i 2.20 ±0.213b,i 0.950 ±0.146a,i d
occlusal devices in long-term use. Regarding artificial
DX, Freeprint Splint; FL, Formlabs Dental LT Clear; ND, NextDent Ortho Clear; TP, Temp aging, for the 3D-printed materials, creep as well as
Premium. a,b,c describe significant differences between materials within one aging level
and one polymerization unit. i,ii,iii describe significant differences between polymerization permanent damage seemed to increase after prolonged
units within one aging level and one material. storage time (Fig. 5). In contrast, the influence of artificial
aging seemed to be negligible for the control group, TP.
From a clinical point of view, this result favors milled
ND (P=.071) and DX (P=.160) reported no impact of
splints for long-term use.
postpolymerization unit on the initial HM values. The
Regarding the different 3D-printed materials, in gen-
lowest values were observed for the specimens post-
eral, the highest HM values were recorded for ND and FL,
polymerized by Labolight (P<.001).
followed by DX. The hardness of a material depends on
With respect to aging level, the initial measurements
its composition. For example, a higher filler content may
reported the highest values, regardless of the 3D-printed
lead to higher hardness. Because the manufacturers do
material and postpolymerization unit (P<.001). In gen-
not release the composition of the materials, it is difficult
eral, the values decreased with the increase in storage
to draw further conclusions from these results. In terms of
days. The exceptions were ND and FL, which were
patient safety and the potential for allergic reactions and
postpolymerized by using Otoflash or Labolight. In these
for further research projects, it would be desirable to
groups, the specimens reported higher values after 28
determine the composition of the different 3D-printed
days of water storage than after 14 days of storage
materials. The milling material TP is promoted by the
(P<.001). The control group reported no differences
manufacturer as a material for the fabrication of trans-
compared with 3D-printed specimens, and no impact of
parent occlusal devices or for long-term tooth colored
aging level was observed.
interim fixed dental protheses. This indication might
explain why TP reported higher HM and EIT values than
DISCUSSION
other milling materials, which are solely formulated for
This study demonstrated the impact of postpolymeriza- occlusal devices. Studies on the mechanical properties of
tion and water storage on the HM and EIT of different 3D-printed materials are scarce. To the authors’ knowl-
3D-printed materials for the fabrication of occlusal de- edge only the Prpic et al21 study is comparable with the
vices. Consequently, the null hypothesis was rejected. present investigation. They investigated the hardness and
All tested materials exhibited elastic-plastic behavior. flexural strength of conventional, 3D-printed, and milled
Their corresponding load-displacement curves revealed materials for the fabrication of occlusal devices. Hardness
different characteristics, which seem to be influenced by was measured after water storage of 50 hours by using the
the material itself, the postpolymerization unit, and Brinell method. The highest hardness was recorded for 1
artificial aging (Fig. 3). The curve peak plateau indicated milled material and 2 conventional materials, followed by
the materials’ creep characteristic under indentation load. 1 3D-printed material. The recorded values of the CSP
The plateau of the control group’s curve tended to be and ORR range are consistent with the corresponding
narrower than those of the 3D print materials, which materials in the present study.
illustrated a lower creep characteristic (Fig. 3). Regarding Devices manufactured by SLA require an appropriate
the creep properties of the 3D-printed materials, ND and posttreatment procedure to produce the mechanical
FL seemed to behave similarly, whereas DX displayed a properties suitable for service in the oral cavity. Post-
longer plateau and thus a higher creep tendency. polymerization of 3D-printed occlusal devices is essential
Consequently, TP was less prone to deformation from because the materials are resin based. The influence of

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Material
ND FL DX

150
125

Printbox
100
75
50
25

150

Polymerization
125

Otoflash
100
HM

75
50
25

150
125

Labolight
100
75
50
25
Initial 14 d 28 d Initial 14 d 28 d Initial 14 d 28 d
Storage
Figure 1. Box plots of HM values (N/mm2) for different 3D-printed materials and different aging levels. FL, Formlabs Dental LT Clear; ND, NextDent
Ortho Clear; DX, Freeprint Splint; HM, Martens hardness.

the postpolymerization unit on hardness was apparent in and pressure made its polymer network more resistant
the present study. In general, specimens post- against degeneration in an aqueous solution. The HM
polymerized in the Printbox or the Otoflash unit had values for ND and FL increased between the aging levels
higher HM values than those postpolymerized in the of 14 days and 28 days but solely after postpolymeriza-
Labolight unit. This was true for each material and each tion in the Otoflash or the Labolight unit. A possible
storage time. That fact might be explained by the light explanation might be that continued polymerization
source of the postpolymerization Labolight unit (light- occurred during the artificial aging in heated water after
emitting diode) and the correlation between hardness the initial water uptake. Such behavior has been reported
and degree of conversion. It seems likely that LL pro- for direct composite resin materials.21 The post-
duced a lower degree of conversion than the other units. polymerization time in the Printbox was the longest for
A possible explanation might be that the emitting energy all the units (30 minutes). After such a long post-
or the wavelength of LL’s light source was not well polymerization period, it might be that there were no
adapted to the 3D-printed materials. more residual C=C double links within the specimens for
During their service time, occlusal devices are exposed later polymerization to occur. The missing occurrence of
to 100% humidity. The artificial aging protocol in this the phenomenon for DX might be explained by the
study aimed to simulate the condition in the oral cavity material’s composition and chemistry, which, again, is
and to investigate its impact on the properties of the not stated by the manufacturer.
materials. In general, a drop in HM values was recorded In contrast with milled materials, which are industri-
with prolonged storage time for 3D-printed materials. ally prefabricated, additively manufactured objects can be
This result is consistent with those of studies of resin- adversely affected by a range of parameters, including
based materials19,20 and might be explained by water their position on the printer platform, the postprocessing
uptake. The control group, TP, however, seems to have method, and the postpolymerization strategy. This might
been unaffected by the selected aging protocol, possibly explain why an abnormal distribution of the data was
because its industrial fabrication under high temperature recorded.

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Material
ND FL DX
5

Printbox
3

Polymerization
4

Otoflash
3
Eit

Labolight
3

0
Initial 14 d 28 d Initial 14 d 28 d Initial 14 d 28 d
Storage
Figure 2. Box plots of EIT values (in kN/mm2) for different 3D-printed materials and different aging levels. FL, Formlabs Dental LT Clear; ND, NextDent
Ortho Clear; DX, Freeprint Splint. EIT, indentation modulus.

12 12

a b c d a b c d
10 10

8 8
Force [N]

Force [N]

6 6

4 4

2 2

0 0
0 20 40 60 0 20 40 60 80 100
µm]
Indentation [µ µm]
Indentation [µ
Figure 3. Load displacement curves of FL (a), ND (b), TP (c), and DX (d), Figure 4. Load displacement curves of TP (a), ND postpolymerized in
all 3D print materials postpolymerized in Otoflash. FL, Formlabs Dental Printbox (b), ND postpolymerized in Otoflash (c), and ND
LT Clear; ND, NextDent Ortho Clear; TP, Temp Premium; DX, Freeprint postpolymerized in Labolight (d) after 2 weeks of water storage.
Splint. TP, Temp Premium; ND, NextDent Ortho Clear.

In general, the EIT values behaved similarly to the HM result is consistent with that of a previous study25 and
values; that is, the elastic properties of the 3D-printed limits the long-term use of additively manufactured
materials decreased with prolonged water storage. This occlusal devices. They seem to become brittle over time

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