1. Introduction
Custom mouthguards provide protection for the stomatognathic system from the impact forces, maintaining adequate retention and comfort for its user [
1,
2,
3,
4,
5,
6]. Polymeric materials and polymeric films are, in the last decade, widely used in dentistry and in preventive and restorative therapies due to their mechanical and biological properties [
7,
8,
9]. There are various materials used in mouthguard fabrication: polyvinylacetate-polyethylene or poly(ethylene-co-vinyl acetate) (EVA copolymer), polyvinylchloride, latex rubber, acrylic resin, and polyurethane [
10,
11]. The main feature of this type of intraoral appliance is to dissipate impact forces and to separate the teeth from soft tissues in case of an injury, thus a material used in their fabrication should have high damping properties, flexibility, low hardness for ease of application, biocompatibility, low fluid sorption, and resistance for regular usage. EVA vacuum-formed custom mouthguards are currently the gold standard in the fabrication of protective splints [
12,
13,
14]. Unfortunately, there are problems with maintaining the correct dimensions of the final splint during thermoforming [
15,
16,
17,
18]. Many authors have described methods to prevent the thinning, but the problem remains unsolved [
15,
16,
18]. Currently, mouthguards may also be prepared using thermal injection or flasking using acrylate hybrid composites [
3,
6,
12,
19], but the materials and equipment used in such procedures are difficult to procure.
Digital techniques change the possibilities of the stomatognatic system rehabilitation [
20,
21]. The use of 3D-printing in mouthguard manufacturing could make it possible to design a single protective splint, which can be printed and duplicated while maintaining its dimensions [
22]. This is an important feature because intraorally used appliances should be replaced regularly due to hygiene issues [
4,
23,
24,
25,
26,
27]. Additionally, according to Kiatwarawut et al. [
28], standards for adequate cleaning of thermoplastic appliances still have to be established. There have been few promising studies published on this subject. Pinho et. al. [
29] compared the mechanical behaviour of multi-material samples that were produced using a double-nozzle 3D-printer. The best results were achieved using the ABS-TPU-ABS combination of materials due to the fact that they have the highest resilience value. Saunders et. al. [
30] assessed the energy dissipation of 3D-printable material (Arnitel ID 2045 Natural; DSM, Heerlen, The Netherlands), showing that the printed samples dissipated 25% more energy than EVA in both a medium and high strain rate. Liang et. al. [
31] proposed a 3D-printing wearable personalised oral delivery device in the form of a mouthguard using fused filament printing (FFF). This method is cheap and fast; however, the final products have a high porosity and an uneven surface [
32]. In view of problems with mouthguards’ microbiological contaminations [
33,
34,
35], it should be considered whether this method should be applied given the current level of printing accuracy. Mouthguards were also produced using computer-aided design and manufacturing (CAD/CAM) with polyetheretherketone (PEEK) [
36] or 3D-printing using photopolymerizable composite [
37].
In dentistry, a common method of 3D-printing is stereolithography (SLA), which gives highly accurate and smooth surfaces [
38,
39,
40]. This technique uses a scanning laser to build parts one layer at a time using light-cured photopolymer resin. The advantage of this method is the possibility to produce high-resolution objects and create complex shapes with undercuts, such as dental devices [
41,
42]. This technology also does not involve complex material preparation for the printable inks or complex post-treatment of printed appliances. However, the use of liquid resin makes the printing process slower than fused deposed modelling (FDM), in which the liquefied filament is extruded from a nozzle [
43]. The purpose of the conducted research was to evaluate the mechanical properties of materials for resin 3D-printing and to select a 3D-printing material with the most favourable physical properties for mouthguard fabrication. The null hypothesis of the analysis was that there are no statistical differences between the compared materials.
4. Discussion
The main feature of the mouthguard is its ability to absorb energy and reduce transmitted forces when impacted [
44]. Their performance depends on the material used, the thickness, and the inclusion of air cells [
7,
8,
12,
13,
19,
24,
47,
48]. According to the literature, the optimal thickness at the labial and buccal surface of a mouthguard should be 4 mm. The EVA material having a thickness of 3 mm transmits more than twice the force that passes through the 4 mm material when impacted with the same force [
47]. The shape of the product should provide adequate protection without excessive thickness, which may impair the stomatognathic system function [
49,
50]. The results of the current study show that the polymeric materials have properties that may be favourable in mouthguard fabrication. The high result achieved in the notch-toughness (3.90 ± 1.06 J/cm
2) and tensile strength test (4.65 ± 0.90 MPa) by the Keyortho IBT material means that it is best suited to absorb the impact energy of the tested samples. It had the lowest result of flexural strength among tested materials. However, none of the samples cracked during the test, and thus, it should not be considered a clinical disadvantage especially because, during usage, mouthguards are not subjected to significant deflections. Applied methodology has not previously been used in the literature for the comparison of mouthguard materials. The dimensions of samples were adjusted to imitate clinically used products—the minimum thickness of EVA providing favourable protective properties while ensuring comfort for a user is 3 mm [
51,
52,
53]. However, there are studies in which a different thickness was used; McNair et al. [
54] compared properties of 6 mm samples. ASTM F697-16 guidelines for design and use of mouthguards does not specify their thickness, only the area they should cover.
The physical properties of materials used in mouthguard fabrication have been previously studied by many authors. The shock absorption capacity, which can be defined as the reduction in impact energy of force transmitted through the mouthguard, was compared for different mouthguard materials [
7,
8,
12,
13,
19,
23,
24,
47,
55,
56,
57,
58]. The most common method used to evaluate this parameter was the pendulum or dropped weight, which directly impacted the samples of the material. The range of shock absorption differed depending on the thickness of the sample, the material used, and its chemical composition. In the current study, the applied methodology to calculate the energy absorption was a notch-toughness test, which makes previous results difficult to compare and can be considered a limitation of this research. In this method, the energy absorption is calculated in the presence of the flaw. The ideal surface of the protective splint should be flat and smooth. However, clinically, the occlusal surface of the mouthguard imitates the labial side of the incisors; therefore, it is never an ideal flat surface. Additionally, the elastic polymers used currently in mouthguard fabrication are shown to have cracks, roughness, and increased hardness after usage, so the real conditions in which mouthguards work are closer to the chosen research method [
35,
59,
60]. It would be beneficial to compare the achieved results with other methods used in the literature, such as impact force damping using a Charpy impact hammer. Further studies should also include the comparison of a new material to the current gold standard—poly(ethylene-co-vinyl acetate)—to directly compare its properties.
There is no uniformity in the methodology of compressive and tensile strength of mouthguards as described in the literature. The tear strength of mouthguard materials was determined in a study by Gould et al. [
46] based on the standard ASTM D624-0 measuring the force of a complete rupture of a sample. Jagger et al. [
61] used samples measuring 50 mm × 10 mm × 2 mm using modification of ASTM D-624 standard. Additionally, McNair et al. [
54] used the ASTM D624-00 standard in their research. Paradowska-Stolarz et al. [
20] conducted research comparing the compression and tensile modulus of two rigid resins used in 3D-printing using PN-EN ISO 604:2003 norm for axial compression test and PN-EN ISO 527-1-2019 for tensile test. The median tensile strength of the evaluated materials was between 2.17 ± 0.37 MPa for Formabs to 4.72 ± 0.47 MPa for Imprimo. This parameter was previously analyzed for different materials by Going et al. [
7]. The tensile strength of 25 mm EVA was between 3 to 20 MPa (mean 11 ± 5). However, they used different parameters and devices, so the achieved results are difficult to compare. The Tinius Olsen Tensile Tester was used according to the method of ASTM D638, samples had dimensions of 3 × 5 × 3/32 inches, and a strain rate was set at 10 inches a minute [
7].
Evaluated 3D-printable resins had the median Shore hardness between 81.09 ± 3.56 (Keyortho IBT) and 89.89 ± 1.22 (Imprimo). Similar results were previously published in studies evaluating the properties of mouthguard materials. Going et al. [
7] described that 25 mm EVA samples had the median hardness of 83 ± 4. According to Gawlak et al. [
12], the median hardness of the single 5 mm plate EVA material (Erkoflex, Erkodent, Pfalzgrafenweiler, Germany) was 74.25 (SD = 1.05), and the most recommended material due to its energy absorption properties, the pressure-injected vinyl polymer (Corflex Orthodontic, Pressing Dental, San Marino, San Marino), had 71.50 (SD = 1.79).
The median water sorption of tested polymers after one month was between 1.61 ± 0.15% for Keyortho IBT to 12.58 ± 0.32% for Formlabs. Previous studies showed that the result of the pressure-injected vinyl polymer was 0.072%, and a 5 mm plate of EVA was 0.134% [
9]. Going et al. [
7] showed a 0.13%–2.07% (mean 0.48 ± 0.37) of water sorption after 24 h incubation of 25 mm EVA samples. However, there is a significant difference in the applied methodology in those studies because the samples were weighed after 24 h of incubation. In the present study, we decided on one month of exposure to assess total sorption of tested materials. This approach may better characterise the behaviour of materials in long-term use. The 1.61% sorption of the Keyortho IBT samples after this period is clinically acceptable.
Most of the evaluated materials had a high percentage of solubility. The protective splint remains in the oral cavity environment during training and the influence of saliva cannot be omitted as mouthguards are mostly used during sports activities. With the increase in CO
2 in the blood owing to the increase in physical load, the pH of saliva decreases [
62]. Additionally, with the increase in oral cavity temperature, the material comes closer to the glass transition temperature (TG), leading to deformations at lower stress levels [
63,
64]. In the current study, the lowest median solubility was observed for Nexdent samples—0.29 ± 0.03%, and the highest for Formlabs—0.68 ± 0.04%. Despite the fact that the simplified in vitro test conducted is a limitation of the present study, it should be stated that due to the achieved results the durability and stability of the physical properties of tested materials should be further considered.
The main limitation of this study is that tested materials have not been compared with the most clinically used EVA due to the difficulty to prepare the same dimensions of samples. For the application in mouthguard formation, this material is bought in the form of plates, which are used for thermoforming. To verify whether tested materials have properties enabling their use in such an application, we decided not only to compare the achieved results with those published in the literature but also to compare the resins while paying special attention to the combination of properties that the mouthguard material should have. The introduction of indexes and the ranking of the results from each test was used to choose a material that may be used in further studies. However, subjectively attributed indexes may be considered a limitation of such methodology. During the 3D-printing process a polymer solution may be transformed into the 3D structure via crosslinking, which significantly influences the mechanical and physicochemical characteristics of the material [
65]. As the effect of crosslinking reactions is more pronounced on the extrusion-based bioprinting methods [
65], crosslinking of PMMA results in increased tensile strength, mechanical stability, elasticity, and solvent resistance [
66]. Further research should also consider the relation between the acrylate matrix of the material and overall performance.