Article 1

Water Sorption and Water Solubility of 3D-Printed and PMMA Den- 2

ture Base Materials, subjected to Artificial Aging – a comparative study 3

Mariya Dimitrova 1,*, Angelina Vlahova 1,2 , Ilian Hristov 1 , Rada Kazakova 1,2, Bozhana Chuchulska 1 and Stoyan 4
Kazakov 3 5

1 Department of Prosthetic Dentistry, Faculty of Dental Medicine, Medical University – Plovdiv, 4000 Plov- 6
div, Bulgaria; maria.dimitrova@mu-plovdiv.bg (M.D.); angelina.vlahova@mu-plovdiv.bg (A.V.); ilian.hris- 7
tov@mu-plovdiv.bg (I. H.); rada.kazakova@mu-plovdiv.bg (R.K.); bozhana.chuchulska@mu-plovdiv.bg (B. 8
C.); 9
2 CAD/CAM Center of Dental Medicine, Research Institute, Medical University – Plovdiv, 4000 Plovdiv, Bul- 10
garia 11
3 Oral Surgeon, Private Dental Practice – Sofia, 1000 Sofia, Bulgaria; kazakovstoyan@gmail.com (S.K.) 12
* Correspondence: maria.dimitrova@mu-plovdiv.bg; 13

Abstract: Background: This in-vitro study aimed to investigate and evaluate the values of water 14
sorption and water solubility of two types of denture base polymers – 3D-printed NextDent 3D 15
Denture + (NextDent, 3D Systems, The Netherlands) and the PMMA conventional Vertex BasiQ 20 16
(Vertex Dental, 3D Systems, The Netherlands), subjected to artificial aging. Materials and methods: 17
A total of 200 specimens were fabricated (n = 100) and have been dried to their optimal mass. They 18
were weighed to obtain optimally precise results, which was followed by immersion in artificial 19
saliva for a certain period (T1 = 7 days, T2 = 14 days, T3 = 1 month) and reading of the new mass of 20
the specimens after water absorption. Then the test samples were placed in a desiccator at a temper- 21
ature of 37 0 C for 24 hours and transferred into a second desiccator at a temperature of 23+/- 1 0 C 22
for 1 hour. Then they were weighed again, which was followed by a subjection to thermocycling for 23
100 hours (5000 cycles) between water baths of 5-55 o C and the water sorption and solubility were 24
measured again through the same procedures. The data was statistically analyzed, using IBM SPSS 25
Statistical Package Version 0.26. Results: The results showed that the direct correlation dependence 26
is visible not only between the obtained values for water sorption but the type of material as well. 27
Citation: Lastname, F.; Lastname, F.; The effects of thermocycling on water sorption varied depending on the material. Thermocycling 28
Lastname, F. Title. Materials, 2023, x, Vertex BasiQ 20 at an upper temperature of 55 o C significantly increased water sorption. Conclu- 29
x. https://doi.org/10.3390/xxxxx sions: The mean values for water sorption were higher for 3D-printed resin NextDent for all dura- 30
Academic Editor: Firstname Last- tions of the current study. The average values for water solubility gradually decrease over time, 31
name being the lowest for the 1-month (30-day) period for the test samples made of 3D-printed dental 32
resin. The direct correlation is evaluated between the values for the type of material and the water 33
Received: date
sorption as well, which is significant for the material’s dimensional properties. The artificial aging 34
Accepted: date
Published: date
had no effect on NextDent's water sorption. Thermocycling did not affect the solubility of the ma- 35
terials tested. 36
Publisher’s Note: MDPI stays neu-
tral with regard to jurisdictional
Keywords: 3D-printing; digital dentures; water sorption; water solubility; dimensional stability; re- 37
claims in published maps and institu-
movable dentures 38
tional affiliations.
39

Copyright: © 2023 by the authors. 1. Introduction 40

Submitted for possible open access
publication under the terms and con-
There are a variety of different dental resins, used nowadays for the fabricating of 41

ditions of the Creative Commons At-

tribution (CC BY) license (https://cre-
ativecommons.org/licenses/by/4.0/).
removable dentures [1]. Polymethyl methacrylate (PMMA) is the most preferred type of 42
dental acrylic, and it is used for the conventional technique of heat polymerization [2]. 43
With the development of modern technologies, three–dimensional (3D) printing enlarges 44
the possibilities for manufacturing removable dentures and saves a lot of the dentist’s and 45
dental technician’s time and effort [3]. This new method of additive manufacturing is 46

Materials 2023, 03, x. https://doi.org/10.3390/xxxxx www.mdpi.com/journal/materials

Materials 2023, 03, x FOR PEER REVIEW 2 of 21

based on stereolithography (SLA) and encompasses techniques that fabricate objects layer 47
by layer [4]. The properties of the CAD/CAM materials differ because of the purpose they 48
are dedicated to, and different physio-mechanical changes may occur during their use [5]. 49
Water sorption is the ability of dental materials to absorb liquids and change their 50
volume and weight. This is a physical and chemical process, which can be defined as a 51
phenomenon of fixation or capture of a gas or a vapor (sorbate) by a substance in a con- 52
densed state (solid or liquid) called sorbent [6]. Water solubility is a measure of the 53
amount of chemical substance that can dissolve in water at a specific temperature. Solu- 54
bility is generally expressed as the number of grams of solute in one liter of saturated 55
solution [6] . Denture base resins have low water solubility, which results from the leach- 56
ing out of unreacted monomer and soluble additives into the oral cavity. This undesired 57
property may cause soft tissue reactions [7]. 58
Dental resins must not change their dimensions over time and be resistant to volu- 59
metric changes under all conditions. The fitting of the denture base to the alveolar ridges 60
is significant for the retention of the removable denture [8]. Water sorption properties in- 61
evitably affect the volumetric changes of dental resins, which might lead to the aging of 62
the material and moreover might seriously affect the stability of the denture during mas- 63
ticatory function [9 ]. 64
Conventional denture base resin has better flexural strength, compared to 3D 65
printed, which showed superior surface roughness and lower hardness values than the 66
heat-cured materials for removable dentures [8]. 67
68
As the polymer material dries, the water is eliminated, and the polymer chains return 69
to their original position. If rewetting follows, the polymer chains expand again [10].In 70
this way, a cycle of micro excursions of the chains is created and microcracks appear be- 71
tween the individual macromolecules, which after mechanical loading can lead to fracture 72
of the removable denture [11, 12]. Saliva absorbed for one month leads to a linear expan- 73
sion of 0.03%, and after nine months - by 0.04% [13 ]. A decrease in moisture or the amount 74
of solvent in the atmosphere results in further drying of the materials. This process con- 75
tinues until a certain percentage of drying of the substance is achieved or until the desic- 76
cant is exhausted [14]. In addition to removing moisture from substances, solvents can 77
also be removed depending on the choice of the appropriate desiccant [15]. 78
According to the study by Perea - Lowery et al. [16] the water sorption of 3D-printed 79
plastics has a higher value compared to heat-polymerized ones. This could be related to 80
the polymerization process of conventional polymers, which takes place at a higher tem- 81
perature and for a longer period. Thus, it causes reduced water sorption, water solubility, 82
and residual monomer concentration, which has been demonstrated in several studies 83
[17]. In addition, differences in the chemical composition of 3D-printed and PMMA acryl- 84
ics for removable dentures must be considered, as the type of dental resin plays a signifi- 85
cant role in the level of water absorption and water solubility [18]. 86
In addition, the differences in the chemical composition of 3D-printed and heat-pol- 87
ymerized resin materials must be considered, since the chemical composition of the dental 88
resin played a role in its water sorption values [19]. 89
A very interesting aspect that occurs in literature lately is the material’s fractal di- 90
mension and texture analysis [20, 21]. These studies showed that the flexural strength of 91
the tested samples was lower for the single-unit restoration of hard tissue [22]. 92
Thermocycling is a laboratory technique for exposing dental materials to tempera- 93
ture ranges similar to those found in the oral cavity, which can have negative conse- 94
quences due to different coefficients of thermal expansion between the mucosa and the 95
tested materials [23]. Thermal cycling is considered to be one of the most severe thermal 96
environments. 97
The purpose of the current study was to evaluate the water sorption and the water 98
solubility of two types of denture base resins – 3D-printed dental resin and PMMA heat- 99
Materials 2023, 03, x FOR PEER REVIEW 3 of 21

polymerized conventional type of acrylic. In order to assess the influence of treatment and 100
storage conditions on the outcome variables the following hypothesis was tested: 101
H0—water sorption/water solubility and thermocycling will not significantly influ- 102
ence the dimensions and the mass of the two groups of test samples. 103
H1—water sorption/water solubility and thermocycling will significantly influence 104
the dimensions and the mass of the two groups of test samples. 105

2. Materials and Methods 106

For the aim of the current study, 200 samples were prepared in the shape of a par- 107
allelepiped with dimensions of 20 mm by 20 mm in width and length and respectively 3 108
mm in cross-sectional diameter, according to ISO standard (ISO 20795 1: 2013) [19]. The 109
shape and size of the test specimens were designed according to the predetermined crite- 110
ria using non-parametric software (Free CAD Version 0.19) and a .STL file was created for 111
this purpose. 112

113

114

115

Figure 1. 3D-model of the resin specimens with dimensions, using the software 3D-Viewer. 116

Two groups of specimens were manufactured, respectively - 100 pieces of each type 117
of dental resin. The first group of experimental samples was made from Vertex BasiQ 118
(Vertex Dental, 3D Systems, The Netherlands) heat-polymerizing acrylic by a conven- 119
tional flasking method. The second group of experimental bodies were made by the 3D 120
printing method from dental resin for removable dentures of NextDent Denture 3D+ 121
(NextDent, 3D Systems, The Netherlands). Figure 1 represents the planned shape of the 122
3D-model, which recreates the actual geometry of the test bodies. 123
Materials 2023, 03, x FOR PEER REVIEW 4 of 21

124
Figure 2. The 3D-printed test specimen 125
126
After the test samples have been dried to their optimal mass (Figure 2), they are 127
weighed using analytical balances with an accuracy of 0.0001 g. to obtain optimally pre- 128
cise results. This is followed by immersion in artificial saliva for certain period (T1 = 7 129
days, T2 = 14 days, T3 = 1 month) and reading of the new mass of the test bodies after 130
water absorption. 131
The test samples were placed on the porcelain tile in one of the desiccators. The des- 132
iccator (ISKO, Gupta Scientific & Glass Works, Haryana, India) was stored at a tempera- 133
ture of 37 0 C for 24 hours. Then the test samples were transferred directly into the second 134
desiccator, in which pre-dried silica gel was placed. The temperature conditions under 135
which the second desiccator was stored for 1 hour were 23+/- 1 0 C. In order not to disturb 136
the vacuum environment, it is of utmost importance that the desiccator is tightly sealed 137
during the test, except for the period necessary to remove and replace the test samples. 138
The same work cycle was repeated until a constant mass known as the conditioned 139
mass was reached, i.e. while the mass loss of each sample was less than 0.2 mg between 140
successive weighings. At this point, the volume (V) of each specimen was calculated, us- 141
ing the average of three length measurements and the average of five thickness measure- 142
ments. We took thickness measurements at the center of the specimen and at four equally 143
spaced points 1.5 mm from its periphery. The temperature storage conditions during the 144
measurements were at room temperature. 145
146
2.1. Water sorption 147
148
The water sorption value for each sample was expressed in micrograms per cubic 149
millimeter using the equation: 150

𝒎𝟐 – 𝒎𝟑 (1)
𝑾𝒔𝒑 =
𝑽
Equation 1. Water sorption equation. 151

Where: 152
Wsp – water sorption 153
Materials 2023, 03, x FOR PEER REVIEW 5 of 21

m2 – the mass of the test body after immersion in artificial saliva 154
m3 – the mass of the reconditioned experimental body in micrograms 155
V – the volume of the test sample 156
157
The samples were immersed in artificial saliva at 37 0 С for 7 days. After this period, 158
we removed the samples from the solution with polymer-coated tweezers and dried with 159
a clean dry cloth until no visible moisture remained. Then they were weighed for 60 sec- 160
onds immediately after removal from the artificial saliva and recorded the mass as m2. 161
This value represents the weight of the test body after liquid absorption. We similarly 162
applied the same methodology for the other two periods of the study - 14 days and 1 163
month. 164
After weight recovery, the test samples are conditioned to a constant mass in the des- 165
iccator under the conditions already described. The mass of the reconditioned samples 166
was referred to as m3. To obtain objective results, it is essential to apply the same condi- 167
tions as in the first drying process (temperature, time, etc.), using the same number of test 168
specimens and freshly dried silica gel. 169
170
2.2. Water solubility 171
172
To perform this task, the experimental setup from the first subtask was used. The test 173
specimens were placed in a desiccator containing dried silica gel, which was used to store 174
the plastic specimens for 24 hours at 37◦C (±1◦C). All test bodies were then placed in a 175
second desiccator for 1 h at 23◦C (±1◦C). They were then weighed using an analytical bal- 176
ance to the nearest 0.1 mg. The drying cycle is continuous until a constant mass (m1) is 177
obtained. 178
The dried test specimens were immersed for three different periods of time – 7 days, 179
14 days and 1 month at a temperature of 37◦C (±1◦C). After removing the plastic samples 180
from the containers, they were left outside for 60 min and dried with a clean paper towel 181
before being weighed again (m2). 182
The water solubility values of the test bodies were calculated using the ISO standard 183
formula. Data was statistically processed using IBM SPSS Statistics Version 26 software 184
program. 185
Water solubility was determined by the ratio of solute per unit volume exposed dur- 186
ing immersion expressed in micrograms per cubic millimeter for each test body using the 187
following formula: 188
189
190

𝒎𝟐 – 𝒎𝟑 (2)
𝑾𝒔𝒍 =
𝑽
191
192
Where: 193
Wsl – water solubility 194
m1 – the conditioned mass of the sample 195
m3 - the mass of the reconditioned experimental body 196
V – the volume of the experimental body 197
198
Means were statistically treated with one-way analysis of variance (ANOVA) fol- 199
lowed by Duncan's multiple range test to determine the significant difference between 200
groups at the p<0.05 level of significance. 201
202
2.3. Thermocycling 203
204
Materials 2023, 03, x FOR PEER REVIEW 6 of 21

Artificial aging was applied to the tested groups. Each group's samples were kept in 205
distilled water (37°C). Thermocycling was performed with 5000 cycles between 5° and 206
55°C (dwell time of 30 s). This procedure is equivalent to a five-year cycle of oral temper- 207
ature conditions. The obtained data were statistically analyzed (One-way ANOVA), and 208
the mean values were compared using the Tukey test ( α = 0.05). 209

3. Results 210
211
3.1. Water sorption 212
213
To statistically process the data obtained from the study, a statistical method for dis- 214
persion analysis was applied (One-Way ANOVA Analysis) for the three periods (confi- 215
dence interval α < 0.05), which aims to find out if there is a correlation between the type 216
of material and the measured values for water sorption (Diagram 1 ). 217

218

Vertex BasiQ 20 – water sorption values

1400

1200

1000

800

600

400

200

0
After 7 days After 14 days After 1 month

Minimal values Maximal values Mean Standard deviation

219

Diagram 1. Water sorption values for different time periods for Vertex BasiQ 20. 220

During a test comparing the obtained values for water sorption after 7 days with the 221
type of material, it was found that the obtained value for P is equal to 2.4789 * 10-17, which 222
is a much smaller value than α < 0.05. Therefore, there is a direct correlation between the 223
type of material and the water sorption values obtained (Diagram 2 ). 224
Materials 2023, 03, x FOR PEER REVIEW 7 of 21

NextDent Denture 3D+ - water soption values

2500

2000

1500

1000

500

0
After 7 days After 14 days After 1 month

Minimal values Maximal values Mean Standard deviation

225

Diagram 2. Water sorption values for different time periods for NextDent Denture 3D+. 226

When the statistical method was carried out analogously for a period of 14 days, in 227
which the obtained values for water sorption are compared with the type of material, it 228
was found that the obtained value for P is equal to 2.2082 * 10-11, which is a much smaller 229
value than α < 0.05. Therefore, we can conclude that there is a direct correlation between 230
the type of material and the obtained values for water sorption for a period after 14 days 231
( Diagram 3). 232

233

234

235

236

237

238

239

240

241

242
Materials 2023, 03, x FOR PEER REVIEW 8 of 21

ONE-WAY ANOVA – immersion in AS for a period of

14 days

380966.523
400000

350000
249217.722
249217.722
300000

250000

200000 131748.8
128.63
150000

100000
2.4817 1937.482
1 6
50000
69
0
In between the In the groups Total
groups

Sum of squares DF Mean of squares F P

243
Diagram 3. One-way ANOVA - Immersion in artificial saliva for a period of 14 days. 244

245
In a test comparing the obtained values for sorption after 1 month with the type of 246
material, it was found that the obtained value for P is equal to 5.3913* 10-28, which is much- 247
less than α < 0.05. Therefore, there is a direct relationship between the type of material and 248
the sorption values obtained (Diagram 4 ). 249
Materials 2023, 03, x FOR PEER REVIEW 9 of 21

ONE-WAY ANOVA – immersion in AS for a period of 1

month
989419.058
1000000
900000
800000
479605.248
700000
479605.248 509813.81
600000
500000
400000
63.971
300000
200000 68 7497.262
1 2.208211 69
100000
0
In between groups In the groups Total
Sum of squares DF Mean of squares F P
250

Diagram 4. ONE-WAY ANOVA - Immersion in artificial saliva for a period of 1 month. 251

252

The mean values for both studied materials are similar for the first 7 days of immersion in artificial 253
saliva, as shown in Diagram 5, with the heat-polymerized material exhibiting greater changes. In 254
both dental resins, there is an increase. For NextDent, the mean values for water sorption are the 255
highest after 1 month of immersion in artificial saliva. 256
Materials 2023, 03, x FOR PEER REVIEW 10 of 21

257
Diagram 5. Mean values of the water sorption for the two types of dental resin in the different 258
time periods. 259

260
The values for water sorption for Vertex BasiQ 20 were more consistent during the 261
three periods of time and there was a steady increase with the highest mean after 1 month. 262
263
3.2. Water solubility 264
To statistically process the data obtained from the conducted research, we chose 265
One-way ANOVA analysis. To determine whether the obtained water solubility values 266
have a correlation dependence with the type of material, we chose a confidence interval 267
= α < 0.05. The values for standard deviation and mean difference for both experimental 268
groups are presented in table 5 and 6. Decreased water solubility is indicated as a nega- 269
tive numerical value. 270
Materials 2023, 03, x FOR PEER REVIEW 11 of 21

NEXTDENT DENTURE 3D+ - WATER SOLUBILITY

VALUES

3.9911 27.2488 27.7762

AFTER 7 DAYS AFTER 14 DAYS AFTER 1 MONTH

-159.1667 -175
-26.75

-15.8333 -20
-1.6667
-51.2619 -62.4048
-4.5262

Minimum Maximum Mean Standard deviation

271
Diagram 6. Standard deviation values of NextDent 3D Denture+ for water solubility 272
273
274
275
Materials 2023, 03, x FOR PEER REVIEW 12 of 21

VERTEX BASIQ 20 – WATER SOLUBILITY VALUES

0.9854 10.6816 18.0598

AFTER 7 DAYS AFTER 14 DAYS AFTER 1 MONTH

-6.6667
-59.1667 -124.1667

-2.5
-12.5
-24.1667

-4.4286 -29.8095
-44.8524

Minimum Maximum Mean Standard deviation

276
Diagram 7. Standard deviation values of Vertex BasiQ 20 for water solubility 277
278
279
In the conducted test, comparing the obtained values for water solubility after a pe- 280
riod of 7 days with the type of material, we found that the value for P is equal to 0.889, 281
which is a much larger value than α < 0.05. Therefore, we can conclude that there is no 282
direct correlation between the type of material and the obtained water solubility values 283
(Diagram 8). 284
285
286
287
288
289
290
291
292
293
294
295
296
297
298
299
300
301
302
Materials 2023, 03, x FOR PEER REVIEW 13 of 21

ONE-WAY ANOVA - RESULTS AFTER 7 DAYS

8.45
69
68
0.889

0.02

0.167
574.61 574.777

0.167

IN BETWEEN THE IN THE GROUPS TOTAL

GROUPS

Sum of squares Degrees of freedom Mean of squares F P

303
Diagram 8. One-way ANOVA analysis results – after 7 days 304
305
As a result of the conducted statistical test, in which we compare the obtained values 306
for water solubility after 14 days with the type of material, it was found that the obtained 307
value for P is equal to 0.007, which is a smaller value than α < 0.05. Therefore, there is a 308
direct correlation between the type of material and the obtained water solubility values 309
(Diagram 9). 310
311
312
Materials 2023, 03, x FOR PEER REVIEW 14 of 21

ONE-WAY ANOVA - RESULTS AFTER 14 DAYS

69

68

253.788
0.007
23308.78
23.844
17257.579
6051.2
1

6051.2

IN BETWEEN IN THE TOTAL

THE GROUPS GROUPS

Sum of squares Degrees of freedom Mean of squares F P

313
Diagram 9. One-way ANOVA analysis results – after 14 days 314
315
316
For a period of 1 month after the test, comparing the obtained values for water solu- 317
bility with the type of material, it is proved that the obtained value for P is equal to 0.002, 318
which is a smaller value than α < 0.05. Therefore, we conclude that there is a direct corre- 319
lation between the type of material and the water solubility values obtained (Diagram 10). 320
321
Materials 2023, 03, x FOR PEER REVIEW 15 of 21

ONE-WAY ANOVA - RESULTS AFTER 1 MONTH

69

68

253.788
0.007
23308.78
23.844
17257.579
6051.2
1

6051.2

IN BETWEEN IN THE TOTAL

THE GROUPS GROUPS

Sum of squares Degrees of freedom Mean of squares F P

322
Diagram 10. One-way ANOVA analysis results – after 1 month 323
324
As a result of the processed statistical data, we can summarize that for a period of 7 325
days, there is no correlation between the period of stay of the materials in artificial saliva 326
and the type of the material itself. For the remaining periods, we observe that there is a 327
dependence between the type and the residence time of the materials in artificial saliva 328
and, accordingly, the degree of their water solubility. 329
A correlation dependence was established between the studied period of time and 330
the value of P, which progressively decreased with an increase in the stay of the materials 331
in artificial saliva (Diagram 11 ). 332
333
Materials 2023, 03, x FOR PEER REVIEW 16 of 21

334
335
Diagram 11. Average values for water solubility over three time periods 336
337
3.3. Thermocycling 338
339
A Tukey test was applied to compare each period before and after thermocycling 340
(control group – before thermocycling) (Diagram 12). All P values are equal to 0.05, con- 341
firming that the process of artificial aging is significant and a factor in the properties 342
changes of the test specimens. For the three immersion periods after thermocycling, the 343
values of the water sorption increased gradually in Vertex BasiQ 20. The process of artifi- 344
cial aging did not affect the values of NextDent. Thermocycling did not have an influence 345
on both tested groups' water solubility values. 346
Materials 2023, 03, x FOR PEER REVIEW 17 of 21

Tuckey Test - multiple comparisons

0.8

0.6

0.4

0.2

-0.2

-0.4

-0.6

-0.8
Control 7 days 14 days 30 days
group
Period Mean values Standard deviation Р Lower Upper

Diagram 12. Tukey test for multiple comparisons 347

4. Discussion 348
The findings show that both types of dental resin materials for removable dentures 349
meet the requirements regarding water sorption and water solubility given in the stand- 350
ard ISO 20795-1, measured according to a modified method, before and after thermocy- 351
cling [19]. 352
The study of Gad et al. investigated that the water sorption of 3D-printed resins in- 353
creased in comparison to the heat-polymerized resin [20]. The results showed that the 354
sorption of 3D-printed resins increased in comparison to the heat-polymerized resin. This 355
finding is similar to a previous study reporting that the sorption of 3D-printed acrylic 356
resins increased in comparison to pressed resin for occlusal devices [21, 22]. 357
According to ISO 20795, during the storage of the specimens, 32 µg/mm3 (water sorp- 358
tion) is the acceptable volumetric mass increase in denture base materials per volume [23]. 359
All water sorption values of the tested 3D-printed specimens were lower than the ISO 360
recommendation for maximum water sorption [24]. After calculation, the average value 361
for water sorption (1.0) was found to be lower than the requirements of ISO. The results 362
for the 3D-printed resin showed that they are suitable for clinical application [25]. How- 363
ever, further investigations are required to present the variations in water sorption be- 364
tween 3D-printed materials and conventional dental resins for removable dentures. 365
The findings of Vallittu et al. showed that the increased amount of water sorption 366
could be caused by the printed layering technique [26]. The absorbed water enters be- 367
tween the layers into the resin’s polymer, thus the interpolymeric spaces are filled with 368
water, which penetrates the empty spaces and voids, forcing the polymer chain away from 369
other chains [27, 28]. This theory was confirmed using the method of electron microscopy 370
Materials 2023, 03, x FOR PEER REVIEW 18 of 21

[29]. Water–polymer chain interactions may cause changes in the mechanical strength, 371
minor chemical degradation, and elution of residual monomers [30 - 32]. 372
The results of the current study showed that the water sorption of 3D-printed resins 373
increased in comparison to the conventional resin for removable dentures [36]. Water 374
sorption is a diffusion-controlled process, which occurs through penetration into empty 375
spaces such as micro-voids, or by a molecular interaction [37]. The degree of resin polarity 376
is of great importance for the progress of this process. As a result, water sorption is one of 377
the most remarkable properties while assessing denture base durability [38]. 378
In our study two groups of test samples of denture base polymers were investigated, 379
similar to the study of Bagheri et al. [39]. According to their investigation, [39], excessive 380
solubility of plastics for removable prosthetic structures can lead to surface deformations. 381
While the solubility of dimethacrylate-based polymers in various solutions has been ex- 382
tensively studied, to our knowledge, very little information is available regarding the sol- 383
ubility of 3D-printed plastics for the purposes of removable prosthetics [40]. 384
In the current research, the experimental specimens were subjected to different stor- 385
age conditions. The temperature in the first desiccator was 37 o C, while in the second it 386
decreased to 23+/- 1 o C. Then all test samples were measured by room temperature. Ac- 387
cording to the investigation of Silva et al. [41], all these changes could influence many of 388
the materials’ mechanical properties, such as fracture toughness and hardness of the pol- 389
ymers. 390
The average solubility values presented by the tested composite resins according to 391
ISO 4049 ranged from 2.3 to 4.2 µg/mm3; these values are lower than the maximum value 392
established by the ISO 4049 standard (<7.5 µg/mm3) [42 ]. The results of the study showed 393
that the solubilities of all materials in all solutions were acceptable to ISO 4049. This coin- 394
cides with the data obtained from our study on the solubility of the two types of plastics 395
for removable prosthetic restorations. 396
According to the study by Labban et al. [43 ], the bond density in methacrylate-based 397
resin composites can vary because of free radical polymerization, causing spatial hetero- 398
geneity that can facilitate the trapping of residual monomers from where they can be eas- 399
ily removed. Compared to the polymerization of methacrylate-based plastics, the photo- 400
activated cationic polymerization process of silorane resins is relatively insensitive to ox- 401
ygen. This not only reduces polymerization shrinkage but also increases the degree of 402
conversion [44, 45 ]. In their study, Petropoulou et al. [46 ], compared the water solubility 403
of four groups of experimental samples. As a result of the results obtained, it is concluded 404
that the reported solubility values are mainly influenced by the material characteristics 405
and the variations occurring between materials of the same type can be attributed to dif- 406
ferences in the composition of the polymer chains [47 – 49 ]. 407
In our research, the test samples were subjected to artificial aging, which provided 408
interesting results – the water solubility of Vertex BasiQ 20 increased significantly, while 409
NextDent was not affected at all. According to the study of Ghavami-Lahiji [50], the pro- 410
cess of thermocycling significantly decreased the hardness and the flexural strength of the 411
experimental bodies. Furthermore, in the study of Yap et al. [51], for all treatment groups, 412
the water solubility values of the experimental samples were not affected. 413
414
The limitations of the conducted study can be summarized in the following: 415
- because this experimental research provides such a high level of control, it can produce 416
results that are specific and relevant with consistency. It is possible to determine the 417
values of the water sorption and water solubility, making it possible to evaluate the 418
properties of the two types of dental resin in a much shorter amount of time compared 419
to other verification methods [50 ]. 420
- secondly, the data can be corrupted to seem like it is positive, but because the clinical 421
environment is so different from the controlled laboratory environment, positive re- 422
sults could never be achieved outside of the experimental research. 423
Materials 2023, 03, x FOR PEER REVIEW 19 of 21

- 424

5. Conclusions 425
From the obtained results, it could be summarized and concluded, that: 426
• The direct correlation dependence is visible not only between the obtained 427
values for water sorption but the type of material as well, which is signifi- 428
cant for the material’s dimensional properties. 429
• The imbibition of artificial saliva was higher with increasing the immersion 430
periods for both types of test samples. 431
• The mean difference values for water sorption were higher for 3D-printed 432
resin for removable dentures NextDent for all durations of the current 433
study.The average values for water solubility gradually decrease over time, 434
being the lowest for the 1-month (30-day) period for the test samples made 435
of 3D-printed dental resin. 436
• Thermocycling of Vertex BasiQ 20 at an upper temperature of 55 o C signif- 437
icantly increased the values of water sorption but had no effect on 438
NextDent's values. 439
• Thermocycling did not affect the water solubility of the materials tested. 440

List of Abbreviations 441

AS – artificial saliva 442
CAD/CAM – computer-aided design/computer-aided manufacturing 443
CD – complete dentures 444
ISO – International Organization of Standardization 445
PMMA – polymethyl methacrylate 446
STL – stereolithography, standard triangle language, standard tessellation language 447
3D – three-dimensional 448

Author Contributions: Conceptualization, M.D.; methodology, M.D., A.V.; software, I.H., A.V.; val- 449
idation, I.H., R.K.; formal analysis, B.C., S.K.; investigation, M.D., S.K.; resources, M.D., S.K.; data 450
curation, B.C., S.K.; writing—original draft preparation, M.D.; writing—review and editing, A.V., 451
I.H.; visualization, M.D.; supervision, B.C., R.K.; project administration, R.K.; funding acquisition, 452
R.K. All authors have read and agreed to the published version of the manuscript. 453

Funding: This research was funded by Medical University of Plovdiv, Bulgaria. 454

Institutional Review Board Statement: Not Applicable. 455

Informed Consent Statement: Not Applicable. 456

Acknowledgments: We are grateful for the support of Medical University of Plovdiv and the 457
CAD/CAM Center of Dental Medicine, Research Institute, Department of Prosthetic Dental Medi- 458
cine, Faculty of Dental Medicine, Medical University of Plovdiv, Bulgaria. 459

Data Availability Statement: Not Applicable.Conflicts of Interest: The authors declare no conflicts 460
of interest. 461

462

463

References 464

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