journal of prosthodontic research 62 (2018) 65–74

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Journal of Prosthodontic Research

journal homepage: www.elsevier.com/locate/jpor

Original article

Does artificial aging affect mechanical properties of CAD/CAM

composite materials$
Ferhan Egilmeza,* , Gulfem Erguna , Isil Cekic-Nagasa , Pekka K. Vallittub ,
Lippo V.J. Lassilac,d
a
Gazi University Faculty of Dentistry, Department of Prosthodontics, Ankara, Turkiye
b
Institute of Dentistry, Department of Biomaterials Science and Turku Clinical Biomaterials Centre — TCBC, University of Turku and City of Turku,
Welfare Division, Turku, Finland
c
Institute of Dentistry, Department of Biomaterials Science and Turku Clinical Biomaterials Centre — TCBC, Finland
d
Turku University of Applied Sciences, Turku, Finland

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

Article history: Purpose: The purpose of this study was to determine the flexural strength and Weibull characteristics of
Received 15 February 2017 different CAD/CAM materials after different in vitro aging conditions.
Received in revised form 12 May 2017 Methods: The specimens were randomly assigned to one of the six in vitro aging conditions: (1) water
Accepted 1 June 2017
storage (37
C, 3 weeks), (2) boiling water (24 h), (3) hydrochloric acid exposure (pH: 1.2, 24 h), (4)
Available online 21 June 2017
autoclave treatment (134
C, 200 kPa, 12 h), (5) thermal cycling (5000 times, 5–55
C), (6) cyclic loading
(100N, 50,000 cycles). No treatment was applied to the specimens in control group. Three-point bending
Keywords:
test was used for the calculation of flexural strength. The reliability of the strength was assessed by
CAD/CAM blocks
In vitro aging
Weibull distribution. Surface roughness and topography was examined by coherence scanning
Flexural strength interferometry. Evaluated parameters were compared using the Kruskall–Wallis or Mann–Whitney U
test.
Results: Water storage, autoclave treatment and thermal cycling significantly decreased the flexural
strength of all materials (p < 0.05), whereas HCl exposure or cyclic loading did not affect the properties
(p > 0.05). Weibull moduli of CerasmartTM and LavaTM Ultimate were similar with control. Vita Enamic1
exhibited similar Weibull moduli in all aging groups except the HCl treated group (p > 0.05). Ra values of
CerasmartTM and LavaTM Ultimate were in the range of 0.053–0.088 mm in the aged groups. However Ra
results of Vita Enamic1 were larger than 0.2 mm.
Conclusions: Flexural strength of newly developed restorative CAD/CAM materials was significantly
decreased by artificial aging. Cyclic loading or HCl exposure does not affect to the flexural strength and
structural reliability of CerasmartTM and LavaTM Ultimate.
© 2017 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

1. Introduction fabrication of dental devices by CAD/CAM have increased in

number remarkably [2].
Rapid evolution of computer-aided design and computer-aided Resin-based composites and ceramics are the two main groups
manufacturing (CAD/CAM) systems has dramatically enhanced of dental restorative materials [3]. On one side, several advantages
prosthetic and restorative dentistry by providing advances in of ceramic restorations were demonstrated such as wear resis-
manufacturing technologies [1]. New dental materials for the tance, highly aesthetic appearance, biocompatibility, and color
stability [4]. On the other side, ceramic restorations may cause
excessive wear to opposing dentition [4]. Additionally, their
drawbacks include brittleness and susceptibility to fracture due
$
This study was partly presented as an oral presentation at the 22nd to the formation of flaws or defects in the intaglio surfaces [4,5].
International Scientific Congress of Turkish Prosthodontics and Implantology Conversely, resin-based composites are known with their superior
Association, Antalya-Turkiye, on 11–15 November 2015.
* Corresponding author at: Mutlukent Mah, 10. Cadde 2065. Sk. No:15, Beysukent,
aesthetics, ease of milling, simple intraoral repair techniques and
Ankara, Turkey. Fax: +90 312 223 92 26. less abrasive effect toward opposing dentition due to their yielding
E-mail addresses: [email protected], [email protected] (F. Egilmez). structure [6]. However, there are concerns about resin-based

http://dx.doi.org/10.1016/j.jpor.2017.06.001
1883-1958/© 2017 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.
66 F. Egilmez et al. / journal of prosthodontic research 62 (2018) 65–74

composites may elicit allergic reactions both in dental personnel imperfecta or microdontia and is especially suitable for patients
and in patients [7]. Several studies investigated the biocompati- still undergoing growth [23] or patients with dental erosion or
bility of these materials show that they have cytotoxic potential in bruxism [24,25]. Also noteworthy is the documented de-bonding
direct contact with cells [8–11]. Additionally, mechanical proper- at a higher than originally anticipated rate of Lava Ultimate (3M
ties, e.g. flexural strength, hardness and flexural modulus of ESPE) composite blocks, having forced the manufacturer to no
resin-based materials are still inferior to those of ceramics [12,13]. longer support the indication to fabricate complete coverage
Considerable progress has been made in composite resin crown restorations [26]. Throughout this perspective, in the
industry with the invention of nanohybrid and nanofilled resin absence of long-term clinical data, clinicians must be cautious in
composites. At the same time, advanced materials that combine specifying the indications for these new materials.
the advantages of composite and ceramic materials have been To date, biomechanical behavior characteristics of resin-based
introduced to the dental community. A CAD/CAM restorative composite CAD/CAM materials have not yet been extensively
material was developed as a polymer-infiltrated-ceramic-network studied. Thus, the objective of this study was to determine the
material in the recent past [5]. This material was called as double flexural strength and Weibull characteristics of resin, hybrid
network hybrid ceramic that has a polymeric second phase with a nano-ceramic and polymer infiltrated ceramic dental
lower modulus of elasticity into ceramic networks [5,14]. The materials after different in vitro aging conditions. The null
manufacturer stated that the mass percentage of the organic hypothesis was that there would be no difference in their
polymer part is 14 wt% and the inorganic ceramic part is 86 wt%. biomechanical characteristics amongst the tested materials after
Accordingly, ceramic network creates the basic structure and aging procedures.
provides stability of the material while polymeric network
contributes the elasticity [5]. As well as hybrid ceramics, 2. Material and methods
CAD/CAM composites with nanohybrid structures based on
nanotechnology with inorganic ceramic fillers have been 2.1. Specimen preparation
developed [14]. These materials contain micro, hybrid and nano
fillers with different sizes including silica fillers nanomers (20 nm), Hybrid and nano CAD/CAM composite blocks (GC CerasmartTM
nanocluster particles derived from the fillers (0.6–10 mm), zirconia A1-LT, LavaTM Ultimate Restorative Resin Nano Ceramic A1–LT and
fillers (4–11 nm) and/or barium glass fillers (300 nm) and resin Vita Enamic1 1M1-T standard translucency for Sirona Cerec AC
matrix [14–16]. Different dimethacrylate thermosets such as System) were selected for the study (Table 1).
ethoxylated bisphenol-A dimethacrylate (BisEMA), ethylene glycol The CAD/CAM blocks were sectioned with a precision cutting
dimethacrylate (EGDMA), bisphenol-A-diglycidyl methacrylate machine (Isomet 1000, Buehler, Lake Bluff, USA), polished with
(BisGMA), urethane dimethacrylate (UDMA), and further metallographic SiC papers (600, 800 and 1200-grit; Federation of
dimethacrylate are in the composition of resin matrix [16]. European Producers of Abrasives) to the final dimension (1.5 mm
Besides to the variations in structure and filler contents, nano  4 mm  17 mm). A total of 315 specimens were fabricated
particle filled resin CAD/CAM composites were shown to have (n = 15 per group) and subsequently cleaned in distilled water
higher flexural strengths than the polymer-infiltrated-ceramic- for 10 min by an ultrasonic device (Quantrex 90, L&R Ultrasonics,
network material and leucite ceramic, but lower than lithium Kearny, NJ) and air dried. Then, they were assigned randomly into
disilicate ceramic [17]. 7 groups. No treatment was provided to the specimens in control
Moreover, differences among these materials with regard to the group.
filler composition and matrix-filler coupling chemistry may
account for different mechanical performances and may further 2.2. In vitro aging procedures
account for differences in the materials’ resistance to mechanical
and chemical degradation [18]. Furthermore, it has been shown 2.2.1. Water storage
previously that, surface roughness increased after accelerated Fifteen specimens from each material were put into plastic
aging [19]. It was implied that the increased roughness of resin containers and 40 ml deionized distilled water was added into the
structured dental materials may foster plaque accumulation on the tubes. Then the tubes were placed into the incubator at 37
C for
restoration surface, that results from surface deterioration due to 21 days. This group was assigned as “Group WS”.
the degradation of resin matrix [20]. Therefore, roughness and
surface analyses become more important especially after aging 2.2.2. Boiling in water
conditions. The specimens in “Group BW” were aged in boiling deionized
Clinical studies have shown that resin-based composite distilled water for 24 h. For this purpose, the specimens were put
CAD/CAM restorative materials could be used as full-coverage into glass bottles with 40 ml distilled water and their caps were
crowns [21] or posterior occlusal veneers [22] and are a viable tightened. Then the bottles were placed into a heating oven at
long-term treatment option for teeth with amelogenesis 100
C for 24 h.

Table 1
Tested materials, their compositions, tested conditions and group codes.

CAD/CAM material Material code Manufacturers Shade-lot # Composition

GC CerasmartTM CS GC Dental Products Europe, Leuven, Belgium A1-HT 1412161 Composite resin material (BisMEPP, UDMA, DMA) with
71 wt% silica and barium glass nanoparticles

LavaTMUltimate LU 3M ESPE, Seefeld, Germany A1-HT N590540 Composite resin material (BisGMA, UDMA, BisEMA,
TEGDMA) with 80 wt% silica and zirconia nanoparticles and
zirconia/silica nanoclusters

Vita Enamic1 VE VITA Zahnfabrik, Bad Säckingen, Germany 1M1-T 37010 Polymer-infiltrated-feldspatic ceramic-network material
(UDMA, TEGDMA) with 86 wt% ceramic

BisGMA: bisphenol A diglycidylether dimethacrylate; UDMA: urethane dimethacrylate; BisEMA: ethoxylated bisphenol A dimethacrylate; TEGDMA: triethylene glycol
dimethacrylate; BisMEPP: 2,2-bis(4-methyacryloxypolyethoxyphenyl)propane; DMA: dodecyl dimethacrylate.
 F. Egilmez et al. / journal of prosthodontic research 62 (2018) 65–74 67

2.2.3. Acid exposure The uniaxial flexural strength [modulus of rupture (s )] were
The specimens in “Group HCl” were exposed to hydrochloric then calculated by using he following formula [28]:
acid (HCl, pH = 1.2), shown previously to cause erosive lesions in
3Wl
enamel similar to those seen clinically [27]. 90 ml, 0.113 wt% HCl s¼ 2
solution in deionized distilled water was prepared. A pHS-3C 2bd
digital pH meter (Hangzhou Dongxing Instrument Works, where W stands for breaking load (N); l is the span length (mm); b
Hangzhou, China) was used to measure the pH value of the HCl is the width of each specimen (mm) and d is the and thickness of
solution. the specimen (mm).
The specimens were placed into glass bottles, 30 ml HCl
solutions were added to each bottle and their caps were tightened.
2.5. Surface analysis with scanning electron microscopy (SEM)
Then the containers were incubated at 37
C under constant slow
agitation using an orbital shaking thermostated bath (Grant OLS
For surface morphology assessments, two fractured specimens
200, Grant Instruments Cambridge Ltd., Shepreth, UK) for 24 h.
from each tested group were randomly selected following flexural
strength test and examined by scanning electron microscopy
2.2.4. Autoclave treatment
(SEM) (JSM-5500LV; JEOL, Tokyo, Japan) at 15 kV and 20 mm
For thermal degradation test, specimens in “Group A” were
working distance. Briefly, the specimens were mounted in
stored in an autoclave (Cisa S.p.A., Pomezia, Rome, Italy) at 134
C
aluminum stubs and dehydrated over night under vacuum in a
under additional 200 kPa pressure for 12 h.
desiccator. Then, they were gold-coated (Balzers SCD 050 sputter
coater; B.U.A., Fürstentum, Germany) and ultra-morphological
2.2.5. Thermal cycling
analysis was performed.
Thermal cycling was applied to the specimens in “Group TC”.
For this aging method, the specimens were submitted to a
thermocycling regimen of 5000 cycles in a 5–55
C distilled water 2.6. Statistical analysis
bath. Each cycle lasted 60 s: 20 s in a 5
C bath, 10 s to transfer
samples to another bath, 20 s in a 55
C bath and 10 s to transfer Two datasets for the statistical analyses of surface roughness
samples back to the 5
C bath. (Ra) and uniaxial flexural strength values were created.
Kolmogorov–Smirnov test was applied to each dataset (Ra or
2.2.6. Cyclic loading uniaxial flexural strength) for the evaluation of the normal
The specimens in “Group CL” were subjected to 50,000 cycles of distribution of variables. Then, Levene test was used for testing
mechanical axial fatigue in a computer-controlled chewing the homogeneity of variance. The statistical differences in uniaxial
simulator (CS-4.8, SD Mechatronik, Feldkirchen–Westerham, flexural strength values (MPa) and Ra data among tested materials
Germany). Fiber reinforced composite molds were fabricated; and aging procedures were compared by Kruskal–Wallis tests with
then, bar specimens were placed into the molds and attached to a significance level of 5% by using a statistical software (SPSS
the main holders of the chewing simulator. A load of 100N was 16.0 for Windows, Microsoft, USA). Further, when the p value from
applied by using steatite ceramic balls (r = 6 mm, Hoechst Ceram Kruskal–Wallis test statistics are statistically significant between
Tec, Wunsiedel, Germany) in the center of the bars. Axial load with the groups, Mann–Whitney U tests were conducted for multiple
only vertical movement and a frequency of 2.1 Hz was applied. pairwise comparisons. All comparative analyses were based on
Simultaneously, specimens were subjected to deionized distilled two-tailed tests and for all possible multiple comparisons, the
water during the fatigue degradation test. Bonferroni–Holm correction was applied for controlling type
1 error.
2.3. Examination of the surface roughness and surface topography The assessment of the reliability in strength testing was done in
terms of Weibull distribution. The method proposed by Quinn and
The surface roughness of the tested specimens was measured Quinn [29] was chosen to perform the Weibull regression analysis.
by coherence scanning interferometry (Contour GT-K, Bruker For each of the seven test groups, the stress values were ranked in
Nano GmbH, Germany). Each scan was performed on a surface ascending order, i = 1, 2, 3, . . . , N, where N is the total number of
area of 0.15 mm  0.1 mm, generating millions of data points. A test specimens and i is the ith datum. Thus, the lowest stress for
50 objective lens and a 1.0 multiplier was selected. The back each configuration represents the first value (i = 1), the next lowest
scan and length parameters were 20 mm and 20 mm in VSI/VXI stress value is the second datum (i = 2), etc., and the highest stress
mode to obtain a 3D rendering of the specimen surfaces. The is represented by the Nth datum. This enables a ranked probability
Vision 64TM software (Bruker Nano GmbH, Germany) which is of failure, Pf (s i), to be assigned to each datum according to the
part of the GT-K1system (Bruker Nano Gmbh, Germany), was used following formula:
to generate surface areas and roughness parameters. The i  0:5
particular parameter of interest was considered to be Ra Pf ðs iÞ ¼
N
(roughness average) measured from a mean line within the
sampling length. Then, the Weibull analysis was performed for calculation of
cumulative fracture probability (Pf) as function of applied stress
2.4. Measurement of uniaxial flexural strength after aging [29]. The form of the Weibull equation (for the two-parameter
distribution) is shown as:
Flexural properties were assessed by using a three point   m 
s
bending test (span 14.0 mm) according to ISO 6872: 2008 [28] with Pf ¼ 1 ¼ exp 
su
a universal testing machine (Lloyd LR 30K Plus; Lloyd Instruments
Ltd., Fareham, UK). A cross-head speed of 0.5 mm/min was applied where the constant m (the Weibull modulus) determines the slope
for loading. The tests were performed under the standard of the distribution function and characterizes the spread of the
laboratory conditions (room temperature of 22  1
C with a failure data with respect to s (fracture stress). s u is known as
relative humidity of 70  5%). Data were recorded with data the scale parameter or characteristic strength, that the stress level
analysis software (Nexygen; Lloyd Instruments Ltd., Fareham, UK). at which 63.21% of the specimens have failed.
68 F. Egilmez et al. / journal of prosthodontic research 62 (2018) 65–74

Fig. 1. Representative surface topographies of tested resin-based composite CAD/CAM specimens after submitted to the aging procedures. CS: GC CerasmartTM,
LU: LavaTMUltimate, VE: Vita Enamic1, C: control, WS: water storage, BW: boiling water, HCl: HCl exposure, A: autoclave treatment, TC: thermal cycling, CL: cyclic loading.

Minitab Version 14 (MINITAB, State College, PA, USA) statistical topographies of tested CAD/CAM materials after submitted to
analysis software was used to perform the Weibull regression the aging procedures. The red areas represent the peaks, the part of
analysis. Maximum Likelihood was used for the estimation of the surface with the highest height. The blue areas represent the
Weibull statistics. Bartlett’s modified likelihood ratio tests for valleys, the part of the surface with the lowest height.
equal shape (standard deviations) and equal characteristic (mean) A moderate irregular surface with heights and valleys was
values were conducted. Further, the appropriate Bonferroni observed in the coherence scanning interferometry images of CS-C.
post-hoc test was applied. Weibull parameters together with Moreover the images from the tested groups exhibited similar
the corresponding 95% confidence intervals were provided. The surface topographies with control. Narrow scratch lines made by
p-value of <0.05 was considered to be statistically significant. the abrasive polishing papers crossed the surfaces causing an
irregular area.
3. Results Additionally, LU-C showed smoother surface with randomly
located pores. A low profile, interrupted by randomly located
3.1. Characterization of the surfaces rounded off projections, characterized the material surface.
Similarly, aged specimens exhibited similar surface topographies
All of the aged groups for each of the tested CAD/CAM materials with control.
exhibited different surface topography when compared to the Moreover, VE-C specimens had non-uniform surface with
control groups. Fig. 1 displays the representative surface distinct sharp projections dotted with pores. Furthermore, VE

Table 2
Experimental groups (codes), mean flexural strength and standard deviation values, characteristic strength (s ) and Weibull modulus (m) and surface roughness (Ra) results.

Materials Aging condition Mean flexural strength  Std. dev. Characteristic strength (s 0) Weibull modulus (m) Surface roughness (Ra)  Std. Dev.
(MPa) (MPa) (Std. error) (Std. error) (nm)
CS C 146  15f,g 155 (5)g,h,i,j 8.18 (1.63)a,b 53.18  11.06a,b
WS 122  7c,d,e 129 (5)d,e 7.37 (1.37)a 61.50  8.12a,b
BW 120  13c,d,e 128 (5)d,e 7.71 (1.52)a 72.86  10.13a,b,c
HCl 147  26f,g 157 (6)j 7.26 (1.52)a 44.23  16.19a
A 124  7c,d,e 131 (5)d,e 7.88 (1.57)a 66.30  16.82a,b,c
TC 119  10c,d,e 127 (5)c,d,e 7.42 (1.49)a 64.35  7.93a,b
CL 138  17e,f 144 (3)g,h,i 12.25 (2.45)a,b,c,d,e 67.47  12.60a,b,c

LU C 149  20f,g 155 (3)i,j 12.52 (2.59)a,b,c,d,e 74.17  15.44a,b,c

WS 92  18a,b 96 (2)a 15.52 (3.17)b,c,d,e 66.19  13.31a,b,c
BW 115  18c,d 121 (3)b,c,d 10.91 (2.17)a,b,c,d 76.57  12.85a,b,c
HCl 162  25f,g 173 (6)k 7.95 (1.67)a 67.95  12.47a,b,c
A 112  19b,c,d 116 (2)b,c 18.34 (3.60)d,e 69.90  5.48a,b,c
TC 90  18a 95 (3)a 9.64 (1.97)a,b,c 88.75  5.13a,b,c
CL 139  14e,f 146 (4)g,h,i,j 11.14 (2.33)a,b,c,d 78.81  4.99a,b,c

VE C 124  18c,d,e 131 (4)d,e 10.00 (2.16)a,b,c 195.16  63.58b,c,d

WS 109  9a,b,c 113 (2)b 13.75 (2.63)a,b,c,d,e 209.40  27.38c,d
BW 131  20d,e,f 138 (4)e,f,g 9.00 (1.89)a,b 256.20  144.41d
HCl 128  9c,d,e 132 (2)d,e,f 19.09 (4.04)e 173.20  35.53a,b,c,d
A 138  11e,f 143 (3)f,g,h 12.75 (2.38)a,b,c,d,e 269.00  130.90d
TC 107  9a,b,c 112 (3)b 11.48 (2.21)a,b,c,d 249.40  64.29d
CL 124  10c,d,e 128 (2)d,e 17.08 (3.60)c,d,e 524.00  116.22e

Different superscript letters indicate statistical difference inside the respective column.
 F. Egilmez et al. / journal of prosthodontic research 62 (2018) 65–74 69

specimens exhibited more porous surface structure with multi across the groups (Levene statistics F = 3.490; p < 0.001). The
dots in BW, A and CL groups. effects of artificial aging conditions on the flexural strength results
The qualitative assessment of the surface characterization was are summarized in Table 2. The strength values in control groups
confirmed by quantitative data obtained by the mean value of ranged from 124.21 to 148.94 MPa. Significant differences were
roughness (Ra) (Table 2). One-sample Kolmogorov–Smirnov found among the flexural strength data of all tested materials
test of normality produced a test statistic of 2.955 (p < 0. 001), (p = 0.014). When overall results were compared, CS exhibited the
indicating substantial non-normality. Levene’s test showed highest flexural strength values, while there was no significant
evidence of heterogeneity of variances (Levene statistics difference in the results of LU and VE. In addition, flexural
F = 22.276; p < 0.001). According to statistical analysis there was strength results were significantly different in each aging condition
no significant difference amongst the Ra values of tested groups (p < 0.001). The flexural strength data were ranked as follows:
(X2 = 6.77, p = 0.342) for CS. Likely, LU specimens had statistically HCl  C  CL  A  BW  WS  TC (Fig. 2).
similar Ra values in each experimental procedures (X2 = 11.241, Additionally, statistical analysis revealed that, the type of tested
p = 0.081). Additionally, the Ra values of VE were not statistically material and aging protocol, and the interaction between these
different in tested groups (X2 = 3.119, p = 0.794). Overall Ra results two parameters were significant (p < 0.001). Furthermore, the
suggested that the ranking between CAD/CAM materials was uniaxial flexural strength of all CAD/CAM materials was
CS  LU < VE (p = 0.140 for CS and LU; p < 0.001 for CS and VE; significantly decreased after water storage, autoclave treatment
p < 0.001 for LU and VE) that indicates CS and LU had the lowest and thermal cycling (p < 0.001 for each aging protocol). HCl
surface roughness (Ra), whereas VE had the highest Ra value. exposure or cyclic loading did not change the flexural strength of
the CAD/CAM materials (p = 0.413; p = 0.161, respectively). Further-
3.2. Uniaxial flexural strength test and Weibull analysis results more, the flexural strength of CS and LU significantly decreased
after boiling in water (p = 0.002 for CS and p < 0.001 for LU).
The normality test of Kolmogorov–Smirnov revealed that data The Weibull moduli and the flexural strength data are
showed a normal distribution (Z = 0.689; p = 0.730). Levene’s test of presented in Table 2. Significant differences were found in Weibull
homogeneity of variance suggested that variances were equal moduli of all tested groups ranging from 7.26 to 19.09 (p < 0.001).

Fig. 2. Surface morphology of CS in each aging group at 4000 magnifications. C: control, WS: water storage, BW: boiling water, HCl: HCl exposure, A: autoclave treatment,
TC: thermal cycling, CL: cyclic loading.
70 F. Egilmez et al. / journal of prosthodontic research 62 (2018) 65–74

The lowest Weibull modulus was observed for CS whereas LU belong to the ceramic network and darker parts that demonstrate
and VE had similar Weibull moduli. For the material CS, Weibull the continuous polymer network. When micrographs of aging
moduli for aging groups, except cyclic loading (m = 12.25), were groups are examined, CS had similar surface patterns in aging
similar values obtained for control data (m = 7.26) (p = 0.030). groups and group C. However, LU-BW, LU-A and LU-HCl exhibited
Moreover, HCl, WS and TC groups’ results were significantly lower different surface characteristic than LU-C. Surface irregularities
than CL group’s for CS (p = 0.034; p = 0.039; p = 0.042, respectively). were observed. In these groups, micro pores and pits were seen.
The material LU exhibited the lowest Weibull moduli in HCl group Moreover, VE-CL group showed a change in surface texture with a
(m = 7.95) whereas the highest value was obtained in A (m = 18.34) rougher surface than control.
(p = 0.003). In addition, HCl and TC group values were significantly
lower than A group for LU (p = 0.003 and p = 0.041 respectively). 4. Discussion
The Weibull moduli of the material VE were ranged between
9.00 to 19.09 which were correspondent to BW and HCl groups, In the current study, hybrid and nano-ceramic composite
respectively. HCl results were significantly higher than BW materials were submitted artificial in-vitro aging conditions of
(p = 0.008) and group C values (p = 0.018) for VE. immersion in distilled water, boiling in water, HCl exposure,
autoclave treatment, thermal cycling and cyclic loading. Uniaxial
3.3. Scanning electron microscopy (SEM) results flexural strength test was selected as a reliable and relatively
simple test procedure. According to our results, CS exhibited the
Microstructure of the tested materials in each aging group is highest flexural strength values, while there was no significant
demonstrated in Figs. 2–4. Scratch lines from using abrasive disks difference in the results of LU and VE. In contrast, the lowest
could be observed in all tested materials. CS showed smoother Weibull modulus was observed in the material CS whereas LU
surface textures with uniformly dispersed small particles, whereas and VE had similar Weibull moduli. Awada and Nathanson [30]
LU revealed larger cluster filler particles protruding from the demonstrated that the polymer-based materials exhibited
surrounding surface. Furthermore, VE displayed brighter areas that relatively higher flexural strength and lower flexural modulus

Fig. 3. Surface morphology of LU in each aging group at 4000 magnifications. C: control, WS: water storage, BW: boiling water, HCl: HCl exposure, A: autoclave treatment,
TC: thermal cycling, CL: cyclic loading.
 F. Egilmez et al. / journal of prosthodontic research 62 (2018) 65–74 71

Fig. 4. Surface morphology of VE in each aging group at 4000 magnifications. C: control, WS: water storage, BW: boiling water, HCl: HCl exposure, A: autoclave treatment,
TC: thermal cycling, CL: cyclic loading.

than the ceramic materials. They reported that the combination hydrothermal degradation tests allow obtaining a reasonable
of low flexural modulus and high flexural strength of these prediction of the increase of monoclinic fraction of zirconia
materials translates to an increased ability to withstand restorations in vivo as a function of the time [38]; autoclave
loading by undergoing more elastic deformation before failure treatment is not a suitable treatment method for resin structured
[30]. materials. On the other hand, autoclave treatment was considered
On the other hand, the mechanical properties of CAD/CAM to have some effect on the present materials tested due to the
composites investigated in the current study were still far inferior higher zirconia filler contents of resin-based composite CAD/CAM
to the reported value of yttria stabilized tetragonal zirconia materials. Therefore, in the present study, autoclave treatment was
polycrystalline (Y-TZP) ceramic [31], fiber reinforced composites selected as an aging method. Since, no technique was used to
[32,33], glass infiltrated aluminum oxide ceramic [34], and lithium quantify phase changes in tested materials further studies should
disilicate glass ceramic for CAD/CAM [34]. Nevertheless, tested be conducted to test the effect of autoclave treatment effect on
CAD/CAM composites in this study were considered to be suitable these new hybrid materials.
when limited to single premolar crowns, but not for fixed partial In the current study, specimens were submitted to either
prostheses [16], since they do not meet the strength criteria autoclave treatment or immersed in boiling water in order to
recommended in ISO 6872:2008. create a combined effect of hydrolytic and thermal breakdown and
In this study, selected aging methods such as water storage, acid to accelerate aging. The results of this study showed that water
exposure, thermal cycling or boiling in distilled water were stated storage, boiling in distilled water, thermal cycling and autoclave
as one of the most common aging methods mentioned in the treatment showed a trend to lower flexural strengths compared to
dental literature [35]. Autoclave treatment was proven to induce the control for the materials CS and LU. Conversely, these aging
some degree of aging and it has been used often to demonstrate methods seemed to have similar effect for the flexural strengths of
low thermal degradation of zirconia [36]. Previous reports VE since there were no significant differences amongst the water
suggested that 1 h of autoclave treatment at 134
C had storage, boiling water, thermal cycling, autoclave treatment and
theoretically the same effect as 3–4 years in vivo [36,37]. Although control. In a recent study, it was demonstrated that, seven-day
72 F. Egilmez et al. / journal of prosthodontic research 62 (2018) 65–74

water storage and thermal cycling decreased the flexural strength Interestingly, flexural strength or Weibull moduli of none of the
of resin and hybrid nano-ceramic CAD/CAM composite blocks materials changed after mechanical fatigue in water. It was
which is in line with our findings [16]. However, in contrast with reported that an average of 250,000 chewing cycles per year is
the study of Lauvahutanon et al. [16], the flexural strength of VE performed [43]. Additionally, normal masticatory loads were
specimens decreased after water storage or thermal cycling. reported to range from 50 to 250 N [44]. In this study, the effect of
Previously, it was reported that, immersion in water might cause cyclic loading on CAD/CAM blocks was also evaluated. For this
water penetration into the resin matrix of the composite purpose, all specimens were subjected to 50,000 cycles with a
structured dental materials and softened the polymer [39]. 100 N load without cracking the specimens prior to the three point
Additionally, it was speculated that the absorbed water would bending tests. With regard to the previous point, 2.1 Hz cycling
cause hydrolysis of the interfacial silane coupling agent that parameter was selected due to the typical mastication frequency
provides the chemical bonding with resin structure and fillers [40]. varies from 1 to 2 Hz. Cyclic fatigue in a wet medium was shown to
Accordingly, the recession of the flexural strengths of CS and LU increase the crack propagation velocity of apatite-based ceramic
after water related aging methods, stated above and were selected materials, resin-based composite supported ceramic layer
in this study, may be the results of these mechanisms. On the other structures [45], or zirconia crowns [46]. However, retardation of
hand, non-significant change in flexural strength of VE after those crack propagation in composite structured dental materials under
aging protocols might be related due to its ceramic network aqueous environments was demonstrated by Takeshige et al. [47].
structure. Thus, the hypothesis that there would be no difference in This finding was explained by the presence of water in the resin
the flexural strength characteristics of the tested materials was matrix which might inhibit crack propagation as resulting
rejected. plasticization of the resin blunts the crack-tip and reduce the
The reliability of the flexural strength data was assessed stress concentration and dissipate the crack [47].
through the Weibull analysis in the current study to give a more Similar to the mechanical aging procedure, chemical degrada-
realistic indication of the material’s clinical performance [31]. tion with HCl had no impact on the flexural strength of all tested
Weibull modulus (m) is used to describe the variation of the materials. On the other hand, HCl treatment increased the Weibull
strength distribution as a result of flaws and micro cracks which modulus of VE, whereas had no significant effect in CS or LU. This
may develop within the microstructure [41]. The lower the value of finding could be attributed due to the differences in the
the Weibull modulus is indicative for the decreased reliability. On composition, filler type, filler concentration, microstructures,
the contrary, high structural reliability and the low inherent flaw and mechanical properties of the tested CAD/CAM restorative
density are characterized by the higher Weibull modulus materials. In the current study, 0.06 M HCl solution in deionized
compared with the lower values [31,41]. For the material CS and distilled water was used simulating the chemical exposure to
LU, Weibull moduli were not significantly different in all aging simulate natural gastric acids. The tested specimens were
groups when compared to the control data. Moreover, for the subjected to HCl for 24 h at 37
C. In a previous study by Wan
material VE, water related aging and cyclic loading groups had Bakar et al. [48] HCl was reported to cause no observable damage
non-significant Weibull moduli results compared to the control. In to composite resin specimens following 16 h exposure. In the light
an interesting manner, HCl acid treatment seemed to increase the of these previous results, the effect of prolonged exposure time
Weibull moduli significantly for the material VE. Although the (24 h) was evaluated in the current study. However, neither the
flexural strengths of all tested materials were lower than that of flexural strength nor surface roughness of the tested CAD/CAM
control groups following water related aging procedures or cyclic materials were affected by HCl exposure which is in line with
loading, they presented with the similar Weibull modulus previous findings [48].
compared to the controls. This might suggest the structural Besides to mechanical properties, surface roughness is an
homogeneity of the materials remain stable after severe aging important character of polymer based dental materials. The
conditions. It was speculated that, selected aging conditions parameter Ra is also one of the vertical parameter and is frequently
seemed to have no effect on the structural reliability of tested used for the quantification of surface roughness. In this study,
materials. Therefore, the hypothesis that there would be no 1200-grit SiC papers were chosen to produce continuous smooth
difference in the structural reliability of the tested materials was flat and standardized surfaces. As shown in Table 2, the Ra of the
confirmed. materials was similar after aging procedures. It was previously
Furthermore, the comparison of control groups of tested implied that the Ra of 0.2 mm is the critical threshold value for
materials revealed that the Weibull moduli of tested materials bacterial retention in vivo [49]. In addition, Jones et al. [50]
showed non-significant slight differences among themselves reported that the surface of finished restorations should
(CS: 8.18, LU: 12.52, VE: 10.00). However, comparing VE to CS have a maximum roughness of 0.50 mm. Moreover Ra values of
and LU materials the microstructural differences were obvious. The 0.2–0.5 mm may be perceived by the patient’s tongue [50]. Our
microstructure of VE is comprised of a feldspar ceramic network study demonstrated that, Ra of the control specimens were lower
that is fully integrated with a low polymer network content (14 wt than 0.2 mm. In addition, Ra values of CS and LU were still in the
%) [14]. On the other hand, regarding the microstructure of LU, it is range of 0.053–0.088 mm after aging procedures. On the other
a polymer network (20 wt%) reinforced by 80 wt% zirconia/silica hand, the Ra results of VE material were larger than 0.2 mm after
nano-ceramic particles. Furthermore, CS is a high-density boiling in water, autoclave, water storage, thermal cycling,
composite material contains 29 wt% polymeric network with and cyclic loading. However, it should be pointed out that
71% silica and barium glass particles [16]. Polymer chains in the minimal difference was found between control and following
polymer phase in VE was reported to spread the plasticity under environmental exposure apart from the VE material following
the increase of load and hence increase the crack resistance with severe etching in HCl. These roughness results were considered to
the crack length [42]. Although the composition of the tested be clinically relevant as implied previously [51].
materials were different, it seems that the existence of the polymer According to our SEM results, CS specimens exhibited similar
structure within the tested composite materials might result in surface characteristics after aging procedures compared to the
high observable Weibull moduli rather than toughening the control. These findings were supported with the surface roughness
materials, as it was reported in a recent study [42]. Therefore, it results that indicate no significant difference amongst the Ra values
can be concluded that the tested CAD/CAM materials have of tested groups for CS. Aged LU specimens also exhibited
comparable structural integrities. similar surface topographies with control although, LU-BW,
 F. Egilmez et al. / journal of prosthodontic research 62 (2018) 65–74 73

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