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

Rapid evolution of computer-aided design and computer-aided
manufacturing (CAD/CAM) systems has dramatically enhanced
prosthetic and restorative dentistry by providing advances in
manufacturing technologies [1]. New dental materials for the
$
This study was partly presented as an oral presentation at the 22nd
International Scientific Congress of Turkish Prosthodontics and Implantology
Association, Antalya-Turkiye, on 11–15 November 2015.
* Corresponding author at: Mutlukent Mah, 10. Cadde 2065. Sk. No:15, Beysukent,
Ankara, Turkey. Fax: +90 312 223 92 26.
E-mail addresses: ferhanegilmez@gmail.com, fegilmez@gazi.edu.tr (F. Egilmez).
number remarkably [2].
Resin-based composites and ceramics are the two main groups
of dental restorative materials [3]. On one side, several advantages
of ceramic restorations were demonstrated such as wear resis-
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
to the formation of flaws or defects in the intaglio surfaces [4,5].
Conversely, resin-based composites are known with their superior
aesthetics, ease of milling, simple intraoral repair techniques and
less abrasive effect toward opposing dentition due to their yielding
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
and in patients [7]. Several studies investigated the biocompati-
bility of these materials show that they have cytotoxic potential in
direct contact with cells [8–11]. Additionally, mechanical proper-
ties, e.g. flexural strength, hardness and flexural modulus of
resin-based materials are still inferior to those of ceramics [12,13].
Considerable progress has been made in composite resin
industry with the invention of nanohybrid and nanofilled resin
composites. At the same time, advanced materials that combine
the advantages of composite and ceramic materials have been
introduced to the dental community. A CAD/CAM restorative
material was developed as a polymer-infiltrated-ceramic-network
material in the recent past [5]. This material was called as double
network hybrid ceramic that has a polymeric second phase with a
lower modulus of elasticity into ceramic networks [5,14]. The
manufacturer stated that the mass percentage of the organic
polymer part is 14 wt% and the inorganic ceramic part is 86 wt%.
Accordingly, ceramic network creates the basic structure and
provides stability of the material while polymeric network
contributes the elasticity [5]. As well as hybrid ceramics,
CAD/CAM composites with nanohybrid structures based on
nanotechnology with inorganic ceramic fillers have been
developed [14]. These materials contain micro, hybrid and nano
fillers with different sizes including silica fillers nanomers (20 nm),
nanocluster particles derived from the fillers (0.6–10 mm), zirconia
fillers (4–11 nm) and/or barium glass fillers (300 nm) and resin
matrix [14–16]. Different dimethacrylate thermosets such as
ethoxylated bisphenol-A dimethacrylate (BisEMA), ethylene glycol
dimethacrylate (EGDMA), bisphenol-A-diglycidyl methacrylate
(BisGMA), urethane dimethacrylate (UDMA), and further
dimethacrylate are in the composition of resin matrix [16].
Besides to the variations in structure and filler contents, nano
particle filled resin CAD/CAM composites were shown to have
higher flexural strengths than the polymer-infiltrated-ceramic-
network material and leucite ceramic, but lower than lithium
disilicate ceramic [17].
Moreover, differences among these materials with regard to the
filler composition and matrix-filler coupling chemistry may
account for different mechanical performances and may further
account for differences in the materials’ resistance to mechanical
and chemical degradation [18]. Furthermore, it has been shown
previously that, surface roughness increased after accelerated
aging [19]. It was implied that the increased roughness of resin
structured dental materials may foster plaque accumulation on the
restoration surface, that results from surface deterioration due to
the degradation of resin matrix [20]. Therefore, roughness and
surface analyses become more important especially after aging
conditions.
Clinical studies have shown that resin-based composite
CAD/CAM restorative materials could be used as full-coverage
crowns [21] or posterior occlusal veneers [22] and are a viable
long-term treatment option for teeth with amelogenesis
Table 1
Tested materials, their compositions, tested conditions and group codes.
CAD/CAM material Material code Manufacturers
GC CerasmartTM CS GC Dental Products Europe, Leuven, Belgium
LavaTMUltimate LU 3M ESPE, Seefeld, Germany
Vita Enamic1 VE VITA Zahnfabrik, Bad Säckingen, Germany
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.
imperfecta or microdontia and is especially suitable for patients
still undergoing growth [23] or patients with dental erosion or
bruxism [24,25]. Also noteworthy is the documented de-bonding
at a higher than originally anticipated rate of Lava Ultimate (3M
ESPE) composite blocks, having forced the manufacturer to no
longer support the indication to fabricate complete coverage
crown restorations [26]. Throughout this perspective, in the
absence of long-term clinical data, clinicians must be cautious in
specifying the indications for these new materials.
To date, biomechanical behavior characteristics of resin-based
composite CAD/CAM materials have not yet been extensively
studied. Thus, the objective of this study was to determine the
flexural strength and Weibull characteristics of resin, hybrid
nano-ceramic and polymer infiltrated ceramic dental
materials after different in vitro aging conditions. The null
hypothesis was that there would be no difference in their
biomechanical characteristics amongst the tested materials after
aging procedures.
2. Material and methods
2.1. Specimen preparation
Hybrid and nano CAD/CAM composite blocks (GC CerasmartTM
A1-LT, LavaTM Ultimate Restorative Resin Nano Ceramic A1–LT and
Vita Enamic1 1M1-T standard translucency for Sirona Cerec AC
System) were selected for the study (Table 1).
The CAD/CAM blocks were sectioned with a precision cutting
machine (Isomet 1000, Buehler, Lake Bluff, USA), polished with
metallographic SiC papers (600, 800 and 1200-grit; Federation of
European Producers of Abrasives) to the final dimension (1.5 mm
 4 mm  17 mm). A total of 315 specimens were fabricated
(n = 15 per group) and subsequently cleaned in distilled water
for 10 min by an ultrasonic device (Quantrex 90, L&R Ultrasonics,
Kearny, NJ) and air dried. Then, they were assigned randomly into
7 groups. No treatment was provided to the specimens in control
group.
2.2. In vitro aging procedures
2.2.1. Water storage
Fifteen specimens from each material were put into plastic
containers and 40 ml deionized distilled water was added into the
tubes. Then the tubes were placed into the incubator at 37
C for
21 days. This group was assigned as “Group WS”.
2.2.2. Boiling in water
The specimens in “Group BW” were aged in boiling deionized
distilled water for 24 h. For this purpose, the specimens were put
into glass bottles with 40 ml distilled water and their caps were
tightened. Then the bottles were placed into a heating oven at
100
C for 24 h.
Shade-lot # Composition
A1-HT 1412161 Composite resin material (BisMEPP, UDMA, DMA) with
71 wt% silica and barium glass nanoparticles
A1-HT N590540 Composite resin material (BisGMA, UDMA, BisEMA,
TEGDMA) with 80 wt% silica and zirconia nanoparticles and
zirconia/silica nanoclusters
1M1-T 37010 Polymer-infiltrated-feldspatic ceramic-network material
(UDMA, TEGDMA) with 86 wt% ceramic
 F. Egilmez et al. / journal of prosthodontic research 62 (2018) 65–74
2.2.3. Acid exposure
The specimens in “Group HCl” were exposed to hydrochloric
acid (HCl, pH = 1.2), shown previously to cause erosive lesions in
enamel similar to those seen clinically [27]. 90 ml, 0.113 wt% HCl
solution in deionized distilled water was prepared. A pHS-3C
digital pH meter (Hangzhou Dongxing Instrument Works,
Hangzhou, China) was used to measure the pH value of the HCl
solution.
The specimens were placed into glass bottles, 30 ml HCl
solutions were added to each bottle and their caps were tightened.
Then the containers were incubated at 37
C under constant slow
agitation using an orbital shaking thermostated bath (Grant OLS
200, Grant Instruments Cambridge Ltd., Shepreth, UK) for 24 h.
2.2.4. Autoclave treatment
For thermal degradation test, specimens in “Group A” were
stored in an autoclave (Cisa S.p.A., Pomezia, Rome, Italy) at 134
C
under additional 200 kPa pressure for 12 h.
2.2.5. Thermal cycling
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
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
samples back to the 5
C bath.
2.2.6. Cyclic loading
The specimens in “Group CL” were subjected to 50,000 cycles of
mechanical axial fatigue in a computer-controlled chewing
simulator (CS-4.8, SD Mechatronik, Feldkirchen–Westerham,
Germany). Fiber reinforced composite molds were fabricated;
then, bar specimens were placed into the molds and attached to
the main holders of the chewing simulator. A load of 100N was
applied by using steatite ceramic balls (r = 6 mm, Hoechst Ceram
Tec, Wunsiedel, Germany) in the center of the bars. Axial load with
only vertical movement and a frequency of 2.1 Hz was applied.
Simultaneously, specimens were subjected to deionized distilled
water during the fatigue degradation test.
2.3. Examination of the surface roughness and surface topography
The surface roughness of the tested specimens was measured
by coherence scanning interferometry (Contour GT-K, Bruker
Nano GmbH, Germany). Each scan was performed on a surface
area of 0.15 mm  0.1 mm, generating millions of data points. A
50 objective lens and a 1.0 multiplier was selected. The back
scan and length parameters were 20 mm and 20 mm in VSI/VXI
mode to obtain a 3D rendering of the specimen surfaces. The
Vision 64TM software (Bruker Nano GmbH, Germany) which is
part of the GT-K1system (Bruker Nano Gmbh, Germany), was used
to generate surface areas and roughness parameters. The
particular parameter of interest was considered to be Ra
(roughness average) measured from a mean line within the
sampling length.
2.4. Measurement of uniaxial flexural strength after aging
Flexural properties were assessed by using a three point
bending test (span 14.0 mm) according to ISO 6872: 2008 [28] with
a universal testing machine (Lloyd LR 30K Plus; Lloyd Instruments
Ltd., Fareham, UK). A cross-head speed of 0.5 mm/min was applied
for loading. The tests were performed under the standard
laboratory conditions (room temperature of 22  1
C with a
relative humidity of 70  5%). Data were recorded with data
analysis software (Nexygen; Lloyd Instruments Ltd., Fareham, UK).
67
The uniaxial flexural strength [modulus of rupture (s )] were
then calculated by using he following formula [28]:
3Wl
s¼ 2
2bd
where W stands for breaking load (N); l is the span length (mm); b
is the width of each specimen (mm) and d is the and thickness of
the specimen (mm).
2.5. Surface analysis with scanning electron microscopy (SEM)
For surface morphology assessments, two fractured specimens
from each tested group were randomly selected following flexural
strength test and examined by scanning electron microscopy
(SEM) (JSM-5500LV; JEOL, Tokyo, Japan) at 15 kV and 20 mm
working distance. Briefly, the specimens were mounted in
aluminum stubs and dehydrated over night under vacuum in a
desiccator. Then, they were gold-coated (Balzers SCD 050 sputter
coater; B.U.A., Fürstentum, Germany) and ultra-morphological
analysis was performed.
2.6. Statistical analysis
Two datasets for the statistical analyses of surface roughness
(Ra) and uniaxial flexural strength values were created.
Kolmogorov–Smirnov test was applied to each dataset (Ra or
uniaxial flexural strength) for the evaluation of the normal
distribution of variables. Then, Levene test was used for testing
the homogeneity of variance. The statistical differences in uniaxial
flexural strength values (MPa) and Ra data among tested materials
and aging procedures were compared by Kruskal–Wallis tests with
a significance level of 5% by using a statistical software (SPSS
16.0 for Windows, Microsoft, USA). Further, when the p value from
Kruskal–Wallis test statistics are statistically significant between
the groups, Mann–Whitney U tests were conducted for multiple
pairwise comparisons. All comparative analyses were based on
two-tailed tests and for all possible multiple comparisons, the
Bonferroni–Holm correction was applied for controlling type
1 error.
The assessment of the reliability in strength testing was done in
terms of Weibull distribution. The method proposed by Quinn and
Quinn [29] was chosen to perform the Weibull regression analysis.
For each of the seven test groups, the stress values were ranked in
ascending order, i = 1, 2, 3, . . . , N, where N is the total number of
test specimens and i is the ith datum. Thus, the lowest stress for
each configuration represents the first value (i = 1), the next lowest
stress value is the second datum (i = 2), etc., and the highest stress
is represented by the Nth datum. This enables a ranked probability
of failure, Pf (s i), to be assigned to each datum according to the
following formula:
i  0:5
Pf ðs iÞ ¼
N
Then, the Weibull analysis was performed for calculation of
cumulative fracture probability (Pf) as function of applied stress
[29]. The form of the Weibull equation (for the two-parameter
distribution) is shown as:
  m 
s
Pf ¼ 1 ¼ exp 
su
where the constant m (the Weibull modulus) determines the slope
of the distribution function and characterizes the spread of the
failure data with respect to s (fracture stress). s u is known as
the scale parameter or characteristic strength, that the stress level
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
analysis software was used to perform the Weibull regression
analysis. Maximum Likelihood was used for the estimation of
Weibull statistics. Bartlett’s modified likelihood ratio tests for
equal shape (standard deviations) and equal characteristic (mean)
values were conducted. Further, the appropriate Bonferroni
post-hoc test was applied. Weibull parameters together with
the corresponding 95% confidence intervals were provided. The
p-value of <0.05 was considered to be statistically significant.
3. Results
3.1. Characterization of the surfaces
All of the aged groups for each of the tested CAD/CAM materials
exhibited different surface topography when compared to the
control groups. Fig. 1 displays the representative surface
topographies of tested CAD/CAM materials after submitted to
the aging procedures. The red areas represent the peaks, the part of
the surface with the highest height. The blue areas represent the
valleys, the part of the surface with the lowest height.
A moderate irregular surface with heights and valleys was
observed in the coherence scanning interferometry images of CS-C.
Moreover the images from the tested groups exhibited similar
surface topographies with control. Narrow scratch lines made by
the abrasive polishing papers crossed the surfaces causing an
irregular area.
Additionally, LU-C showed smoother surface with randomly
located pores. A low profile, interrupted by randomly located
rounded off projections, characterized the material surface.
Similarly, aged specimens exhibited similar surface topographies
with control.
Moreover, VE-C specimens had non-uniform surface with
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
specimens exhibited more porous surface structure with multi
dots in BW, A and CL groups.
The qualitative assessment of the surface characterization was
confirmed by quantitative data obtained by the mean value of
roughness (Ra) (Table 2). One-sample Kolmogorov–Smirnov
test of normality produced a test statistic of 2.955 (p < 0. 001),
indicating substantial non-normality. Levene’s test showed
evidence of heterogeneity of variances (Levene statistics
F = 22.276; p < 0.001). According to statistical analysis there was
no significant difference amongst the Ra values of tested groups
(X2 = 6.77, p = 0.342) for CS. Likely, LU specimens had statistically
similar Ra values in each experimental procedures (X2 = 11.241,
p = 0.081). Additionally, the Ra values of VE were not statistically
different in tested groups (X2 = 3.119, p = 0.794). Overall Ra results
suggested that the ranking between CAD/CAM materials was
CS  LU < VE (p = 0.140 for CS and LU; p < 0.001 for CS and VE;
p < 0.001 for LU and VE) that indicates CS and LU had the lowest
surface roughness (Ra), whereas VE had the highest Ra value.
3.2. Uniaxial flexural strength test and Weibull analysis results
The normality test of Kolmogorov–Smirnov revealed that data
showed a normal distribution (Z = 0.689; p = 0.730). Levene’s test of
homogeneity of variance suggested that variances were equal
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.
69
across the groups (Levene statistics F = 3.490; p < 0.001). The
effects of artificial aging conditions on the flexural strength results
are summarized in Table 2. The strength values in control groups
ranged from 124.21 to 148.94 MPa. Significant differences were
found among the flexural strength data of all tested materials
(p = 0.014). When overall results were compared, CS exhibited the
highest flexural strength values, while there was no significant
difference in the results of LU and VE. In addition, flexural
strength results were significantly different in each aging condition
(p < 0.001). The flexural strength data were ranked as follows:
HCl  C  CL  A  BW  WS  TC (Fig. 2).
Additionally, statistical analysis revealed that, the type of tested
material and aging protocol, and the interaction between these
two parameters were significant (p < 0.001). Furthermore, the
uniaxial flexural strength of all CAD/CAM materials was
significantly decreased after water storage, autoclave treatment
and thermal cycling (p < 0.001 for each aging protocol). HCl
exposure or cyclic loading did not change the flexural strength of
the CAD/CAM materials (p = 0.413; p = 0.161, respectively). Further-
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 Weibull moduli and the flexural strength data are
presented in Table 2. Significant differences were found in Weibull
moduli of all tested groups ranging from 7.26 to 19.09 (p < 0.001).
70 F. Egilmez et al. / journal of prosthodontic research 62 (2018) 65–74
The lowest Weibull modulus was observed for CS whereas LU
and VE had similar Weibull moduli. For the material CS, Weibull
moduli for aging groups, except cyclic loading (m = 12.25), were
similar values obtained for control data (m = 7.26) (p = 0.030).
Moreover, HCl, WS and TC groups’ results were significantly lower
than CL group’s for CS (p = 0.034; p = 0.039; p = 0.042, respectively).
The material LU exhibited the lowest Weibull moduli in HCl group
(m = 7.95) whereas the highest value was obtained in A (m = 18.34)
(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).
The Weibull moduli of the material VE were ranged between
9.00 to 19.09 which were correspondent to BW and HCl groups,
respectively. HCl results were significantly higher than BW
(p = 0.008) and group C values (p = 0.018) for VE.
3.3. Scanning electron microscopy (SEM) results
Microstructure of the tested materials in each aging group is
demonstrated in Figs. 2–4. Scratch lines from using abrasive disks
could be observed in all tested materials. CS showed smoother
surface textures with uniformly dispersed small particles, whereas
LU revealed larger cluster filler particles protruding from the
surrounding surface. Furthermore, VE displayed brighter areas that
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.
belong to the ceramic network and darker parts that demonstrate
the continuous polymer network. When micrographs of aging
groups are examined, CS had similar surface patterns in aging
groups and group C. However, LU-BW, LU-A and LU-HCl exhibited
different surface characteristic than LU-C. Surface irregularities
were observed. In these groups, micro pores and pits were seen.
Moreover, VE-CL group showed a change in surface texture with a
rougher surface than control.
4. Discussion
In the current study, hybrid and nano-ceramic composite
materials were submitted artificial in-vitro aging conditions of
immersion in distilled water, boiling in water, HCl exposure,
autoclave treatment, thermal cycling and cyclic loading. Uniaxial
flexural strength test was selected as a reliable and relatively
simple test procedure. According to our results, CS exhibited the
highest flexural strength values, while there was no significant
difference in the results of LU and VE. In contrast, the lowest
Weibull modulus was observed in the material CS whereas LU
and VE had similar Weibull moduli. Awada and Nathanson [30]
demonstrated that the polymer-based materials exhibited
relatively higher flexural strength and lower flexural modulus
 F. Egilmez et al. / journal of prosthodontic research 62 (2018) 65–74
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
of low flexural modulus and high flexural strength of these
materials translates to an increased ability to withstand
loading by undergoing more elastic deformation before failure
[30].
On the other hand, the mechanical properties of CAD/CAM
composites investigated in the current study were still far inferior
to the reported value of yttria stabilized tetragonal zirconia
polycrystalline (Y-TZP) ceramic [31], fiber reinforced composites
[32,33], glass infiltrated aluminum oxide ceramic [34], and lithium
disilicate glass ceramic for CAD/CAM [34]. Nevertheless, tested
CAD/CAM composites in this study were considered to be suitable
when limited to single premolar crowns, but not for fixed partial
prostheses [16], since they do not meet the strength criteria
recommended in ISO 6872:2008.
In this study, selected aging methods such as water storage, acid
exposure, thermal cycling or boiling in distilled water were stated
as one of the most common aging methods mentioned in the
dental literature [35]. Autoclave treatment was proven to induce
some degree of aging and it has been used often to demonstrate
low thermal degradation of zirconia [36]. Previous reports
suggested that 1 h of autoclave treatment at 134
C had
theoretically the same effect as 3–4 years in vivo [36,37]. Although
71
hydrothermal degradation tests allow obtaining a reasonable
prediction of the increase of monoclinic fraction of zirconia
restorations in vivo as a function of the time [38]; autoclave
treatment is not a suitable treatment method for resin structured
materials. On the other hand, autoclave treatment was considered
to have some effect on the present materials tested due to the
higher zirconia filler contents of resin-based composite CAD/CAM
materials. Therefore, in the present study, autoclave treatment was
selected as an aging method. Since, no technique was used to
quantify phase changes in tested materials further studies should
be conducted to test the effect of autoclave treatment effect on
these new hybrid materials.
In the current study, specimens were submitted to either
autoclave treatment or immersed in boiling water in order to
create a combined effect of hydrolytic and thermal breakdown and
to accelerate aging. The results of this study showed that water
storage, boiling in distilled water, thermal cycling and autoclave
treatment showed a trend to lower flexural strengths compared to
the control for the materials CS and LU. Conversely, these aging
methods seemed to have similar effect for the flexural strengths of
VE since there were no significant differences amongst the water
storage, boiling water, thermal cycling, autoclave treatment and
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
of resin and hybrid nano-ceramic CAD/CAM composite blocks
which is in line with our findings [16]. However, in contrast with
the study of Lauvahutanon et al. [16], the flexural strength of VE
specimens decreased after water storage or thermal cycling.
Previously, it was reported that, immersion in water might cause
water penetration into the resin matrix of the composite
structured dental materials and softened the polymer [39].
Additionally, it was speculated that the absorbed water would
cause hydrolysis of the interfacial silane coupling agent that
provides the chemical bonding with resin structure and fillers [40].
Accordingly, the recession of the flexural strengths of CS and LU
after water related aging methods, stated above and were selected
in this study, may be the results of these mechanisms. On the other
hand, non-significant change in flexural strength of VE after those
aging protocols might be related due to its ceramic network
structure. Thus, the hypothesis that there would be no difference in
the flexural strength characteristics of the tested materials was
rejected.
The reliability of the flexural strength data was assessed
through the Weibull analysis in the current study to give a more
realistic indication of the material’s clinical performance [31].
Weibull modulus (m) is used to describe the variation of the
strength distribution as a result of flaws and micro cracks which
may develop within the microstructure [41]. The lower the value of
the Weibull modulus is indicative for the decreased reliability. On
the contrary, high structural reliability and the low inherent flaw
density are characterized by the higher Weibull modulus
compared with the lower values [31,41]. For the material CS and
LU, Weibull moduli were not significantly different in all aging
groups when compared to the control data. Moreover, for the
material VE, water related aging and cyclic loading groups had
non-significant Weibull moduli results compared to the control. In
an interesting manner, HCl acid treatment seemed to increase the
Weibull moduli significantly for the material VE. Although the
flexural strengths of all tested materials were lower than that of
control groups following water related aging procedures or cyclic
loading, they presented with the similar Weibull modulus
compared to the controls. This might suggest the structural
homogeneity of the materials remain stable after severe aging
conditions. It was speculated that, selected aging conditions
seemed to have no effect on the structural reliability of tested
materials. Therefore, the hypothesis that there would be no
difference in the structural reliability of the tested materials was
confirmed.
Furthermore, the comparison of control groups of tested
materials revealed that the Weibull moduli of tested materials
showed non-significant slight differences among themselves
(CS: 8.18, LU: 12.52, VE: 10.00). However, comparing VE to CS
and LU materials the microstructural differences were obvious. The
microstructure of VE is comprised of a feldspar ceramic network
that is fully integrated with a low polymer network content (14 wt
%) [14]. On the other hand, regarding the microstructure of LU, it is
a polymer network (20 wt%) reinforced by 80 wt% zirconia/silica
nano-ceramic particles. Furthermore, CS is a high-density
composite material contains 29 wt% polymeric network with
71% silica and barium glass particles [16]. Polymer chains in the
polymer phase in VE was reported to spread the plasticity under
the increase of load and hence increase the crack resistance with
the crack length [42]. Although the composition of the tested
materials were different, it seems that the existence of the polymer
structure within the tested composite materials might result in
high observable Weibull moduli rather than toughening the
materials, as it was reported in a recent study [42]. Therefore, it
can be concluded that the tested CAD/CAM materials have
comparable structural integrities.
Interestingly, flexural strength or Weibull moduli of none of the
materials changed after mechanical fatigue in water. It was
reported that an average of 250,000 chewing cycles per year is
performed [43]. Additionally, normal masticatory loads were
reported to range from 50 to 250 N [44]. In this study, the effect of
cyclic loading on CAD/CAM blocks was also evaluated. For this
purpose, all specimens were subjected to 50,000 cycles with a
100 N load without cracking the specimens prior to the three point
bending tests. With regard to the previous point, 2.1 Hz cycling
parameter was selected due to the typical mastication frequency
varies from 1 to 2 Hz. Cyclic fatigue in a wet medium was shown to
increase the crack propagation velocity of apatite-based ceramic
materials, resin-based composite supported ceramic layer
structures [45], or zirconia crowns [46]. However, retardation of
crack propagation in composite structured dental materials under
aqueous environments was demonstrated by Takeshige et al. [47].
This finding was explained by the presence of water in the resin
matrix which might inhibit crack propagation as resulting
plasticization of the resin blunts the crack-tip and reduce the
stress concentration and dissipate the crack [47].
Similar to the mechanical aging procedure, chemical degrada-
tion with HCl had no impact on the flexural strength of all tested
materials. On the other hand, HCl treatment increased the Weibull
modulus of VE, whereas had no significant effect in CS or LU. This
finding could be attributed due to the differences in the
composition, filler type, filler concentration, microstructures,
and mechanical properties of the tested CAD/CAM restorative
materials. In the current study, 0.06 M HCl solution in deionized
distilled water was used simulating the chemical exposure to
simulate natural gastric acids. The tested specimens were
subjected to HCl for 24 h at 37
C. In a previous study by Wan
Bakar et al. [48] HCl was reported to cause no observable damage
to composite resin specimens following 16 h exposure. In the light
of these previous results, the effect of prolonged exposure time
(24 h) was evaluated in the current study. However, neither the
flexural strength nor surface roughness of the tested CAD/CAM
materials were affected by HCl exposure which is in line with
previous findings [48].
Besides to mechanical properties, surface roughness is an
important character of polymer based dental materials. The
parameter Ra is also one of the vertical parameter and is frequently
used for the quantification of surface roughness. In this study,
1200-grit SiC papers were chosen to produce continuous smooth
flat and standardized surfaces. As shown in Table 2, the Ra of the
materials was similar after aging procedures. It was previously
implied that the Ra of 0.2 mm is the critical threshold value for
bacterial retention in vivo [49]. In addition, Jones et al. [50]
reported that the surface of finished restorations should
have a maximum roughness of 0.50 mm. Moreover Ra values of
0.2–0.5 mm may be perceived by the patient’s tongue [50]. Our
study demonstrated that, Ra of the control specimens were lower
than 0.2 mm. In addition, Ra values of CS and LU were still in the
range of 0.053–0.088 mm after aging procedures. On the other
hand, the Ra results of VE material were larger than 0.2 mm after
boiling in water, autoclave, water storage, thermal cycling,
and cyclic loading. However, it should be pointed out that
minimal difference was found between control and following
environmental exposure apart from the VE material following
severe etching in HCl. These roughness results were considered to
be clinically relevant as implied previously [51].
According to our SEM results, CS specimens exhibited similar
surface characteristics after aging procedures compared to the
control. These findings were supported with the surface roughness
results that indicate no significant difference amongst the Ra values
of tested groups for CS. Aged LU specimens also exhibited
similar surface topographies with control although, LU-BW,
 F. Egilmez et al. / journal of prosthodontic research 62 (2018) 65–74
LU-A and LU-HCl exhibited different surface characteristic with
micro pores and pits than LU-control by SEM evaluation.
Additionally, VE-CL group showed a change in surface texture
with a rougher surface than control with SEM evaluation.
One of the limitations of this study may be the smaller
dimensions of the specimens suggested that in the ISO 6872:2008
[28]. However, these dimensions are not possible to obtain from
CAD/CAM blocks due to they are fabricated only exist for milling
crowns. The other limitation might be the small sample size of
tested specimens, which are less than 30 to provide adequate
Weibull strength distribution parameters. On the other hand,
several reports have shown the level of structural reliability of
different dental materials with lower numbers of specimens by
Weibull analysis [17,31,42]. Actually, the optimal number of test
specimens depends on many variables, such as the values of the
distribution parameters, testing procedures, the desired precision
for an intended application and cost of material [29,31]. However,
it should be pointed out that, interpretation of the results of the
current study should be made carefully, since 15 specimens in each
group were subjected to Weibull analysis. However, it is believed
the results have some useful validity, as the results of the current
study follow the Weibull curve quite well.
Another limitation of the present study is that applied aging
and cyclic loading periods might be considered as short periods for
the data to have meaningful correlation to possible clinical
outcomes. Additional studies are needed to clarify the influence
of longer periods of aging and cyclic loading on mechanical
properties and longevity of resin-based composite CAD/CAM
materials.
From the clinical point of view and in contrast to common
clinical opinions, the mechanical properties of new polymer based
CAD/CAM composite materials remain stable even in extreme
in-vitro aging conditions. However, long-term clinical trials should
be provided for the evidence of in-vivo success. Thus, further study
designs are needed to investigate the process of mechanical
behavior of polymer based CAD/CAM materials.
5. Conclusions
Within the limitations of this in-vitro study, it can be concluded
that:
1. CS exhibited the highest flexural strength values, while there
was no significant difference in the results of LU and VE.
2. Water storage, boiling in water, thermal cycling and autoclave
treatment decreased the flexural strengths compared to the
control for the materials CS and LU. Conversely, these aging
methods seemed no effect on the flexural strengths of VE.
3. For the material CS and LU, Weibull moduli were similar in aging
groups compared with control. For the material VE, water
related aging and cyclic loading groups had also similar Weibull
moduli compared to the control. However, HCl acid treatment
increased the Weibull moduli of the material VE.
4. Ra values of CS and LU were in the range of clinically suggested
values after aging procedures. However, Ra values of VE material
were larger than 0.2 mm after boiling in water, autoclave
treatment, water storage, thermal cycling, and cyclic loading
treatments.
Acknowledgments
The authors would like to thank GC Corp., Vita Zahnfabrik, and 3
M ESPE for donation of their materials. This study was financed by
the BioCity Turku Biomaterials and Medical Device Research
Program (www.biomaterials.utu.fi).
73
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