Composites Part B 216 (2021) 108852

Contents lists available at ScienceDirect

Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

A review of dental composites: Challenges, chemistry aspects, filler

influences, and future insights
Alireza Aminoroaya a, Rasoul Esmaeely Neisiany b, **, Saied Nouri Khorasani a, ***,
Parisa Panahi a, Oisik Das c, 1, *, Henning Madry d, Magali Cucchiarini d, ****,
Seeram Ramakrishna e
a
Department of Chemical Engineering, Isfahan University of Technology, Isfahan, 84156-83111, Iran
b
Department of Materials and Polymer Engineering, Faculty of Engineering, Hakim Sabzevari University, Sabzevar, 9617976487, Iran
c
Structural and Fire Engineering Division, Department of Civil, Environmental and Natural Resources Engineering, Luleå University of Technology, Luleå, 97187, Sweden
d
Center of Experimental Orthopaedics, Saarland University and Saarland University Medical Center, Kirrbergerstr. Bldg 37, D-66421, Homburg, Saar, Germany
e
Centre for Nanofibers and Nanotechnology, Department of Mechanical Engineering, National University of Singapore, Singapore, 117575, Singapore

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

Keywords: Resin-based dental composites are promising tooth-resembling materials in restorative dentistry. The limited
Dental composite longevity of dental composite restorations due to the bulk/marginal fracture and secondary caries as well as
Dental composite challenges possible health risks are the critical challenges faced by such materials. Therefore, developments of resin-based
Monomer chemistry
dental composites received considerable attention in academic researches for clinical applications. A compre­
Filler phase characteristics
hensive review of the recent developments in the scientific literature on resin-based dental composites is pre­
sented in this article. Firstly, in the article, the challenges in dental composites are introduced and then the
chemical aspects of the systems are classified through a review of employed resins. Subsequently, the different
characteristics related to the fillers employed for the development of the resin-based dental composites are
described. Finally, conclusions are drawn and future insights are proposed. This article provides an insight that
paves the way for tailoring and designing resin-based dental composites for clinical applications.

1. Introduction literature review by Eltahlah et al. [4], resin-based dental composites

Oral diseases negatively impact human health, well-being, and
quality of life worldwide. Moreover, poor oral health linked to systemic
bacterial and inflammatory vulnerability can cause undesired outcomes,
including uncontrolled diabetes, cardiovascular disease, and respiratory
disease [1]. Despite the widespread advancements in oral hygiene ed­
ucation and practice, dental decay (or dental caries) treatment remains
an inseparable part of everyday dentistry. More than 90% of adults and
approximately 20% of people in all age groups in the United States and
more than one-third of people in all age groups worldwide have expe­
rienced tooth decay [2]. Restorative dentistry approximately costs 46
billion dollars in the United States annually [3]. According to the
(44%), amalgams (40.9%), glass ionomers/resin-modified glass ion­
omers/dental compomers (13.4%), and other types of restoration (e.g.,
indirect and temporary restorations) (1.7%) have been used as dental
restorative materials since 1981. Placement of restorations are divided
into two groups: 1) initial restoration placement due to primary caries
and non-carious defects and 2) restoration replacement that is reported
to be performed for more than half of the initial restorations due to
secondary caries, bulk/marginal fracture, poor anatomic form, and
bulk/marginal discoloration [4]. The trend of using resin-based dental
composites instead of amalgam is increasing in dentistry. Furthermore,
56% of the total dental restoration placement was related to the
replacement of restoration before 2000, which increased to 58% for the

* Corresponding author.
** Corresponding author.
*** Corresponding author.
**** Corresponding author.
E-mail addresses: r.esmaeely@hsu.ac.ir (R.E. Neisiany), saied@iut.ac.ir (S.N. Khorasani), oisik.das@ltu.se (O. Das), magali.madry@uks.eu (M. Cucchiarini).
1
Oisik Das dedicates this manuscript to his uncle, Late Dr (Prof) Devdutta Das, who succumbed to COVID-19 in September 2020. Dr (Prof) Devdutta Das
dedicated his entire life to the service of dental education and research.

https://doi.org/10.1016/j.compositesb.2021.108852
Received 23 February 2021; Accepted 26 March 2021
Available online 31 March 2021
1359-8368/© 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
A. Aminoroaya et al.
total restoration placement after 2000 [4]. These statistics reveal the
poor longevity of dental restorations and increased dental care cost
related to the subsequent clinical interventions.
Resin-based dental composite materials (also referred to as “dental
composite” or “dental composite resin” or “dental resin composite” or
“dental polymer composite” in the literature) are widely used in
dentistry to provide direct aesthetic tooth-resembling restorations [5].
They are used in dental practices as a restorative material, pit and fissure
sealant, cavity liner, veneer, crown, endodontic sealers, and orthodontic
devices. These materials are composed of two phases: an organic resin
matrix and the inorganic/organic filler [6,7]. Organic resin matrix phase
is made from a mixture of multifunctional monomers and light-sensitive
initiators while inorganic/organic filler phase contains
micro/nano-sized fillers, which are mainly used as reinforcement [8,9].
In situ polymerization of dental resin composite by light-irradiation (in
the blue region of the light spectrum) forms a highly crosslinked poly­
mer network that restores the missing dentin/enamel structure [10].
Dental resin composites with different curing systems, known as “self-­
cure” and “dual-cure” are also commercially available for special ap­
plications. Despite many signs of progress in the performance of
resin-based dental composites, their service life and longevity as
dental restoration are limited. Annual failure rates of up to 3–11% have
been reported for dental composite restoration in posterior and anterior
teeth [11–15]. Secondary caries and bulk/margin fracture of the dental
composite are the main reasons for restoration failures. From the ma­
terial properties perspective, health risks and limited longevity of
resin-based dental composite materials have been generally related to
the complicated interaction of high surface bacterial biofilm formation
tendency, polymerization shrinkage related strain and stress, low frac­
ture toughness (FT), incomplete degree of monomer conversion (DC),
high water sorption (WS) and water solubility (WSl), and the possibility
of human exposure to bisphenol-A.
Web of Science search reveals that there are several beneficial review
papers on dental composite, which studied different monomers, initia­
tors and fillers utilized as dental composites components and discussed
the impact on physical, mechanical, antibacterial and self-healing
properties of dental composites [16–20]. However, these articles did
not provide an overall and comparative classification of the chemistry of
monomers and various structural features related to fillers in order to
address the design of dental composites, which can face their main
clinical challenges from the material design point of view. Therefore, the
current paper aims to review the main clinical challenges of dental
composites and provide a comprehensive classification of monomer
chemistry and structural filler properties, which encompass the progress
of resin-based dental composites after 2010. In addition, characteriza­
tion methods of dental composites were comprehensively reviewed and
described in our previous review paper [21]. Section 2 of the current
study is dedicated to present the current challenges of resin-based dental
composites and to clarify the strategies for future improvements. Section
3 provides the progress related to the matrix phase of the dental com­
posites. Investigation of bulky dimethacrylate monomers, Bisphenol A
glycidyl methacrylate (BisGMA) or triethylene glycol dimethacrylate
(TEGDMA) monomer substituents, liquid crystalline monomers, fluori­
nated dimethacrylates, diallyl and divivylbenzyl monomers are pro­
vided in this section. Moreover, new monomer chemistry with
alternative polymerization mechanisms for free radical chain-growth,
including thiol-enes, thio-micheals, thio-urethane oligomers, spi­
roorthocarbonates, vinylcyclopropanes, and epoxy monomers are thor­
oughly discussed. Monomers with antibacterial activity, which are
incorporated in the dental composite formulation such as quaternary
ammonium methacrylate and furanone derivatives, are also discussed in
section 3. Section 4 delves into the introduction of the recent advance­
ments related to the investigation of various characteristics of the filler
phase such as size, distribution, shape, porosity, and interfacial prop­
erties on the characteristics of dental composites. Nano/micro-sized
fillers with different shapes including particulates, fibers, whiskers,
2
Composites Part B 216 (2021) 108852
plate-like, and nano-porous structured fillers are discussed, while it is
attempted to draw specific trends and mechanisms related to the char­
acteristics of the filler phase, which influence the properties of dental
composites. Finally, section 5 provides the possible and expected future
advances of resin-based dental composite materials. This article there­
fore delivers an overview of the subject possibly paving the path for
designing tailored dental composites for practical applications.
2. Challenges and strategies
In order to achieve superior performance and increased longevity of
dental resin composites, recent research is facing three main challenges,
including 1) secondary caries, 2) bulk/marginal fracture, and 3) health
risk, which are pinpointed in the following subsections.
2.1. Secondary caries
According to in vitro and in vivo assessments, dental resin composite
materials form more plaque biofilm on their surfaces compared with
other types of dental restorative materials [22]. Gram-positive bacteria
present in the human oral environment, including Streptococcus mutans,
Actinomyces naeslundii, and Lactobacillus casei are the main constituting
bacterial species of human dental plaque [23]. In addition, the increased
surface roughness of dental composites, over time, intensifies the degree
of bacterial colonization [24,25]. Combination of these behaviors
coupled with the gap formation in the tooth-restoration interface due to
the polymerization shrinkage of the composites and cyclic mechanical
and thermal loading of the oral environment provide suitable host lo­
cations at the margin of the restoration for colonization of bacteria. This
leads to subsequent secondary caries and failure of the dental composite
restoration. Dental composites with low polymerization shrinkage stress
(SS-S) and strain (SS-N) may lead to lessened restoration failure due to
the formation of secondary caries. As such, various studies on the
reduction of polymerization shrinkage of dental composites are
reviewed in the following sections. Other strategies such as formulating
dental composites with antibacterial and bacteriostatic properties that
have been developed in recent research are beyond the scope of this
article, but will be briefly addressed in section 5.
2.2. Bulk/marginal fracture
Bulk/marginal fracture is also a prevalent dental composite resto­
ration failure mode. Diminished mechanical properties of dental com­
posites, over time, in the oral environment, leads to this type of failure.
Several factors such as incomplete monomer conversion after polymer­
ization, significant SS-N and SS-S, high WS, low FT of the material, poor
filler-matrix interaction, and inefficient stress dissipation by filler phase
are assumed to deteriorate the mechanical properties of dental com­
posite over time. The DC depends on monomer(s) chemistry, concen­
tration and composition of the initiator(s), polymerization conditions,
and light scattering effects of filler particles. However, it has never
reached 100% due to vitrification or gelation phenomenon during
polymerization [26]. A higher DC leads to improved mechanical and
chemical stability [27]. Stress and strain induced by polymerization of
the dental resin composite in the cavity generally depend on the
monomer type, initiator system reactivity, and filler size and load in the
resin composite formulation [28]. It can lead to marginal gap formation,
diminished mechanical properties, and crack formation in the tooth
structure [28]. Additionally, WS has a plasticization effect on the
polymer network of dental composite that reduces the mechanical
properties and wear resistance [29,30] leading to the chemical insta­
bility of the resin and deteriorated resin-filler interface via hydrolysis,
which further reduces the mechanical properties over time [29]. The WS
and subsequent swelling of dental resin composite have been reported to
produce micro-cracks in the composite [31]. The degree of dental
composite WS is dependent on the chemistry of the polymer matrix,
A. Aminoroaya et al. Composites Part B 216 (2021) 108852

crosslink density, and hydrophilicity [32]. Furthermore, crack nucle­

ation at the filler-matrix interface of dental composites due to the
different modulus of inorganic filler phase and organic polymer matrix
as well as crack propagation are influenced by the FT of the organic
matrix and stress transition/dissipation through the composite medium,
which is related to the filler phase and interface properties [33]. The
aforementioned factors along with the cyclic mechanical and thermal
loading of the oral environment cause significantly lowered mechanical
properties and microcracking of the dental composites over time. The
combination of reduced mechanical properties and growth and accu­
mulation of the cracks cause premature fracture of the dental composite
restoration. To address the challenges, several strategies regarding the
modification of monomer chemistry and filler/interface phase charac­
teristics have been proposed and investigated in the literature, which are
detailed in the following sections.

2.3. Health-associated risks

The presence of leachable species in dental composites as a result of

incomplete monomer conversion, enzymatic and hydrolytic degradation
of the components of the dental composite may cause biocompatibility
problems, harm to surrounding tissues, and increase systematic health
risks [34]. More importantly, in the case of BisGMA containing dental
resin composites, the possibility of human exposure to the bisphenol-A
compound, which is known to be responsible for several diseases like
spermatogenesis impairment and male reproductive abnormalities, is a
cause of great concern to many research [35–38]. In this regard, many
researchers tried to propose non-bisphenol-A monomers as an alterna­
tive to BisGMA (section 3.2).
3. Matrix phase: chemistry aspects
3.1. Initiators and co-initiators
The camphorquinone (CQ)/amine initiating system is commonly used
in commercial dental composite materials [39,40]. This photo-initiation
system produces radical active centers, which lead to polymerization of
monomers when irradiated by visible light sources especially in the blue
region of the spectrum. Different types of amines, including ethyl
4-(dimethylamino)benzoate, N,N-dimethylaminoethyl methacrylate,
2-ethyl-dimethylbenzoate, N,N-dimethyl-p-toluidine, and N-phenylglycine
have been used as co-initiator for CQ in order to accelerate the photo­
polymerization. Alternative choices for CQ includes other visible light ini­
tiators such as trimethylbenzoyl-diphenyl-phosphine oxide, 2,3
buanedione, phenyl bis(2,4,6-trimethylbenzoyl) phosphineoxide, ivocerin,
and UV-initiators 2,2-dimethoxy-2-phenyloacetophenone (Irgacure 651),
and bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (Irgacure 891).
For a monomer system that utilizes ion-mediated polymerization mecha­
nisms such as spiroorthocarbonate, vinylcyclopropanes, and epoxides,
initiator capable of producing ionic active agent to trigger polymerization
are utilized. The examples of such initiators are phenyl iodonium hexa­
fluoroantimoate [41], bis(4-methaoxybenzoyl)diethylgermane [42],
4-octylpheyl phenyliodoniumhexafluoroantimoate [43], and [4-(octyloxy)
phenyl]phenyliodonium SbF6 [44].
Fig. 1. Chemical structures of conventional dimethacrylate monomers used in
dental composite materials.
[45]. According to ongoing research studies, several types of monomers
have been synthesized and characterized to address the deficiencies of
conventional dimethacrylates in terms of enhanced polymerization ki­
netics, rheology, mechanical properties, and cytocompatibility. These
new monomers are classified according to their chemistry as I)
methacrylated-based monomers, II) vinyl monomers, III) click chemistry
monomers, and IV) ring-opening polymerization monomers (Fig. 2).
3.2.1. Methacrylate-based monomers
Methacrylate-based monomers are widely used in the formulation of
commercial dental composites that polymerize by the chain radical
polymerization mechanism of double bonds [70]. Highly crosslinked
methacrylate-based monomer mixture obtained after
photo-polymerization of dental composites have displayed satisfying
mechanical properties in clinical practices [71]. However, the chain
radical polymerization mechanism of methacrylate-based monomers
leads to a heterogeneous polymeric network, which is correlated to high
SS-S and SS-N, and high values of WS [72]. Furthermore, high viscosities
of methacrylate monomers such as BisGMA have imposed several limi­
tations on DC as well as on the design/incorporation of suitable filler
phase (section 4). Several modifications and introduction of newly
designed methacrylate monomers are studied in the literature in order to
address these shortcomings, which can be classified as follows.
Furthermore, a summary of highlighted research studies on
methacrylate-based monomers utilized in the preparation of dental resin
are summarized in Table 3, and the chemical structure of related
monomers are depicted in Fig. 3.

3.2. Monomers I) Synthesis of methacrylate monomer with higher molecular vol/wt:

Three conventional dimethacrylate monomers (Fig. 1) have been
widely used in the resin formulation of dental composite materials.
Generally, all new proposed dental resins in research studies have been
compared with the conventional dimethacrylate monomers. In this re­
gard, the different physicochemical and mechanical properties of these
conventional monomers and their homopolymer/copolymer are pro­
vided in Table 1 and Table 2, respectively. Variances in reported values
are mainly due to the different characterization methods, curing pro­
cedure, and initiation compositions utilized in different research studies
Polymerization shrinkage of resin matrix is due to the reduction of
intermolecular distance between monomer molecules into the intra­
molecular covalent bond in the polymer chains during polymerization.
Therefore, several studies have synthesized dimethacrylate monomers
with increased molecular weight to reduce the SS-N. As the molecular
weight of dimethacrylate monomers increases the subsequent reduction
in the concentration of carbon-carbon double bond in the organic matrix
leads to lessened polymerization. Such modifications include the

3
A. Aminoroaya et al. Composites Part B 216 (2021) 108852

Table 1
Physicochemical properties of conventional dimethacrylate monomers employed in methacrylate-based dental composites.
Monomer(s) Molecular weight Concentration of double bonds (mol/kg) Density Viscosity (Pa.s) Refractive index In vitro cytotoxicity (ED50
concentrations)a [46]

BisGMA 510.6 3.9 1.1741 [47] 1200 [49] 15.50 [47] 0.11 ± 0.01 (3T3)
1.161 [48] 1369 [50] 15.40 [48] 0.10 ± 0.01 (HGF)
1188 [51] 0.14 ± 0.02 (HFP)
0.08 ± 0.03 (HPLF)
UDMA 470 4.25 1.1195 [47] 23 [53] 1.485 [47] 0.10 ± 0.05 (3T3)
1.11 [52] 28 [50] 1.483 [48] 0.13 ± 0.05 (HGF)
22 [51] 0.47 ± 0.14 (HFP)
0.06 ± 0.02 (HPLF)
TEGDMA 286.3 6.99 1.092 [54] 0.011 [49] 1.532 0.19 ± 0.04 (3T3)
1.09 [48] 0.05 [50] 0.23 ± 0.6 (HGF)
0.01 [51] 0.26 ± 0.2 (HFP)
0.12 ± 0.06 (HPLF)
BisGMA: – – – 0.28 [51] – –
TEGDMA (1:1, wt:wt) 0.155 [55]
BisGMA: – – – 3.5 [51] – –
TEGDMA (7:3, wt:wt) 1.5 [56]
a
ED50 Values (mM) of monomers were obtained by Permanent 3T3 Cells, Primary Human Gingival Fibroblasts (HGF), Primary Human Pulp Fibroblasts (HPF), and
Primary Human Periodontal Ligament Fibroblasts (HPLF).

Table 2
Physicochemical and mechanical properties of conventional dimethacrylate homopolymer/copolymer in methacrylate-based dental composites.
Homopolymer/copolymer DC (%) FS (MPa) FM (GPa) SS-N (vol. %) SS-S (MPa) WS WSl
( μg ) ( μg )
mm3 mm3

poly(BisGMA) 47.3 [47] 84.8 [47] 4.12 [47] 4.88 [47] 0.3 [51] 3.1 [49] –
41.46 [57] 85.9 [57] 3.872 [52] 3.43 [57] 11.1 [60]
39.15 [58] 5.3 [59] 32.18 [52]
poly(UDMA) 69.6 [61] 118.7 [47] 3.12 [47] 6.88 [47] 6.8 [51] 33.6 [62] 8 [62]
70 [47] 117.5 [62] 3.93 [62] 8.7 [59] 23.85 [52]
63.5 [58] 135 [52] 3.488 [52] 6.95 [52]
poly(TEGDMA) 75.7 [61] 48 [64] 0.63 [64] 14.1 [59] 14.2 [51] 6 [49] 1.48 [64]
81.3 [63] 82.2 [54] 0.71 [54] 13.8 [54] 6.18 [64] 6.9 [65]
79.4 [54] 76.3 [65] 3.91 [52] 11.4 [65] 53.6 [65]
poly(BisGMA): 60.9 [61] 128.7 [57] 2.7 [67] 5.1 [67] 4.1 [67] 28.6 [68] 2.38 [68]
TEGDMA (1:1, wt:wt) 67.3 [57] 120.5 [55] 3.48 [55] 9.51 [55] 8.2 [51] 36 [55] 2.9 [55]
72 [55] 64.6 [66] 0.94 [66] 57.3 [66] 33.8 [66]
poly(BisGMA): 54.9 [61] 66 [69] 3.1 [69] – 4.4 [51] 39 [56] 7 [56]
TEGDMA (7:3, wt:wt) 62 [58] 135 [56] 4.3 [56] 1.16 [56]

synthesis of dimethacrylate monomers having bulky bicycloaliphatic

rings [73] and aromatic rings [55,66] with different hydrocarbon
segment lengths. These monomers showed lower SS-N at similar DC in
comparison to the BisGMA/TEGDMA resin composites.

II) Synthesis of low viscosity methacrylates as novel diluent

monomer:

Several shortcomings of conventional resin mixture such as in vitro

cytotoxicity, low mechanical properties, high polymerization shrinkage
are attributed to the utilization of TEGDMA monomer. Thus, several
attempts were made in recent studies to propose new dimethacrylate
monomers with low viscosity as a substitute for TEGDMA in
methacrylate-based resin formulations. In this regard, several low-
viscosity dimethacrylate monomers including acetyloxypropylene
dimethacrylate (Acet-GDMA) [54], bio-based Ethoxylated Isosorbide
Dimethacrylate (ISETMDA) [65], and poly (propylene glycol) dime­
thacrylate (PPGDMA) [74] were proposed as a possible substitute of
TEGDMA in the dental resin mixture formulation. These monomers
generally exhibited comparable viscosity to TEGDMA as well as reduced
volumetric shrinkage (VS), increased/comparable mechanical proper­
ties, and lower in vitro cytotoxicity compared to the TEGDMA-based
analogous composites.

III) Synthesis of non-bisphenol-A methacrylate monomers:

Fig. 2. Classification of proposed dental monomers based on their chemistry
and their characteristic functional groups.

4
A. Aminoroaya et al. Composites Part B 216 (2021) 108852

Table 3
Summary of highlighted research studies related to the utilization of methacrylate monomers in dental resin.
Purpose Modification/Monomer(s) Results Ref

Reduction of SS-N Dimethacrylate esters having ● Reduction of SS-N compared to BisGMA, UDMA, and TEGDMA [73]
bicycloaliphatic rings homopolymers
NA-EG, NA-BG, and NA-HG
Dimethacrylate esters having aromatic rings ● Similar SS-N at higher DC compared to BisGMA/TEGDMA copolymer [55]
PhA-13, PhA-14, PhA-15, PhA-16, and Acet- ● Higher FS, hardness, and Young’s modulus than BisGMA/TEGDMA
PhA-15 based control
● Reduction of FS, hardness, and Young’s modulus by the increase of
monomer aliphatic hydrocarbon length
Dimethacrylate monomer having aromatic ● Lower DC, VS, WS and WSl compared to BisGMA/TEGDMA based [66]
rings control
BMPB
Synthesis of novel diluent monomer Acet-GDMA ● Comparable viscosity, refractive index, density, DC, and FS to [54]
(TEGDMA substitutes) TEGDMA
● Reduced VS compared to poly(TEGDMA)
Bio-based Ethoxylated Isosorbide ● Low viscosity [65]
Dimethacrylate ISETMDA ● Lower VS and higher Tg at similar DC compared to BisGMA/TEGDMA
based control
PPGDMA ● Reduction of VS, WS and increase of DC compared to methacrylated- [74]
based control
● Increased BFS and lowered modulus compared to methacrylate-based
control
● Improved in vitro cytotoxicity (by resazurin, WST8, and MPS assays)
compared to TEGDMA
Reduction of human exposure to bisphenol-A Bio-based isosorbide urethane methacrylic ● High DC [75]
(BisGMA substitutes) monomer/Is-UDMA ● Lower VS, WS, and WSl compared to BisGMA based control
● Increased storage modulus, FS, and FM compared to BisGMA based
control
Non-bisphenol-A monomers/SiMA ● Lower FS, FM, VS, WS, higher DC, and similar WSl compared to [36]
BisGMA-based control
● Higher relative growth rate than the commercial dental composite of 3
M ESPE FiltekTM Z250
Non-bisphenol-A monomers/SiMA ● Higher DC and VS compared to BisGMA/TEGDMA based control [48]
● Similar FS and water contact angle with BisGMA/TEGDMA based
control
Modification of BisGMA structure Synthesis of BisGMA analogous ● Higher hydrophobicity and lower viscosity than BisGMA [77,
● Lower VS and comparable mechanical properties compared to 78]
BisGMA-based control

In order to reduce human exposure to bisphenol-A, several research
studies proposed a new formulation as a substitution for BisGMA
monomer in resin formulations. For this purpose, several recent studies
synthesized non-bisphenol-A dimethacrylates as a possible dental
monomer to limit human exposure with bisphenol-A derivatives [36,48,
75]. Especially, bio-based monomers synthesis based on isosorbide
resulted in lessened in vitro cytotoxicity, which served as appropriate
choices for substitution of BisGMA and TEGDMA monomers [65,75,76].
These studies suggested that new monomer structures should exhibit a
balance between rigidity (provided by stiff moieties such as ring struc­
tures or urethane group) and flexibility to maintain mechanical prop­
erties compared to BisGMA-based formulations as along with high DC
[36,48,75].
IV) Modification of conventional dimethacrylate monomers:
Modification of the BisGMA chemical structure also exhibited several
enhancements. In this regard, recent studies investigated the effects of
new BisGMA-analogous monomers, obtained by the substitution of hy­
droxyl groups of BisGMA monomer by various ester groups having
different alkyl chain length and branching structures, on dental resin
composite properties [77,78]. The results showed that the functional
group of the alkyl chain group increased the hydrophobicity of the resin,
which result in lower WS, WSl and consequently lessened their adverse
consequences. Incorporation of new dimethacrylates in the formulation
leads to higher DC. Also, new monomers significantly reduced the VS,
which is related to their higher molecular weights than BisGMA and
their side-chain length (not the branching structure) prevent the close
packing of polymer chains.
3.2.2. Vinyl monomers
In the recent years, research on new multi-functional monomers
capable of polymerizing by chain radical polymerization mechanism,
especially allyl monomers, introduced new monomer choices for dental
resin composite development with promising outcomes [29,79–82].
These recent researches are summarized in Table 4, and the related
chemical structure of the utilized monomers are depicted in Fig. 4.
Several recent studies have investigated various diallyl monomers as
reactive diluent monomer for the development of BisGMA-based resin
composites [79,83,84]. These studies generally concluded that the uti­
lization of diallyl monomers instead of TEGDMA offers a higher DC,
lower VS, and appropriate mechanical properties and cytocompatibility.
In fact, the characteristic of allyl monomers is that the polymerization
rate of allyl functional group is lower than methacrylate functional
group, which leads to lower SS-S, and also encourage radicals to
terminate by combination mechanism during copolymerization result­
ing in a higher DC [84]. Moreover, in another set of studies, some new
vinyl monomers including triethyleneglycol-divinylbenzyl ether
(TEG-DVBE) [29] and N-methyl-bis(ethyl-carbamate-isoproply- ∝
-methylstyryl)-amine (Phene) [80] were studied as co-monomer for the
development of methacrylate based dental composites. These monomers
resulted in improved mechanical properties, lower VS and SS-S, and
higher DC, which may promote the lifespan of the material [29,80].
3.2.3. Click chemistry monomers
Since the appearance of click chemistry in 2001, many thiol-X re­
actions have been introduced to dental resin formulations. These mod­
ifications including thiol-ene [72,85–88], thiol-Micheal binary
monomer systems [69], and thio-urethane oligomers [89–93] provided
several kinetic-related advantages. In contrast to the radical

5
A. Aminoroaya et al.
Fig. 3. Chemical structure of dimethacrylate monomers proposed in recent research studies as a dental monomer.
chain-growth polymerization of methacrylate-based monomers, a
thiol-ene binary monomer system is converted to the polymer through a
radical step-growth polymerization mechanism [94–98]. First, the
anti-Markovnikov addition reaction of the thyl radical to the
carbon-carbon double bond of the ene monomer produces a carbor­
adical. Following that, a chain transfer reaction of the carboradical to a
thiol, via abstracting the hydrogen of the thiol, reproduces a thyl radical.
This step-growth mechanism continues cyclically. This polymerization
mechanism is related to thiol-ene binary monomer systems with
non-homopolymerizable ene monomers including norbonenes, vinyl
ethers, and allyl ethers [99]. Compared to methacrylates, thiol-enes
demonstrated several advantages such as rapid photopolymerization
6
Composites Part B 216 (2021) 108852
rates terminating with low amounts of unreacted functional groups and
insignificant polymerization inhibition by oxygen. Furthermore, due to
the evolving nature of the polymer molecular weight by step growth
mechanism, the high molecular weight polymers are obtained at high
degree of functional group conversions, and the gelation or vitrification
phenomenon is delayed. Therefore, the more uniform the polymer
network (with narrow glass transition), the lower is the SS-S [72,85,86,
100]. The thiol-ene binary systems, however, exhibited some short­
comings, particularly in flexural strength (FS) and flexural modulus
(FM) [101,102]. To compensate for this limitation, several studies uti­
lized ternary methacrylate-thiol-ene monomer formulations for dental
resin composite preparation [72,85,86]. These systems synergistically
A. Aminoroaya et al. Composites Part B 216 (2021) 108852

Table 4 Table 5
Summary of highlighted research studies related to the utilization of vinyl Summary of highlighted research studies related to the utilization of click
monomers in dental resin. chemistry-based monomers in dental resin.
Purpose Monomer Results Ref. Type Monomer(s) Results Ref.

Reactive diluent HMFBA ● Lower FS, VS,SS-S, and SS-S [84] Thiol-ene binary Thiol-terminated ● Comparable SS-S to [56]
monomer compared to BisGMA/TEGDMA systems oligomers BisGMA/TEGDMA
based control TATATO based control even at
● Higher DC compared to the control higher DC
● Superior cytocompatibility ● Low values of WS, WSl,
35DACBzA ● Lower FS,FM, VS and SS-S, higher DC [83] and swelling in water
than BisGMA/TEGDMA based control Methacrylate- PETMP, TMPTN, ● Off-stoichiometric [85]
● Lower WS and WSl than control thiol-ene TATATO, BisGMA, molar ratio of thiol:ene
● Superior cytocompatibility (by WST- ternary BisEMA, and TEGDMA (>1) in ternary
1 assay) systems methacrylate-thiol-ene
BPhADAC ● Lower VS and SS-S, higher DC [79] systems increases the
● Superior cytocompatibility ene functional group
Comonomer TEG-DVBE ● Enhanced FS and FT [29] conversion
● Higher DC, lower VS and WSl ● Lower SS-S and flexural
Phene ● Lower VS and SS-S [80] properties compared to
● Higher DC BisGMA/TEGDMA
● Comparable FS and FT based control
PETMP, TATATO, and ● Increasing the molar [86]
BisEMA thiol:ene ratio results in
higher ene conversion,
lower VS and SS-S
● Higher FM, FS, WS and
WSl than those of the
controls
UTAE, PTEMP, BisGMA ● Increased FT and a [72]
and TEGDMA narrower glass
transition temperature
as the thiol:ene content
was increased in the
resin formulations
Thio-urethane six thiol-terminated ● Significant reduction of [103]
oligomers thio-urethane SS-S and an increase in
oligomers by using FT for all thio-
PETMP and TMP as urethane-methacrylate
thiol monomers and composites compared
BDI, HMDI, and HDDI to the BisGMA/
as diisocyanates, in TEGDMA based control
BisGMA/TEGDMA
resin
Thiol-Micheal SR368 and DVS as ● Higher degree of [104]
based systems electron-deficient functional group
vinyls and PETMP and conversion and lower
SiTSH as thiols SS-S than the control
● Lower Glass transition
temperature, FS,
Young’s modulus, and
toughness than the
control
● Better water-
immersion behavior
than the control

another thiol-based class reaction of click chemistry, thiol-Micheal

Fig. 4. Chemical structures of allyl monomers proposed as potential monomers
for the incorporation in an organic resin matrix of dental composites.
benefit from the kinetic advantages of thiol-ene and the good mechan­
ical performance of methacrylates. Utilization of both types of ene
monomers, homopolymerizable and non-homopolymerizable, in those
systems leads to a dual mechanism of radical step-growth and free
radical chain growth. In another set of studies, incorporation of
thio-urethane oligomers in the mixture of methacrylates monomer
favorably resulted in reduced VS and higher FT [90,103]. These results
originated from the transfer reaction of radicals during photo­
polymerization of methacrylate monomers to thiol groups. It leads to
delayed gelation or virtification phenomenon, a higher degree of DC,
and a more homogeneous polymer network [90]. Furthermore, as
polymerization systems became a candidate for new dental resin for­
mulations recently [104]. Thiol-Michael resin systems include
multi-functional thiols and electron-deficient vinyl monomers that
polymerize by an anion-mediated step-growth mechanism. Summarized
research studies on click chemistry-based dental resin composites and
the related monomer structures are provided in Table 5 and Fig. 5,
respectively.
3.2.4. Ring-opening polymerization monomers
Owing to the ring-opening polymerization mechanisms, many
monomer chemistry including spiro orthocarbonates (SOCs) [41,105],
vinylcyclopropanes [42,106,107], epoxies [43,44,108,109], and silor­
ane [110,111] have effectively alleviated the VS and SS-S of dental
materials. Due to the nature of their double ring-opening polymerization
mechanism, allylic or methacrylic modified-SOCs presented promising
reductions in VS and SS-S for dental composite materials. In addition,
the novel vinyl cyclopropanes and epoxy monomers have shown to be

7
A. Aminoroaya et al.
Fig. 5. Chemical structures of thiol-ene monomers proposed as possible dental resin.
useful for the reduction of VS and SS-S. This behavior is attributed to the
different character of their ring-opening polymerization mechanism
compared to previously utilized monomers. The summary of recent
research studies on dental resin composites and the related chemical
structures of their monomers, with ring-opening mechanism, are sum­
marized in Table 6 and Fig. 6, respectively.
4. Fillers phase: structural characteristics
Various inorganic particles with different components such as silica,
alumina, zirconia, silicate glass, quartz, and ceramics have been
employed in the resin matrix of dental composites as reinforcing filler
phase in research studies as well as commercial formulations [115]. The
first key property for the selection of a filler for dental composites is the
similarity of the refractive indices of the filler particles with organic
matrix resin to provide sufficient DC and depth of cure as well as
appropriate aesthetic properties [116]. In order to achieve an ideal
dental restoration material, filler phase is incorporated in the organic
matrix of dental composites to tailor different mechanical properties to
ideally mimic the properties of the dental tissue that they replace. Some
values reported for the mechanical properties of human dentin and
enamel are summarized in Table 7. In addition to the composition of the
fillers, several other characteristics such as content, size, distribution of
size, shape, morphology, porosity, and surface properties of filler par­
ticle play a critical role in the development of dental composites with
desired properties for their special applications, which are presented in
Fig. 7. The role of each of these characteristics of the filler phase of
dental composites has been investigated in several recent research works
by utilization of a controlled case study in order to clarify the perfor­
mance of each characteristic on the property outcome of dental com­
posites. Thus, the following subsections review the influence of the filler
8
Composites Part B 216 (2021) 108852
phase from a different point of view on the properties of dental
composites.
4.1. Content
Mechanical properties, polymerization shrinkage, and handling
properties are dominated by the filler content of dental composites
[123–125]. The role of the content of particulate fillers on the properties
of dental composites is more straightforward than other characteristics
of the filler (e. g. size, distribution, shape, etc.), and several studies have
investigated this relationship. However, more specific research works
considering the influence of the content of various fillers with specific
characteristics (e.g. size, distribution, shape, and surface properties) to
provide a more accurate investigation of its influence on the different
properties of dental composites will be influential.
Generally, mechanical reinforcement is developed as the content of
an inorganic filler increases in the polymer matrix of dental composites
materials [123]. Considering a filler phase with specific characteristics,
the mechanical properties development for the dental resin composite is
better studied with regards to the three filler content zone [123]:
Zone I: low filler concentrations in which the particles are in a non-
aggregated form and a small fraction of them may come together to
form aggregates.
Zone II: intermediate filler concentration in which the particles are in
close proximities to form a particle gel-like system known as perco­
lated particle network. The minimum volume fraction of the filler
resembling percolated particle network is known as the percolation
threshold.
Zone III: maximum possible filler concentration at which the
network does not allow the incorporation of additional fillers.
A. Aminoroaya et al. Composites Part B 216 (2021) 108852

Table 6 refinement of the percolation model by introducing new parameters

Summary of highlighted research studies related to the utilization of ring- accounting for the influence of polymer-filler interface, particle braches
opening polymerization monomers in dental resin. or isolated particle aggregates are needed. Gonçalves et al. [124] re­
Type/mechanism Monomer(s) Results Ref. ported an exponential increase in elastic modulus of a
Spiro orthocarbonates BMSOC, ● Lower VS and SS-S than [105]
methacrylate-based resin by increasing the content of barium glass
(SOCs)/Step double BisGMA and the control particles (2 μm). This accentuated increase of elastic modulus could be
ring-opening TEDMA related to the formation of percolation network structure at high filler
polymerization SOC-UDMA, ● Increasing [41] concentration. However, the authors attributed it to the reduced elastic
SOC-IP-UDMA, spiroorthocarbonates
deformation of the organic matrix due to bonding with the filler surface
BisGMA, content decreased the
UDMA, and SS-S, while increased the and shortening of polymer chains as the result of filler content increase.
TEGDMA DC, WS and WSl, as well SS-S development in the dental composite is a complex phenomenon,
as FM of the composites and it is related to several variables including DC, polymerization re­
Vinylcyclopropanes Four di- ● Lower VS (1.3–1.33 vol [112] action kinetics, shrinkage strain, and elastic modulus [124]. A recent
(VCPs)/Radical functional vinyl %), and SS-S, and com­
ring-opening cyclopropane parable FS relative to the
research study investigated the influence of micron-sized glass filler and
polymerization monomers dimethacrylate-based methacrylate monomer composition on SS-S and its variables [130]. The
(VCP1-4) control composite study showed that SS-S, polymerization reaction kinetics, and DC are
● The FM and hardness mostly influenced by monomers composition in the resin, while filler
were slightly lower than
content has a stronger influence on SS-N, elastic modulus and loss
the control
VCP1-4 ● Lower VS and SS-S than [113] tangent. Thus, the study suggests formulating low SS-S dental compos­
UDMA/TEGDMA-based ites by modification of resin chemistry and composition instead of
control sacrificing the filler phase content. As filler content increase, the number
Epoxy monomers/ BP and ECH ● Higher Vickers hardness [43] of reactive functional groups decreases in the resin matrix leading to
Cationic ring- and FM
lower SS-N [130,131]. As long as the filler surface area is not too high,
opening ● Lower FS
polymerization ● The post-gelation VS was filler content does not affect the DC of dental composites, and the DC
significantly lower than variable is eliminated when a research study investigates the role of
the methacrylate-based filler content on polymerization shrinkage [124,128]. However, the
control
thickness of the specimen should be kept less than 2 mm in order to
● Similar cytotoxicity to
commercial dental eliminate the light attenuation effect for composite with high filler
composites content [124]. Considering the effect of filler content on SS-S, contra­
EP5000 and ● Reduced SS-S at a similar [114] dicting results have been reported in the literature. A research study by
DPHA VS compared to the Gonçalves et al. [124] resulted in an inverse correlation between SS-S
BisGMA/TEGDMA based
and filler content/elastic modulus, while other similar research studies
control
demonstrated a direct correlation [132,133]. Both sets of studies utilized
the same measuring technique (a universal testing machine) for the
With the increase of filler content, the hydrodynamic effects of in­ determination of SS-S but with high compliance poly (methyl methac­
dividual particles are responsible for mechanical reinforcement (espe­ rylate) (PMMA) and low compliance metal or glass as a substrate. These
cially modulus and strength) in zone I (before percolation threshold) contradicting results may originate from different used substrates and
[126]. However, the formation of the percolation network structure is two-sided influence of elastic modulus on SS-S development as following
responsible for mechanical reinforcement in zones II and III (after [124]: I) dental composites with higher elastic modulus have lower
percolation threshold) [123]. Stress transfer at the filler-matrix interface strain capacity, which intensifies the SS-S, and II) dental composites
is the predominant mechanism for mechanical reinforcement in zone I with higher elastic modulus lead to higher elongation of bonding sub­
[127], however, enhanced stress dissipation as a result of interparticle strates, which reduces the load cell sensitivity to SS-S.
frictions as well as stress transmission to nearby fillers in the percolated
network structure is responsible for highly improved mechanical rein­ 4.2. Size
forcement in zone II [128]. It is noteworthy to mention that the increase
in filler phase content leads to mechanical reinforcement as long as the In addition to the importance of filler phase content on the properties
integrated filler-matrix interactions and strength are maintained and the of dental composites, filler phase size and its distribution play a critical
quality of filler dispersion is acceptable (e.g. negligible filler particle role in the outcome performance of dental composite materials [17,
agglomeration and void formation) [123]. These pre-requirements 134]. Several research studies have been designed carefully to investi­
strongly depend on the filler surface characteristics and quality of the gate the influence and role of filler size and/or distribution on maximum
mixing equipment utilized for the preparation of dental composites. filler load content [123,128,135,136], mechanical properties [33,123,
Percolation threshold can be identified experimentally by scanning 128,131,136–140], polymerization shrinkage [141,142], DC [125,131,
electron microscopy (SEM)/field emission scanning electron microscopy 137,143], and rheology [125] of dental composites. Although the in­
(FESEM) analysis of the fracture surface of the dental composite as the fluence of filler phase content on DC of dental composites was reported
concentration at which a loose interconnected particle network or to be insignificant, the filler phase size exhibited considerable effects on
gel-like particle structure network is formed. Rodrígueza et al. [123] DC and depth of cure [143]. Thus, it is important to trace the DC when
evaluated the percolation threshold, maximum filler content, flexural the filler size influence on other properties of dental composites is being
and compression properties of three different composite containing studied in order to draw a correct interpretation of the results. The filler
monomodal silica fillers in the form of spherical nanoparticles (150–160 size and distribution determine the degree of light scattering during
nm), nanoclusters (3.5 μm), and irregular-shaped glass (1 μm). The au­ photo-polymerization of dental composite by visible-light cure unit, in
thors compared the experimental results with the percolation threshold which the increase of light scattering reduces the light intensity going
and elastic modulus was calculated theoretically according to the through the medium leading to lower DC and depth of cure [143]. Ac­
percolation model [129]. The authors demonstrated the reinforcing ef­ cording to Ruyter et al. [143] the light scattering is influenced by surface
fects of the fillers especially after their percolation threshold as well as reflection, refraction and diffraction of the filler particles present in the
the agreement of the results obtained from experiments and theory. matrix. The authors investigated the effect of filler size on the degree of
However, the authors reported that for more accurate estimation, some light scattering according to a semiempirical equation proposed by

9
A. Aminoroaya et al. Composites Part B 216 (2021) 108852

Fig. 6. Chemical structures of dental resin composites utilizing monomers, with ring-opening polymerization mechanism.

Clewell et al. [144], which relates the light scattering to the particle
diameter (size), refractive indices of organic matrix and inorganic filler,
and wavelength of the visible-light curing unit. They concluded the
following (by considering only the particle size as a variable):
I) maximum scattering (related to lowest DC) is achieved when the
particle size is approximately half of the wavelength of visible
light curing unit,
II) for micron-sized filler particles, reduction of size increases the
light scattering that leads to lower DC, and

10
A. Aminoroaya et al. Composites Part B 216 (2021) 108852

Fig. 7. Classification of filler phase influencing factors on the properties of dental composites.

III) for nano-sized filler particles, reduction of size reduces the light attrition (enhanced wear resistance) (Fig. 8a and b), which was mainly
scattering, which increases the DC. attributed to the reduction of the mean distance between neighboring
particles and the increased number of particles at the surface by the filler
These conclusions were in accordance with the recent studies [125, size-reduction providing a higher contact area between the filler parti­
137]. Three different research studies investigated the size influence of cles and antagonist. Less particle protrusion at the composite surface due
spherical silica (100–1000 nm) and irregularly-shaped Ba-Al-B to filler size-reduction prevent particles from pulling out, which may
(450–1500 nm) silicate glass-filled composites on their wear behavior contribute to enhanced wear resistance. Moreover, composites with
[137], SS-N [141], and SS-S [142]. Organic matrix composition and specific bimodal and trimodal filler sizes (spherical or irregular)
filler content were the same for all the studies and formulations, and the exhibited high wear resistance in addition to acceptable DC level, which
influence of monomodal, bimodal, and trimodal dental composite using advocates the reason for utilizing multimodal filler distribution in
various filler size were studied. Spherical silica fillers with the size of commercial dental composite formulations (known as microhybrids and
250 and 500 nm showed lower DC than the other spherical silica sizes nanohybrids) in order to maintain required characteristics of dental
(100 and 1000 nm) [137]. Additionally, irregular glass with a size of composites as well as a high level of filler loading [137]. Additionally,
450 nm showed lower DC than the other sizes (700, 1,000, and 1500 an increase in filler size (spherical or irregular) showed the reduction of
nm) [137]. This behavior was due to the filler particle size approaching SS-N [141] and SS-S [142], with the exception of spherical silica with
approximately half of the wavelength of the visible-light cure unit and is the size of 1000 nm (Fig. 8c,e). However, the insignificant difference
in accordance with the previously mentioned study by Ruyter et al. between the minimum and maximum values obtained for SS-N (only
[143]. Reduction of filler particle size resulted in lower abrasion and 0.55 vol%) shows the importance of other factors such as organic matrix
chemistry and filler content in regulating the SS-N of dental composites.
Table 7 DC has a direct correlation with SS-N, and it is also influenced by the
Mechanical properties of human enamel and dentin. filler size. However, this correlation was not observed for
irregularly-shaped fillers, which was possibly related to the low differ­
Property Enamel Dentin
ence of DC because of the wider distribution of filler size and mor­
Young’s modulus (GPa) 40-100 [117] 10-30 [117]
phologies than the spherical fillers [141]. Spherical bimodal filler sizes
20-25 [118]
Tensile strength (MPa) – 52-105 [118]
of 100 and 1000 nm showed similar values to the lowest shrinkage strain
⎛
1
⎞
0.7–1.27 [119] 1.13–3.13 [120,121] obtained. These results suggest the investigative importance of the filler
Fracture toughness ⎝MPa m 2 ⎠ packing structure and e DC effects on the SS-N for future studies.
−
1.5–2.7 [122]

Vickers Hardness 300-500 [117] 50-100 [117]

Generally, the influence of filler size on SS-S is two-fold. As filler size

11
A. Aminoroaya et al. Composites Part B 216 (2021) 108852

Fig. 8. Influence of filler size and distribution (monomodal, bimodal, and trimodal) of spherical (S) and irregular-shaped (I) silica fillers on (a) abrasion, (b) attrition,
(c,d) SS-N, and (e,f) SS-S. S and I are related to the spherical fillers and irregular-shaped fillers, respectively. The numbers following these letters show the size of the
utilized fillers in monomodal, bimodal, and trimodal composites. Panels a and b were reproduced with permission from Ref. [137]. Copyright 2005 Elsevier. Panels
d and c were reproduced with permission from Ref. [141]. Copyright 2009 Elsevier. Panels e and f were reproduced with permission from Ref. [142]. Copyright
2012 Elsevier.

reduces in the matrix (at a constant filler volume load):
I) the surface area of the fillers increases and impose more con­
straints upon the matrix phase and
II) the ability for translational/rotational movements by the filler
increases, which leads to enhanced stress relaxation within the
matrix phase [142].
The first effect increases the SS-S while the second leads to lower
values. For more accurate interpretation, other properties such as DC
and SS-N should be considered.
Modulus of dental composites depends on the stress transfer at the
filler-matrix interface, which is influenced by the interfacial properties
and surface area of the filler phase [127]. Finite element analysis of
dental composites containing spherical silica particles at constant filler
volume content showed that filler size reduction results in more uniform
stress distribution and reduction of stress at the filler-matrix interface
(Fig. 9d–f) [127] leading to an enhanced FM. It is expected that an in­
crease in filler size increases stress concentration at the filler-matrix
interface causing more susceptibility to crack nucleation in this area
due to the different rigidities of organic matrix and inorganic filler,
leading to lower mechanical performance such as lower strength of the
dental composites. Karabela et al. [138] investigated the influence of
primary particle size of pyrogenic silica nanocluster (commercially
known as Aesrosil) in the range of 7–40 nm on the properties of
methacrylate-based resin at constant filler weight content (55 wt %).

12
A. Aminoroaya et al.
Fig. 9. FESEM image of the spherical silica nanoparticles synthesized by Stober method (a–c). Reproduced with permission from Ref. [136]. Copyright 2018 Elsevier.
Finite element analysis of Von Mices equivalent stress distribution of dental composites reinforced by different spherical silica sizes (d–f). Reproduced with
permission from Ref. [127]. Copyright 2006 Elsevier.
Despite the agglomerate structure of nanoparticles in the form of
nanocluster particles, fillers with lower primary particle size resulted in
increased DC, which was in accordance with previously discussed
trends. Silica nanocluster with lower primary particle size with similar
surface modification resulted in increased FS. It was attributed to the
higher surface area provided by smaller filler sizes, which increase the
surface energy and lower the stress concentration at the filler-matrix
interface. FM was not influenced by filler primary particle size, and it
was reported to be mainly governed by the stress transition at the
filler-matrix interface that depends on the interfacial properties between
filler and matrix. In another study by Fujita et al. [139], the effect of a
wide range of spherical silica sizes (50, 400, 900, and 2000 nm) at
constant filler weight content revealed that the reduction of silica par­
ticle size increases the depth of cure and reduces the top (irradiating
surface) and bottom (floor surface) Knoop hardness difference.
Increased depth of cure for smaller sized filled composites, provided by
the filler phase in the range of 50 nm-2 μm, cannot be related solely to
the size effect. This is because the size effect in the range of 50nm-2μm
significantly affects the filler refractive index, which may decrease the
DC. As a general trend, when the difference between the refractive
indices of the inorganic filler phase and organic monomer/polymer
13
Composites Part B 216 (2021) 108852
matrix increases, the light transmission of visible light cure unit reduces
due to the intensified refraction/diffraction of the light at filler-matrix
interfaces and results in lower DC and depth of cure [139]. Therefore,
both the filler size and difference between the refractive indices of the
inorganic filler phase and organic monomer/polymer matrix should be
considered for comprehending the accurate influence of filler phase on
DC and depth of cure. Another research study reported opposite results
by investigating the influence of spherical silica particles size (75–1000
nm) of methacrylate-based dental composite on DC, where a decrease in
particle size resulted in lower DC [125]. The authors reported that the
formation of localized nanogel particles before completion of
photo-polymerization of dental composites due to the high intensity of
visible light irradiation and high initiation reaction rates may be the
reason for higher conversion obtained for higher irradiation intensities.
Therefore, the decrease in interparticle spacing as the result of filler size
reduction may limit the size of the nanogel particles leading to lower DC.
As discussed in section 4.1, the mechanical properties of dental
composites are related to the packing structure of the filler phase, which
is developed in the range of percolation from threshold concentration to
maximum filler loading of the filler phase. Percolation threshold con­
centration and maximum filler loading of the filler phase depends on the
A. Aminoroaya et al.
filler size, distribution, and morphology [123,128]. This exceeding
enhancement in the modulus and strength is proportional to the number
of inter-particle contacts, which transmit and dissipate the stress across
the filler phase network [128]. Thus, increased filler loading increases
the mechanical properties of dental composites. In this regard, filler size
has an indirect influence on the mechanical properties of dental com­
posite by affecting filler content. According to Habib et al. [128],
reduction in the size of spherical silica (in the range of 75–1000 nm) in a
methacrylate-based resin resulted in increased viscosity as well as
reduced maximum filler loading. This behavior was explained by the
increased interaction between filler and organic monomer matrix due to
the enhancement of the filler surface area. Considering composites with
maximum filler loading, reduction of filler size exhibited lower FM and
FS. However, it was reported that filler size did not influence FM and FS
for composite with a filler content of 60 wt %. In another research study,
a methacrylate resin showed increased percolation threshold concen­
tration and maximum filler loading for micro-glass filler particles (1 μm)
compared with silica nanoparticles (80 nm) [123]. However, the utili­
zation of doughnut-shaped silica nanoclusters synthesized by using sil­
ica nanoparticles showed similar values of percolation threshold
concentration and maximum filler loading as the micro glass-filled
composite [123]. The authors reported that although reduction of
filler size at constant filler content increases strength, the increased filler
maximum loading achieved by larger filler particles leads to more
enhanced modulus and strength. This reveals the importance of filler
packing density in relation to the mechanical properties of the dental
composite, which may be influenced by several factors such as filler
content, and filler size.
4.3. Distribution of size
Distribution of filler phase size has a vital influence on the packing
14
Composites Part B 216 (2021) 108852
Fig. 10. Schematic representation of the
packing of spherical particles with FCC and
HCG. Arrangement models within the unit
cell (a, d), a ball-and-stick model (b, e), and
an arrangement of atoms in a unit cell (c, f).
Reproduced with permission from
Ref. [135]. Copyright 2017 Elsevier. (g)
Schematic representation of enhanced
packing of the spherical particles by incor­
poration of secondary spherical particle size
of 360 nm (S-360) 195 nm (S-195) with
embedding in the octahedral or tetrahedral
interparticle voids of primary spherical par­
ticles with the size of 920 nm with FCC or
HCG arrangements. Reproduced with
permission from Ref. [136]. Copyright 2018
Elsevier.
structure of the filler phase, which results in the development of me­
chanical properties of dental composites. Wang et al. [135] studied the
theoretical basis of maximum filler loading of spherical particles based
on the theory of close-packed structure. Based on two close-packed
spherical particle arrangement of face centred cubic (FCC) and hexag­
onal close-packed (HCG) (Fig. 10a–f), the authors reported that mono­
modal spherical filler particle (with narrow particle size distribution)
can reach a maximum filler loading of 74.05 vol% regardless of their
particle size. According to their calculation, maximum filler loading can
be further improved by the incorporation of smaller secondary spherical
particles, which can be embedded in the tetrahedral and hexagonal
interparticle spacing of the primary particles according to FCC and HCG
arrangements [135] (Fig. 10g). FCC and HCG arrangements have the
highest packing efficacy compared with other close-packed spherical
particle arrangements including body-centred cubic (BCC), random
close-packed (RCP), and random loose-packed (RLP). In contrary to the
ideal close-packed models of FCC and HCG, more realistic random
packing modes (RCP and RLP with packing efficacy of 64 and 55 vol%,
respectively) consider the interparticle sliding friction in their models
[136]. A research study investigated the packing properties of spherical
silica sizes of 920, 360, and 195 nm on the methacrylate-based resin
(Fig. 9a–c) [136]. Monomodal dental composites based on the silica
filler size of 920 nm were prepared at its maximum filler loading. Then,
bimodal and trimodal formulations were prepared by incorporation of
secondary 360 and/or 195 nm silica particles in the monomodal
formulation to the maximum filler loading. Secondary particle size was
designed based on the sphere sizes that can be embedded in the tetra­
hedral and octahedral interparticle spacing of the FCC and HCP ar­
rangements of the primary particles. According to the experimental
results, the maximum filler loading for monomdal (920 nm), filler
fraction of secondary particles (360 and 195 nm) in bimodals and tri­
modal formulation were lower than the values calculated for ideal
A. Aminoroaya et al.
Fig. 11. Schematic representation of the enhanced packing structure of organic matrix filled with nano-sized particles as the result of the incorporation of secondary
particles in the form micron/sub-micron size particles or nanoclusters/mesoporous fillers.
FCC/HCG models. These results revealed that RLP is probably the best
model for the simulation of real close-packing of the experimental
composites. Moreover, the addition of secondary particles improved the
FS, FM, and CS of the composites, and trimodal formulation showed the
best mechanical properties as well lowest polymerization shrinkage.
The greater size distribution of ground micron-sized glass powders
resulted in enhanced mechanical properties of dental composite mate­
rials [33]. In this regard, Ornaghi et al. [33] determined the subcritical
crack growth susceptibility (SCG) parameters by biaxial flexure dynamic
fatigue test for dental composite containing micron glass powder fillers
at constant filler volume content but with various sizes. This type of
mechanical analysis in combination with fractographic and Weibull
analysis provide beneficial information about the failure mechanism of
dental composites, which can be correlated to the longevity of the ma­
terials [33]. The authors reported that composites with wider granulo­
metric filler size resulted in enhanced SCG parameters, which are related
to better mechanical property stability over time and enhanced
longevity. The authors attributed the results to the increased particle
packing of formulation with wider filler size distribution as smaller
particles occupy the interparticle spaces of larger ones, leading to more
stable mechanical properties by hindering crack propagation by crack
deflection mechanism as well as hindering water penetration.
Monomodal filler (or narrow particle size filler) dental composites
suffer from a lack of mechanical strength and high polymerization
shrinkage due to the inefficient packing network of their filler phase.
Nanocomposites containing monomodal nano-sized fillers exhibited
excellent esthetics and polishability, although they presented insuffi­
cient mechanical property development. To address these issues,
micron-sized filler particles or nanoclusters were incorporated in
conjunction with nano-size particles as co-filler into the formulation of
15
Composites Part B 216 (2021) 108852
dental composites to obtain multi-modal filler sizes with efficient filler
packing (Fig. 11). In this regard, nanoclusters present several advan­
tages over micron-size fillers, which include [123,131,140]:
I) nanoclusters present excellent aesthetic properties when com­
bined with nano-sized fillers. When the composite is subjected to
abrasion, the agglomerated structure of the nanoclusters tends to
break apart instead of total debonding of the filler compared to
micron-size fillers, resulting in high surface polish stability over
time, and
II) nanoclusters exhibit better filler-matrix interface properties due
to their higher surface area than micron-size fillers.
In this regard, Wang et al. [131,140] investigated the properties of a
methacrylate resin by a combination of silica nanoparticles (70 nm) and
silica nanoclusters (0.07–2.7 μm with a primary particle size of 70 nm)
at a different ratio at constant filler content (Fig. 12). The authors re­
ported that at specific nanoparticle/nanocluster ratio (50:20, wt:wt) the
maximum FM, FS, CS, and lowest SS-N, as well as highest wear resis­
tance, is obtained (Fig. 12), which is attributed to the most efficient
packing structure of the fillers at specific filler particles combination.
4.4. Shape and morphology
Particle fillers that generally are utilized in the formulation of dental
composites are produced by top-bottom, such as grinding and sieving,
and bottom-top procedures such as Stöber reaction for the synthesis of
size-controlled silica particles [145,146]. The former generally results in
particulate fillers with irregular morphology and wide distribution of
size, however, the latter results in spherical particles with a narrow
A. Aminoroaya et al. Composites Part B 216 (2021) 108852

Fig. 12. FESEM images of (a) spherical nanoparticles and (b) related nanoclusters synthesized based on the spherical nanoparticles The results of (c) FM, (d) FS, (e)
CS, and (f) wear related to the composites prepared by a different combination of nanoparticles and nanoclusters. Panel a, b, and f were reproduced with permission
from Ref. [140]. Copyright 2013 Elsevier. Panels c, d and e were reproduced with permission from Ref. [131]. Copyright 2015 Elsevier.

distribution of size. Compared with irregular and spherical fillers with
the same filler contents and similar size, irregular morphology provided
improved wear resistance than the spherical morphology [137]. This is
because of the irregular morphology provides higher surface area
leading to stronger filler-matrix adhesion [137,147], however, the effect
of wider filler size distribution, which may lead to more efficient packing
was not taken into account. On the other hand, spherical fillers resulted
in lower values of SS-N and SS-S [141,142].
The influence of fibrillar fillers in the form of fiber/nano-fibers,
nanotubes, and whiskers on the performance of dental composites has
been investigated [148,149]. Incorporation of silica and short glass
fiber, ceramic whiskers, carbon nanotubes, and organic nanofibers
resulted in improved FM, FS, FT, and fatigue resistance. However, poor
esthetics due to refractive index mismatch and poor chemical and me­
chanical stability over time were the major problems of these fillers
[150]. However, utilization of appropriate nanoscale fibrillar filler (such
as silica) as a co-filler may overcome these shortcomings [151]. Wang
et al. [151] investigated the reinforcing mechanisms of silica nanofiber
(diameter: 300–500 nm and length: 5–10 μm) as a single filler and
co-filler for the silica microparticle filled methacrylated resin
(Fig. 13a–c). The authors reported that silica nanofiber as a single filler
with the content of 5–10 wt% exhibits the best FS and FM. Crack
bridging and energy absorption during fiber pull-out were accounted as
the main mechanisms for reinforcement according to the fractographic
analysis by FESEM. Additionally, silica nanofiber as co-filler (5–10 wt%)
with silica microparticles resulted in significant mechanical properties
development. In addition to the reinforcing mechanism mentioned for
silica nanofibers, the special packing structure formed by shielding
network arrangements of nanofibers around silica microparticles
(Fig. 13d–f) might act as a skeleton that leads to enhanced stress transfer

16
A. Aminoroaya et al.
Fig. 13. FESEM images of (a) micron-size spherical silica, (b) silica nanofiber and (c) silica nanoparticles synthesized as the filler and co-filler for the reinforcement
of the dental composites. Schematic representations of the packing arrangement of micron size silica particles and silica nanofibers in the organic matrix of dental
composites (d–f). Reproduced with permission from Ref. [151]. Copyright 2016 Elsevier.
through the materials, yielding enhanced FS and FM. Furthermore, this
skeleton like packing structure of the filler phase resulted in lower
polymerization shrinkage and higher wear resistance. Lower polymeri­
zation shrinkage is attributed to higher network stability as the result of
the incorporation of silica nanofibers. Additionally, enhanced wear
resistance was attributed to the shielding role of nanofiber, which pro­
tects silica microparticles from being detached during the wear process.
However, more research studies investigating the packing arrangements
of nanofibrillar filler with different size and combination ratios would be
desirable in order to clarify the reinforcing mechanisms of these type of
filler in dental composites.
4.5. Interfacial properties and porosity
Filler-matrix interaction in dental composites plays a critical role for
the development of mechanical properties of dental composites [152,
153]. Stress transfer through the organic matrix phase to the inorganic
filler phase strongly depends on the quality of filler-matrix interface
strength. Generally, inorganic filler surfaces are chemically modified by
using an appropriate silane coupling agent in order to provide covalent
interaction between filler surface and organic matrix. 3-methacryloxy­
propyltrimethoxy silane (MPS) is frequently utilized for surface modi­
fication of inorganic filler for incorporation in methacrylate-based resins
[154]. Other coupling agents utilized for the surface modification of the
inorganic fillers incorporated in methacrylate-based resins include
urethane dimethacrylate silane (UDMS) [155], octyltrimethoxysilane
(OTMS) and 10-Methacryloyloxydecyl dihydrogen phosphate (10-MDP)
[156]. Depending on the monomer functional groups in the resin matrix
(refer to sec.3), thiol-based, styrylethyl-based, and ally-based silane
coupling agents have been utilized in the related research studies [157].
Schematic modification of MPS-treatment of inorganic filler surface and
the chemical structure of different coupling agents are illustrated in
Fig. 14.
Since the modulus of dental composites is related to the stress
transfer at the filler-matrix interface, strength of interface adhesion and
quality of surface modification govern the modulus of dental composites
[9,127,158]. The quality of silane surface modification is generally
investigated by spectroscopic and thermogravimetric analyses of filler
particles [158]. The interfacial filler-matrix adhesion can be evaluated
according to the height of tanδ at glass transition temperature of dental
composites according to the dynamic mechanical analyses [21,138].
Furthermore, interfacial properties have been investigated according to
17
Composites Part B 216 (2021) 108852
the microscopic imaging of the fracture surface of dental composites.
According to the fracture surface images, three cases are important
observations [33]:
I) the presence of exposed particles or naked particles, which shows
the weak adhesion of filler-matrix interface (Fig. 15b and c),
II) the presence of particles that are fully covered by the organic
polymer matrix, which shows a good and intact filler-matrix
interface (Fig. 15b), and
III) the fracture surface with high topography, which shows the crack
deflection mechanism by the filler particles.
As the case for nanoclusters, fillers with porous structure have
showed improved filler-matrix interface through the formation of micro-
mechanical interlocking between inorganic filler and organic resin
matrix [159,160]. This type of fillers can result in the enhancement of
mechanical properties of dental composites. In this regard, Wang et al.
[160] prepared silica micron-sized particles (wrinkled mesoporous silica
(WMS), diameter: 496 nm) with mesoporous structure and high specific
surface area (530 m2/g), and compared it to its spherical silica particle
with approximately the same size (Si-507 nm). Both of the filler surfaces
were silane-modified by MPS, and WMS filled formulations resulting in
enhanced FM, FS and VH over the filler weight content of 0–35 wt%
(Fig. 15d–g). This enhancement was related to the increased
filler-matrix adhesion due to the porosity of the WMS fillers. The frac­
ture surface of WMS reinforced composite (Fig. 15b) shows fewer par­
ticle detachments than the fracture surface of Si-507 reinforced
composite (Fig. 15c), which implies a better bonding of WMS filler and
resin matrix. However, more research studies arerequired to reveal the
effect of silane-modification of mesoporous filler structures to clarify the
degree of filler-matrix adhesion improvement by micro-mechanical
interlocking. The summary of important mechanisms and general
tends of results regarding the influence of various filler phase charac­
teristics on the properties of dental composites are provided in Tables 8
and 9.
5. Conclusion and future insights
In light of the aforementioned discussions, it is evident that dental
composite materials are a complex system due to material related factors
affecting their physical, mechanical, and chemical properties to satisfy
the clinical expectations inside the harsh oral environment conditions.
A. Aminoroaya et al. Composites Part B 216 (2021) 108852

Fig. 14. (a) Schematic for the modification in MPS-treatment of inorganic filler surface and (b–g) the chemical structure of different coupling agents.

Furthermore, dental composites are expected to exhibit a collection of
desired properties for their applications. However, the enhancement of
different properties may contrast each other adversely, which add to the
complexity of the design of optimized dental composites formulations.
Based on the scope of study of this review article, it is suggested that
modification of organic resin matrix of a dental composite play a more
significant role regarding the reduction of polymerization shrinkage-
related strain and stress compared with the modification of the filler
phase characteristics. Various types of resin, based on methacrylate
monomers, vinyl monomers, click chemistry-based resin systems, and

18
A. Aminoroaya et al.
Fig. 15. FE-SEM images of the fracture surfaces of (a) unfilled resin matrix, (b) WMS reinforced composite, and (c) Si-507 reinforced dental composite (arrows in the
picture show the filler particles detachment at the fracture surfaces). (d) FS, (e) FM, (f) CS, and (g) VH of WMS or Si507 reinforced composites at different filler
content. Reproduced with permission from Ref. [160]. Copyright 2017 Elsevier.
ring-opening polymerization monomer systems were investigated in the
recent studies. Dental composites based on the monomers with reduced
polymerization shrinkage-related strain and stress can be correlated
with enhanced longevity due to lower secondary caries and bulk/mar­
ginal fracture. Additionally, the introduction of bio-based monomers
with new structures for the replacement of conventional monomers (e.
g., BisGMA and TEGDMA) will be of great importance to future research
studies in order to limit the health-related risks of dental composites. On
the other hand, monomers with reduced viscosities that maintain/
improve other important properties such as DC, mechanical character­
istics, and polymerization shrinkage of the resin are crucial in future
research regarding formulation of dental composites with higher filler
content and more efficient packing arrangements of the filler phase.
Moreover, refractive index and in vitro cytotoxicity analysis of new
proposed monomers as an alternative for conventional monomers are
recommended to exhibit the true potential of the monomer for further
investigations. Filler phase characteristics play a more significant role
regarding the development of the mechanical properties of dental
composites such as modulus, strength, fracture toughness, fatigue life,
hardness, and wear resistance compared to the modification of organic
resin matrix. It was comprehended that content, size, distribution,
shape, porosity, and surface modification of filler particles are very
19
Composites Part B 216 (2021) 108852
important for designing a filler phase with efficient packing and
enhanced filler-matrix interactions in order to provide exceeding
improvement into the mechanical properties of dental composites as
well as maintaining acceptable DC and depth of cure. Further in­
vestigations of theoretical studies to model and simulate the packing
structure of the filler phase with various combination and morphology
in future studies will be beneficial. Additionally, utilization of nano-
fibrillar fillers as a co-filler in the matrix of particulate filled dental
composites in order to improve the packing structure of filler phase is
favorable. More research studies are also necessary to elucidate the
impact of various characteristics of porous fillers (such as surface area,
type of porosity, and pore size distribution) on the mechanical proper­
ties of dental composites. Investigation of new type of chemical surface
modifications with respect to new monomer chemistry (such as thiol-X
resin and ring-opening polymerization resin) is interesting that can
reveal their potential for future dental composites. In addition, the
development of dental composites with novel properties such as anti­
bacterial properties, bioactive activity (remineralizing), and self-healing
properties have been investigated in recent studies and will be the
interesting subjects for future studies. However, the investigation of this
type of modifications was not in the scope of this study.
A. Aminoroaya et al. Composites Part B 216 (2021) 108852

Table 8 Table 9
Summary of filler content and size influences on the performance of dental Summary of filler size distribution, shape, morphology, and interfacial proper­
composites. ties, influences on the performance of dental composites.
Filler phase Important mechanisms General trends of results Filler phase Important mechanisms General trends of results
characteristics characteristic

Content Three filler content zone are
important regarding the filler
packing structure: I) Low
particle concentration (non-
aggregated), II) Intermediate
particle concentration
(percolation threshold), and
III) Maximum possible filler
concentration
● In zone, I, the development
of mechanical properties is
governed by hydrodynamic
effects of individual
particles (or stress
transition at the filler-
matrix interface) [126,127]
● In zone, I and II,
development of mechanical
properties is governed by
stress transition/dissipation
at the interparticle contacts
across the percolation
network of filler particles
[123,128]
Size ● Filler size-reduction
decrease interparticle
spacing, which limits the
formation of localized
nanogel in the matrix lead­
ing to lower DC [125]
● Filler size reduction has
two-fold influence on SS-S:
I) increase of filler surface
area provides more con­
straints on matrix phase,
which increase SS-S, and II)
facilitation of the trans­
lational/rotational move­
ment of filler particles
increases stress relaxation
during photo-
polymerization, which
lower SS-S [142]
● Filler size reduction
increases filler surface area,
which increases the
uniformity of stress
distribution through the
medium and decreases the
stress concentration at the
filler-matrix interface [127]
● Filler size-reduction re­
duces the maximum filler
loading due to increase of
composite matrix viscosity,
which limits the develop­
ment of mechanical prop­
erties [128] and control of
SS-N [141]
● Filler size-reduction de­
creases mean distance be­
tween neighboring
particles, increases parti­
cles at the surface, and de­
creases particle protrusion
at the surface, which en­
hances wear resistance
[137]
● Increase of filler content
does not affect DC (when
filler surface area is not too
high) [124]
● Exceeding increase of
modulus and strength at
high filler content (after
percolation threshold
concentration) [123,128]
● SS-S is mainly governed by
matrix phase composition
and chemistry [130,131],
and filler content
exhibited contradicting
effects on SS-S [124,132,
133]
● Increase in filler content
decreases SS-N [124,128]
● Filler size affects its
refractive index and
degree of light scattering
in the matrix phase, which
can impact DC and depth
of cure [139,143]
● Maximum light scattering
of fillers, which is
associated with lowest DC,
is provided when filler size
is approximately half of
the wavelength of visible
light curing unit [125,
143]
● Filler size reduction
generally increases DC and
Depth of cure [125,137]
● At constant filler content,
reduction of size increases
modulus and strength
[127], but the reduction of
size lowers the modulus
and strength at maximum
filler loading [128]
Author contributions
publication.
Declaration of competing interest
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Distribution of ● Multi-modal filler phase or
Size wide size distribution filler
phase increases maximum
filler loading as smaller
particles occupy the
interparticle spaces of larger
ones leading to more
efficient packing [33,135,
136]
Shape and ● Irregular shaped particulate
morphology fillers exhibit wide size
distribution and higher
surface area than
monomodal spherical
particulate fillers, which
provide stronger filler-
matrix adhesion and more
efficient packing leading to
enhanced wear resistance
[137]
● Nanofibers increase modulus
and strength by crack
bridging and energy
adsorption during fiber
pullout [151]
● Nanofibers as co-filler can
provide special packing
structure by providing
shielding network arrange­
ment of nanofibers around
other particulate fillers
leading to higher wear
resistance and lower poly­
merization shrinkage [151]
Interfacial ● Surface silane modification
properties and of inorganic fillers can
porosity improve the filler-matric
interface strength leading to
improved stress transfer at
the interface [157]
● Fillers with porous structure
provide high surface area
and micromechanical
interlocking interaction at
the filler-matrix interface
that can increase mechanical
properties [160]
All authors contributed to the work and approved the article for
The authors declare that they have no known competing financial
● Multi-modal filler phase
or wide size distribution
filler phase provides
better packing structure,
increased mechanical
properties and wear
resistance in comparison
to unimodal/narrow size
distribution filler phase
[136]
● Specific combination of a
micron size (or
nanocluster)/nano-size
filler phase exhibits the
best packing, which
leads to the highest me­
chanical properties as
well as wear resistance
[131,140]
● Spherical shaped
particulate fillers exhibit
lower SS-N and SS-S than
irregularly shaped par­
ticulate fillers [141,142]
● Modulus is mainly
governed by stress
transition at the
interface, which depends
on interfacial adhesion
strength at the interface
[127,158]
● Quality of filler-matrix
interaction can be traced
according to the fracture
surface imaging [123,
160]

20
A. Aminoroaya et al. Composites Part B 216 (2021) 108852

Acknowledgements [26] Cramer N, Stansbury J, Bowman C. Recent advances and developments in

composite dental restorative materials. J Dent Res 2011;90(4):402–16.
[27] Braga R, Ferracane J. Contraction stress related to degree of conversion and
Oisik Das expresses his gratitude towards his uncle, Dr (Prof) Dev­ reaction kinetics. J Dent Res 2002;81(2):114–8.
dutta Das of Maharishi Markandewshwar University, Ambala, India. [28] Calheiros FC, Sadek FT, Boaro LCC, Braga RR. Polymerization stress related to
Devdutta Das lost the battle against COVID-19 but won the war in radiant exposure and its effect on microleakage of composite restorations. J Dent
2007;35(12):946–52.
creating an academic environment that is conducive to high-class dental [29] Wang X, Huyang G, Palagummi SV, Liu X, Skrtic D, Beauchamp C, et al. High
education and research. One of his exceptional attributes was to spot the performance dental resin composites with hydrolytically stable monomers. Dent
defect or disease in an individual from feet away even before examining Mater 2018;34(2):228–37.
[30] Yuan S, Liu F, He J. Preparation and characterization of low polymerization
the patient. shrinkage and bis-GMA-free dental resin system. Adv Polym Technol 2015;34(3).
[31] Wei Y-j, Silikas N, Zhang Z-t, Watts DC. Diffusion and concurrent solubility of self-
References adhering and new resin–matrix composites during water sorption/desorption
cycles. Dent Mater 2011;27(2):197–205.
[32] Imazato S, Tarumi H, Kato S, Ebi N, Ehara A, Ebisu S. Water sorption, degree of
[1] Health UDo, Committee HSOHC. US department of health and human services
conversion, and hydrophobicity of resins containing Bis-GMA and TEGDMA. Dent
oral health strategic framework, 2014–2017. Publ Health Rep 2016;131(2):
Mater J 1999;18(1):124–32.
242–57.
[33] Ornaghi BP, Meier MM, Rosa V, Cesar PF, Lohbauer U, Braga RR. Subcritical
[2] Dye BA, Li X, Beltrán-Aguilar ED. Selected oral health indicators in the United
crack growth and in vitro lifetime prediction of resin composites with different
States, 2005-2008. 2012.
filler distributions. Dent Mater 2012;28(9):985–95.
[3] Beazoglou T, Eklund S, Heffley D, Meiers J, Brown LJ, Bailit H. Economic impact
[34] Chang M-C, Lin L-D, Chuang F-H, Chan C-P, Wang T-M, Lee J-J, et al.
of regulating the use of amalgam restorations. Publ Health Rep 2007;122(5):
Carboxylesterase expression in human dental pulp cells: role in regulation of
657–63.
BisGMA-induced prostanoid production and cytotoxicity. Acta Biomater 2012;8
[4] Eltahlah D, Lynch CD, Chadwick BL, Blum IR, Wilson NH. An update on the
(3):1380–7.
reasons for placement and replacement of direct restorations. J Dent 2018;72:
[35] Gao Y, Sagi S, Zhang L, Liao Y, Cowles DM, Sun Y, et al. Electrospun nano-scaled
1–7.
glass fiber reinforcement of bis-GMA/TEGDMA dental composites. J Appl Polym
[5] Yingchao Z, Haihuan G, Dan F, Tengjiaozi F, Danfeng C, Zuosen S, et al. New
Sci 2008;110(4):2063–70.
strategy for overcoming microleakage: an elastic layer for dental caries
[36] Liang X, Liu F, He J. Synthesis of none Bisphenol A structure dimethacrylate
restoration. J Mater Chem B 2015;3(21):4401–5.
monomer and characterization for dental composite applications. Dent Mater
[6] Zhang Y, Huang C, Chang J. Ca-Doped mesoporous SiO2/dental resin composites
2014;30(8):917–25.
with enhanced mechanical properties, bioactivity and antibacterial properties.
[37] Zhang L, Gao Y, Chen Q, Tian M, Fong H. Bis-GMA/TEGDMA dental composites
J Mater Chem B 2018;6(3):477–86.
reinforced with nano-scaled single crystals of fibrillar silicate. J Mater Sci 2010;
[7] Cho K, Yasir M, Jung M, Willcox MDP, Stenzel MH, Rajan G, et al. Hybrid
45(9):2521–4.
engineered dental composites by multiscale reinforcements with chitosan-
[38] Chadda H, Satapathy BK, Patnaik A, Ray AR. Mechanistic interpretations of
integrated halloysite nanotubes and S-glass fibers. Compos B Eng 2020;202:
fracture toughness and correlations to wear behavior of hydroxyapatite and
108448.
silica/hydroxyapatite filled bis-GMA/TEGDMA micro/hybrid dental restorative
[8] Taheri MM, Abdul Kadir MR, Shokuhfar T, Hamlekhan A, Shirdar MR,
composites. Compos B Eng 2017;130:132–46.
Naghizadeh F. Fluoridated hydroxyapatite nanorods as novel fillers for improving
[39] Contreras PP, Tyagi P, Agarwal S. Low volume shrinkage of polymers by
mechanical properties of dental composite: synthesis and application. Mater Des
photopolymerization of 1,1-bis(ethoxycarbonyl)-2-vinylcyclopropanes. Polym
2015;82:119–25.
Chem 2015;6(12):2297–304.
[9] Cho K, Sul J-H, Stenzel MH, Farrar P, Prusty BG. Experimental cum
[40] Ye Q, Abedin F, Parthasarathy R, Spencer P. Chapter 11 photoinitiators in
computational investigation on interfacial and mechanical behavior of short glass
dentistry: challenges and advances. Photopolymerisation initiating systems. The
fiber reinforced dental composites. Compos B Eng 2020;200:108294.
Royal Society of Chemistry; 2018. p. 297–336.
[10] Gong H, Guo X, Cao D, Gao P, Feng D, Zhang X, et al. Photopolymerizable and
[41] Berlanga Duarte ML, Reyna Medina LA, Torres Reyes P, Esparza González SC,
moisture-curable polyurethanes for dental adhesive applications to increase
Herrera González AM. Dental restorative composites containing methacrylic
restoration durability. J Mater Chem B 2019;7(5):744–54.
spiroorthocarbonate monomers as antishrinking matrixes. J Appl Polym Sci 2019;
[11] Demarco FF, Corrêa MB, Cenci MS, Moraes RR, Opdam NJ. Longevity of posterior
136(9):47114.
composite restorations: not only a matter of materials. Dent Mater 2012;28(1):
[42] Tauscher S, Catel Y, Fässler P, Fischer U, Moszner N. Development of low-
87–101.
shrinkage composites based on novel crosslinking vinylcyclopropanes. J Appl
[12] Opdam N, Van de Sande F, Bronkhorst E, Cenci M, Bottenberg P, Pallesen U, et al.
Polym Sci 2017;134(48):45577.
Longevity of posterior composite restorations: a systematic review and meta-
[43] Hsu S-H, Chen R-S, Chang Y-L, Chen M-H, Cheng K-C, Su W-F. Biphenyl liquid
analysis. J Dent Res 2014;93(10):943–9.
crystalline epoxy resin as a low-shrinkage resin-based dental restorative
[13] Ástvaldsdóttir Á, Dagerhamn J, van Dijken JW, Naimi-Akbar A, Sandborgh-
nanocomposite. Acta Biomater 2012;8(11):4151–61.
Englund G, Tranaeus S, et al. Longevity of posterior resin composite restorations
[44] Danso R, Hoedebecke B, Whang K, Sarrami S, Johnston A, Flipse S, et al.
in adults–A systematic review. J Dent 2015;43(8):934–54.
Development of an oxirane/acrylate interpenetrating polymer network (IPN)
[14] Demarco FF, Collares K, Coelho-de-Souza FH, Correa MB, Cenci MS, Moraes RR,
resin system. Dent Mater: Off. Publ. Acad. Dent. Mater. 2018;34(10):1459.
et al. Anterior composite restorations: a systematic review on long-term survival
[45] Sherborne C, Owen R, Reilly GC, Claeyssens F. Light-based additive
and reasons for failure. Dent Mater 2015;31(10):1214–24.
manufacturing of PolyHIPEs: controlling the surface porosity for 3D cell culture
[15] Collares K, Opdam N, Laske M, Bronkhorst E, Demarco F, Correa M, et al.
applications. Mater Des 2018;156:494–503.
Longevity of anterior composite restorations in a general dental practice-based
[46] Geurtsen W, Lehmann F, Spahl W, Leyhausen G. Cytotoxicity of 35 dental resin
network. J Dent Res 2017;96(10):1092–9.
composite monomers/additives in permanent 3T3 and three human primary
[16] Habib E, Wang R, Wang Y, Zhu M, Zhu XX. Inorganic fillers for dental resin
fibroblast cultures. J Biomed Mater Res 1998;41(3):474–80.
composites: present and future. ACS Biomater Sci Eng 2016;2(1):1–11.
[47] Labella R, Braden M, Clarke RL, Davy KWM. THFMA in dental monomer systems.
[17] Ferracane JL. Resin composite—state of the art. Dent Mater 2011;27(1):29–38.
Biomaterials 1996;17(4):431–6.
[18] Makvandi P, Jamaledin R, Jabbari M, Nikfarjam N, Borzacchiello A. Antibacterial
[48] Yin M, Guo S, Liu F, He J. Synthesis of fluorinated dimethacrylate monomer and
quaternary ammonium compounds in dental materials: a systematic review. Dent
its application in preparing Bis-GMA free dental resin. J. Mech. Behav. Biomed.
Mater 2018;34(6):851–67.
Mater. 2015;51:337–44.
[19] Althaqafi KA, Satterthwaite J, Silikas N. A review and current state of autonomic
[49] Kalachandra S, Taylor DF, DePorter CD, Grubbs HJ, McGrath JE. Polymeric
self-healing microcapsules-based dental resin composites. Dent Mater 2020;36(3):
materials for composite matrices in biological environments. Polymer 1993;34
329–42.
(4):778–82.
[20] Xu X, He L, Zhu B, Li J, Li J. Advances in polymeric materials for dental
[50] Dickens SH, Stansbury J, Choi K, Floyd C. Photopolymerization kinetics of
applications. Polym Chem 2017;8(5):807–23.
methacrylate dental resins. Macromolecules 2003;36(16):6043–53.
[21] Aminoroaya A, Esmaeely Neisiany R, Nouri Khorasani S, Panahi P, Das O,
[51] Charton C, Falk V, Marchal P, Pla F, Colon P. Influence of Tg, viscosity and
Ramakrishna S. A review of dental composites: methods of characterizations. ACS
chemical structure of monomers on shrinkage stress in light-cured
Biomater Sci Eng 2020;6(7):3713–44.
dimethacrylate-based dental resins. Dent Mater 2007;23(11):1447–59.
[22] Svanberg M, Mjör I, Ørstavik D. Mutans streptococci in plaque from margins of
[52] Barszczewska-Rybarek IM. Characterization of urethane-dimethacrylate
amalgam, composite, and glass-ionomer restorations. J Dent Res 1990;69(3):
derivatives as alternative monomers for the restorative composite matrix. Dent
861–4.
Mater 2014;30(12):1336–44.
[23] Kidd E, Joyston-Bechal S, Beighton D. Microbiological validation of assessments
[53] Davy KWM, Kalachandra S, Pandain MS, Braden M. Relationship between
of caries activity during cavity preparation. Caries Res 1993;27(5):402–8.
composite matrix molecular structure and properties. Biomaterials 1998;19(22):
[24] Marsh P. The role of microbiology in models of dental caries. Adv Dent Res 1995;
2007–14.
9(3):244–54.
[54] Podgórski M. Synthesis and characterization of acetyloxypropylene
[25] Reis A, Giannini M, Lovadino J. The effect of six polishing systems on the surface
dimethacrylate as a new dental monomer. Dent Mater 2011;27(8):748–54.
roughness of two packable resin-based composites. Am J Dent 2002;15(3):193–7.
[55] Podgórski M. Structure–property relationship in new photo-cured
dimethacrylate-based dental resins. Dent Mater 2012;28(4):398–409.

21
A. Aminoroaya et al.
[56] Podgórski M, Becka E, Claudino M, Flores A, Shah PK, Stansbury JW, et al. Ester-
free thiol–ene dental restoratives—Part A: resin development. Dent Mater 2015;
31(11):1255–62.
[57] Khatri CA, Stansbury JW, Schultheisz CR, Antonucci JM. Synthesis,
characterization and evaluation of urethane derivatives of Bis-GMA. Dent Mater
2003;19(7):584–8.
[58] Gonçalves F, Pfeifer CS, Ferracane JL, Braga RR. Contraction stress determinants
in dimethacrylate composites. J Dent Res 2008;87(4):367–71.
[59] Chung CM, Kim JG, Kim MS, Kim KM, Kim KN. Development of a new
photocurable composite resin with reduced curing shrinkage. Dent Mater 2002;
18(2):174–8.
[60] Łukaszczyk J, Janicki B, Frick A. Investigation on synthesis and properties of
isosorbide based bis-GMA analogue. J Mater Sci Mater Med 2012;23(5):1149–55.
[61] Sideridou I, Tserki V, Papanastasiou G. Effect of chemical structure on degree of
conversion in light-cured dimethacrylate-based dental resins. Biomaterials 2002;
23(8):1819–29.
[62] Kerby RE, Knobloch LA, Schricker S, Gregg B. Synthesis and evaluation of
modified urethane dimethacrylate resins with reduced water sorption and
solubility. Dent Mater 2009;25(3):302–13.
[63] Pfeifer CS, Shelton ZR, Braga RR, Windmoller D, Machado JC, Stansbury JW.
Characterization of dimethacrylate polymeric networks: a study of the crosslinked
structure formed by monomers used in dental composites. Eur Polym J 2011;47
(2):162–70.
[64] Inagaki LT, Dainezi VB, Alonso RCB, Paula ABd, Garcia-Godoy F, Puppin-
Rontani RM, et al. Evaluation of sorption/solubility, softening, flexural strength
and elastic modulus of experimental resin blends with chlorhexidine. J Dent
2016;49:40–5.
[65] Łukaszczyk J, Janicki B, Kożuch J, Wojdyła H. Synthesis and characterization of
low viscosity dimethacrylic resin based on isosorbide. J Appl Polym Sci 2013;130
(4):2514–22.
[66] He J, Liu F, Luo Y, Jia D. Synthesis and characterization of a dimethacrylates
monomer with low shrinkage and water sorption for dental application. J Appl
Polym Sci 2012;125(1):114–20.
[67] Gonçalves L, Filho JDN, Guimarães JGA, Poskus LT, Silva EM. Solubility, salivary
sorption and degree of conversion of dimethacrylate-based polymeric matrixes.
J Biomed Mater Res B Appl Biomater 2008;85B(2):320–5.
[68] Nie J, Lovell LG, Bowman CN. Synthesis and characterization of N-isopropyl, N-
methacryloxyethyl methacrylamide as a possible dental resin. Biomaterials 2001;
22(6):535–40.
[69] Huang S, Podgórski M, Zhang X, Sinha J, Claudino M, Stansbury J, et al. Dental
restorative materials based on thiol-michael photopolymerization. J Dent Res
2018;97(5):530–6.
[70] Schoerpf S, Catel Y, Moszner N, Gorsche C, Liska R. Enhanced reduction of
polymerization-induced shrinkage stress via combination of radical ring opening
and addition fragmentation chain transfer. Polym Chem 2019;10(11):1357–66.
[71] Ligon-Auer SC, Schwentenwein M, Gorsche C, Stampfl J, Liska R. Toughening of
photo-curable polymer networks: a review. Polym Chem 2016;7(2):257–86.
[72] Beigi S, Yeganeh H, Atai M. Evaluation of fracture toughness and mechanical
properties of ternary thiol–ene–methacrylate systems as resin matrix for dental
restorative composites. Dent Mater 2013;29(7):777–87.
[73] Podgórski M. Synthesis and characterization of novel dimethacrylates of different
chain lengths as possible dental resins. Dent Mater 2010;26(6):e188–94.
[74] Walters NJ, Xia W, Salih V, Ashley PF, Young AM. Poly(propylene glycol) and
urethane dimethacrylates improve conversion of dental composites and reveal
complexity of cytocompatibility testing. Dent Mater 2016;32(2):264–77.
[75] Berlanga Duarte ML, Reyna Medina LA, Reyes PT, González Pérez SE, Herrera
González AM. Biobased isosorbide methacrylate monomer as an alternative to
bisphenol A glycerolate dimethacrylate for dental restorative applications. J Appl
Polym Sci 2017;134(11).
[76] Herrera-González AM, Pérez-Mondragón AA, Cuevas-Suárez CE. Evaluation of
bio-based monomers from isosorbide used in the formulation of dental composite
resins. J. Mech. Behav. Biomed. Mater. 2019;100:103371.
[77] Srivastava R, Liu J, He C, Sun Y. BisGMA analogues as monomers and diluents for
dental restorative composite materials. Mater Sci Eng C 2018;88:25–31.
[78] Srivastava R, Wolska J, Walkowiak-Kulikowska J, Koroniak H, Sun Y. Fluorinated
bis-GMA as potential monomers for dental restorative composite materials. Eur
Polym J 2017;90:334–43.
[79] Cuevas-Suárez CE, González-López JA, da Silva AF, Piva E, Herrera-González AM.
Synthesis of an allyl carbonate monomer as alternative to TEGDMA in the
formulation of dental composite resins. J. Mech. Behav. Biomed. Mater. 2018;87:
148–54.
[80] He J, Garoushi S, Säilynoja E, Vallittu PK, Lassila L. The effect of adding a new
monomer “Phene” on the polymerization shrinkage reduction of a dental resin
composite. Dent Mater 2019;35(4):627–35.
[81] Herrera-González AM, González-López JA, Cuevas-Suárez CE, García-Castro MA,
Vargas-Ramírez M. Formulation and evaluation of dental composite resins with
allylcarbonate monomer as eluent for Bis-GMA. Polym Compos 2018;39:
E342–50.
[82] Pérez-Mondragón AA, Cuevas-Suárez CE, Castillo ORS, González-López JA,
Herrera-González AM. Evaluation of biocompatible monomers as substitutes for
TEGDMA in resin-based dental composites. Mater Sci Eng C 2018;93:80–7.
[83] Herrera-González AM, González-López JA, Cuevas-Suárez CE, García-Castro MA,
Vargas-Ramírez M. Formulation and evaluation of dental composite resins with
allylcarbonate monomer as eluent for Bis-GMA. Polym Compos 2018;39(S1):
E342–50.
22
Composites Part B 216 (2021) 108852
[84] Pérez-Mondragón AA, Cuevas-Suárez CE, Suárez Castillo OR, González-López JA,
Herrera-González AM. Evaluation of biocompatible monomers as substitutes for
TEGDMA in resin-based dental composites. Mater Sci Eng C 2018;93:80–7.
[85] Cramer NB, Couch CL, Schreck KM, Boulden JE, Wydra R, Stansbury JW, et al.
Properties of methacrylate–thiol–ene formulations as dental restorative materials.
Dent Mater 2010;26(8):799–806.
[86] Boulden JE, Cramer NB, Schreck KM, Couch CL, Bracho-Troconis C,
Stansbury JW, et al. Thiol–ene–methacrylate composites as dental restorative
materials. Dent Mater 2011;27(3):267–72.
[87] Schreck KM, Leung D, Bowman CN. Hybrid organic/inorganic thiol–ene-based
photopolymerized networks. Macromolecules 2011;44(19):7520–9.
[88] Podgórski M, Becka E, Chatani S, Claudino M, Bowman CN. Ester-free thiol-X
resins: new materials with enhanced mechanical behavior and solvent resistance.
Polym Chem 2015;6(12):2234–40.
[89] Bacchi A, Yih JA, Platta J, Knight J, Pfeifer CS. Shrinkage/stress reduction and
mechanical properties improvement in restorative composites formulated with
thio-urethane oligomers. J. Mech. Behav. Biomed. Mater. 2018;78:235–40.
[90] Bacchi A, Pfeifer CS. Rheological and mechanical properties and interfacial stress
development of composite cements modified with thio-urethane oligomers. Dent
Mater 2016;32(8):978–86.
[91] Bacchi A, Consani RL, Martim GC, Pfeifer CS. Thio-urethane oligomers improve
the properties of light-cured resin cements. Dent Mater 2015;31(5):565–74.
[92] Bacchi A, Nelson M, Pfeifer CS. Characterization of methacrylate-based
composites containing thio-urethane oligomers. Dent Mater 2016;32(2):233–9.
[93] Ferracane J, Consani R, Pfeifer C. Thio-urethanes improve properties of dual-
cured composite cements. 2014.
[94] Cramer NB, Bowman CN. Kinetics of thiol–ene and thiol–acrylate
photopolymerizations with real-time fourier transform infrared. J Polym Sci
Polym Chem 2001;39(19):3311–9.
[95] Cramer NB, Davies T, O’Brien AK, Bowman CN. Mechanism and modeling of a
Thiol− ene photopolymerization. Macromolecules 2003;36(12):4631–6.
[96] Cramer NB, Reddy SK, O’Brien AK, Bowman CN. Thiol− ene photopolymerization
mechanism and rate limiting step changes for various vinyl functional group
chemistries. Macromolecules 2003;36(21):7964–9.
[97] Hoyle CE, Lee TY, Roper T. Thiol–enes: chemistry of the past with promise for the
future. J Polym Sci Polym Chem 2004;42(21):5301–38.
[98] Reddy SK, Cramer NB, Bowman CN. Thiol− vinyl mechanisms. 1. Termination
and propagation kinetics in Thiol− ene photopolymerizations. Macromolecules
2006;39(10):3673–80.
[99] Cramer NB, Bowman CN. Thiol-ene and thiol-yne chemistry in ideal network
synthesis. Thiol-X Chemistries in Polymer and Materials Science. 2013. p. 1–27.
[100] Chiou B-S, Khan SA. Real-time FTIR and in situ rheological studies on the UV
curing kinetics of thiol-ene polymers. Macromolecules 1997;30(23):7322–8.
[101] Lu H, Carioscia JA, Stansbury JW, Bowman CN. Investigations of step-growth
thiol-ene polymerizations for novel dental restoratives. Dent Mater 2005;21(12):
1129–36.
[102] Senyurt AF, Wei H, Hoyle CE, Piland SG, Gould TE. Ternary thiol− ene/acrylate
photopolymers: effect of acrylate structure on mechanical properties.
Macromolecules 2007;40(14):4901–9.
[103] Bacchi A, Yih JA, Platta J, Knight J, Pfeifer CS. Shrinkage/stress reduction and
mechanical properties improvement in restorative composites formulated with
thio-urethane oligomers. J. Mech. Behav. Biomed. Mater. 2018;78:235–40.
[104] Huang S, Podgórski M, Zhang X, Sinha J, Claudino M, Stansbury JW, et al. Dental
restorative materials based on thiol-michael photopolymerization. J Dent Res
2018;97(5):530–6.
[105] Fu J, Liu W, Hao Z, Wu X, Yin J, Panjiyar A, et al. Characterization of a low
shrinkage dental composite containing bismethylene spiroorthocarbonate
expanding monomer. Int J Mol Sci 2014;15(2):2400–12.
[106] Moszner N, Völkel T, Zeuner F, Rheinberger V. Synthesis and radical
polymerization of 2-vinylcyclopropanes. Macromolecular Symposia: Wiley Online
Library; 2000. p. 151–9.
[107] Catel Y, Fässler P, Fischer U, Gorsche C, Schörpf S, Tauscher S, et al. Evaluation of
difunctional vinylcyclopropanes as reactive diluents for the development of low-
shrinkage composites. Macromol Mater Eng 2017;302(7):1700021.
[108] Xiong J, Sun X, Li Y, Chen J. Polymerization shrinkage, stress, and degree of
conversion in silorane-and dimethacrylate-based dental composites. J Appl Polym
Sci 2011;122(3):1882–8.
[109] Gao B-T, Lin H, Zheng G, Xu Y-X, Yang J-L. Comparison between a silorane-based
composite and methacrylate-based composites: shrinkage characteristics, thermal
properties, gel point and vitrification point. Dent Mater J 2012:1201190226.
[110] Ilie N, Hickel R. Silorane-based dental composite: behavior and abilities. Dent
Mater J 2006;25(3):445–54.
[111] Weinmann W, Thalacker C, Guggenberger R. Siloranes in dental composites. Dent
Mater 2005;21(1):68–74.
[112] Tauscher S, Catel Y, Fässler P, Fischer U, Moszner N. Development of low-
shrinkage composites based on novel crosslinking vinylcyclopropanes. J Appl
Polym Sci 2017;134(48):45577.
[113] Catel Y, Fässler P, Fischer U, Gorsche C, Schörpf S, Tauscher S, et al. Evaluation of
difunctional vinylcyclopropanes as reactive diluents for the development of low-
shrinkage composites. Macromol Mater Eng 2017;302(7):1700021.
[114] Danso R, Hoedebecke B, Whang K, Sarrami S, Johnston A, Flipse S, et al.
Development of an oxirane/acrylate interpenetrating polymer network (IPN)
resin system. Dent Mater 2018;34(10):1459–65.
[115] Dong Z, Ni Y, Yang X, Hu C, Sun J, Li L, et al. Characterization and analysis of
fluoride calcium silicate composite interface in remineralization of dental enamel.
Compos B Eng 2018;153:393–7.
A. Aminoroaya et al.
[116] Sowan N, Lu Y, Kolb KJ, Cox LM, Long R, Bowman CN. Enhancing the toughness
of composites via dynamic thiol–thioester exchange (TTE) at the resin–filler
interface. Polym Chem 2020;11(29):4760–7.
[117] Zhang Y-R, Du W, Zhou X-D, Yu H-Y. Review of research on the mechanical
properties of the human tooth. Int J Oral Sci 2014;6(2):61–9.
[118] Kinney JH, Marshall SJ, Marshall GW. The mechanical properties of human
dentin: a critical review and Re-evaluation of the dental literature. Crit Rev Oral
Biol Med 2003;14(1):13–29.
[119] Hassan R, Caputo AA, Bunshah RF. Fracture toughness of human enamel. J Dent
Res 1981;60(4):820–7.
[120] El Mowafy OM, Watts DC. Fracture toughness of human dentin. J Dent Res 1986;
65(5):677–81.
[121] Iwamoto N, Ruse ND. Fracture toughness of human dentin. J Biomed Mater Res
2003;66A(3):507–12.
[122] Nalla RK, Kinney JH, Ritchie RO. Effect of orientation on the in vitro fracture
toughness of dentin: the role of toughening mechanisms. Biomaterials 2003;24
(22):3955–68.
[123] Rodríguez HA, Kriven WM, Casanova H. Development of mechanical properties in
dental resin composite: effect of filler size and filler aggregation state. Mater Sci
Eng C 2019;101:274–82.
[124] Gonçalves F, Kawano Y, Braga RR. Contraction stress related to composite
inorganic content. Dent Mater 2010;26(7):704–9.
[125] Habib E, Wang R, Zhu XX. Correlation of resin viscosity and monomer conversion
to filler particle size in dental composites. Dent Mater 2018;34(10):1501–8.
[126] Song Y, Zheng Q. Concepts and conflicts in nanoparticles reinforcement to
polymers beyond hydrodynamics. Prog Mater Sci 2016;84:1–58.
[127] Tanimoto Y, Kitagawa T, Aida M, Nishiyama N. Experimental and computational
approach for evaluating the mechanical characteristics of dental composite resins
with various filler sizes. Acta Biomater 2006;2(6):633–9.
[128] Habib E, Wang R, Zhu XX. Monodisperse silica-filled composite restoratives
mechanical and light transmission properties. Dent Mater 2017;33(3):280–7.
[129] Ouali N, Cavaillé J, Perez J. Elastic, viscoelastic and plastic behavior of
multiphase polymer blends. Plast, Rubber Compos Process Appl 1991;16(1):
55–60.
[130] Gonçalves F, Azevedo CLN, Ferracane JL, Braga RR. BisGMA/TEGDMA ratio and
filler content effects on shrinkage stress. Dent Mater 2011;27(6):520–6.
[131] Wang R, Zhang M, Liu F, Bao S, Wu T, Jiang X, et al. Investigation on the
physical–mechanical properties of dental resin composites reinforced with novel
bimodal silica nanostructures. Mater Sci Eng C 2015;50:266–73.
[132] Condon JR, Ferracane JL. Assessing the effect OF composite formulation ON
polymerization stress. J Am Dent Assoc 2000;131(4):497–503.
[133] Boaro LC, Gonçalves F, Braga RR. Influence of the bonding substrate in dental
composite polymerization stress testing. Acta Biomater 2010;6(2):547–51.
[134] Bindu MG, Satapathy BK, Jaggi HS, Ray AR. Size-scale effects of silica on bis-
GMA/TEGDMA based nanohybrid dental restorative composites. Compos B Eng
2013;53:92–102.
[135] Wang R, Habib E, Zhu XX. Application of close-packed structures in dental resin
composites. Dent Mater 2017;33(3):288–93.
[136] Wang R, Habib E, Zhu XX. Evaluation of the filler packing structures in dental
resin composites: from theory to practice. Dent Mater 2018;34(7):1014–23.
[137] Turssi CP, Ferracane JL, Vogel K. Filler features and their effects on wear and
degree of conversion of particulate dental resin composites. Biomaterials 2005;26
(24):4932–7.
[138] Karabela MM, Sideridou ID. Synthesis and study of properties of dental resin
composites with different nanosilica particles size. Dent Mater 2011;27(8):
825–35.
[139] Fujita K, Ikemi T, Nishiyama N. Effects of particle size of silica filler on
polymerization conversion in a light-curing resin composite. Dent Mater 2011;27
(11):1079–85.
23
Composites Part B 216 (2021) 108852
[140] Wang R, Bao S, Liu F, Jiang X, Zhang Q, Sun B, et al. Wear behavior of light-cured
resin composites with bimodal silica nanostructures as fillers. Mater Sci Eng C
2013;33(8):4759–66.
[141] Satterthwaite JD, Vogel K, Watts DC. Effect of resin-composite filler particle size
and shape on shrinkage–strain. Dent Mater 2009;25(12):1612–5.
[142] Satterthwaite JD, Maisuria A, Vogel K, Watts DC. Effect of resin-composite filler
particle size and shape on shrinkage-stress. Dent Mater 2012;28(6):609–14.
[143] Ruyter IE, Øysæd H. Conversion in different depths of ultraviolet and visible light
activated composite materials. Acta Odontol Scand 1982;40(3):179–92.
[144] Clewell DH. Scattering of light by pigment particles. JOSA 1941;31(8):521–7.
[145] Zhang R, Xie R, Liu D, Jia X, Cai Q, Yang X. Nanoporous fibers built with carbon-
bound SiO2 nanospheres via electrospinning and calcination. Mater Des 2017;
130:231–8.
[146] Lewandowska-Łańcucka J, Staszewska M, Szuwarzyński M, Zapotoczny S,
Kepczynski M, Olejniczak Z, et al. Design and characterization of silicone
micromaterials: a systematic study. Mater Des 2018;146:57–68.
[147] Bakhtiar NSAA, Akil HM, Zakaria MR, Kudus MHA, Othman MBH. New
generation of hybrid filler for producing epoxy nanocomposites with improved
mechanical properties. Mater Des 2016;91:46–52.
[148] Rameshbabu AP, Mohanty S, Bankoti K, Ghosh P, Dhara S. Effect of alumina, silk
and ceria short fibers in reinforcement of Bis-GMA/TEGDMA dental resin.
Compos B Eng 2015;70:238–46.
[149] Chen Q, Zhao Y, Wu W, Xu T, Fong H. Fabrication and evaluation of Bis-GMA/
TEGDMA dental resins/composites containing halloysite nanotubes. Dent Mater
2012;28(10):1071–9.
[150] Guo G, Fan Y, Zhang J-F, Hagan JL, Xu X. Novel dental composites reinforced
with zirconia–silica ceramic nanofibers. Dent Mater 2012;28(4):360–8.
[151] Wang X, Cai Q, Zhang X, Wei Y, Xu M, Yang X, et al. Improved performance of
Bis-GMA/TEGDMA dental composites by net-like structures formed from SiO2
nanofiber fillers. Mater Sci Eng C 2016;59:464–70.
[152] Yang D-L, Sun Q, Niu H, Wang R-L, Wang D, Wang J-X. The properties of dental
resin composites reinforced with silica colloidal nanoparticle clusters: effects of
heat treatment and filler composition. Compos B Eng 2020;186:107791.
[153] Algellai AA, Tomić N, Vuksanović MM, Dojčinović M, Volkov-Husović T,
Radojević V, et al. Adhesion testing of composites based on Bis-GMA/TEGDMA
monomers reinforced with alumina based fillers on brass substrate. Compos B Eng
2018;140:164–73.
[154] Matinlinna JP, Lassila LV, Özcan M, Yli-Urpo A, Vallittu PK. An introduction to
silanes and their clinical applications in dentistry. Int J Prosthod 2004;17(2).
[155] Moszner N, Völkel T, Cramer von Clausbruch S, Geiter E, Batliner N,
Rheinberger V. Sol-gel materials, 1. Synthesis and hydrolytic condensation of new
cross-linking alkoxysilane methacrylates and light-curing composites based upon
the condensates. Macromol Mater Eng 2002;287(5):339–47.
[156] Rebholz-Zaribaf N, Özcan M. Adhesion to zirconia as a function of primers/silane
coupling agents, luting cement types, aging and test methods. J Adhes Sci Technol
2017;31(13):1408–21.
[157] Cramer NB, Stansbury JW, Bowman CN. Recent advances and developments in
composite dental restorative materials. J Dent Res 2010;90(4):402–16.
[158] Karabela MM, Sideridou ID. Effect of the structure of silane coupling agent on
sorption characteristics of solvents by dental resin-nanocomposites. Dent Mater
2008;24(12):1631–9.
[159] Yang Q, Lin Y-H, Li M, Shen Y, Nan C-W. Characterization of mesoporous silica
nanoparticle composites at low filler content. J Compos Mater 2015;50(6):
715–22.
[160] Wang R, Habib E, Zhu XX. Synthesis of wrinkled mesoporous silica and its
reinforcing effect for dental resin composites. Dent Mater 2017;33(10):1139–48.