Recent Advances and Developments in Composite Dental Restorative Materials

CRITICAL REVIEWS IN ORAL BIOLOGY & MEDICINE
N.B. Cramer1, J.W. Stansbury1,2,

and C.N. Bowman1,2*
Recent Advances and
1
Dept. of Chemical & Biological Engineering, University of
Developments in Composite
Colorado, UCB 424, Boulder, CO 80309, USA; and 2Dept. of
Craniofacial Biology, School of Dental Medicine, University Dental Restorative Materials
of Colorado Denver, Aurora, CO 80045, USA; *correspond-
ing author, [email protected]
J Dent Res 90(4):402-416, 2011
Abstract Introduction
Composite dental restorations represent a unique
class of biomaterials with severe restrictions on
biocompatibility, curing behavior, esthetics, and
C omposite restorative materials represent one of the many successes of
modern biomaterials research, since they replace biological tissue in both
appearance and function. At least half of posterior direct restoration place-
ultimate material properties. These materials are
ments now rely on composite materials (Sadowsky, 2006). Unfortunately,
presently limited by shrinkage and polymeriza-
demands on these restorations with regard to mechanical properties, place-
tion-induced shrinkage stress, limited toughness,
ment, and need for in situ curing leave significant room for advancements,
the presence of unreacted monomer that remains
particularly with respect to their mechanical properties, polymerization
following the polymerization, and several other
shrinkage and polymerization-induced stress, thermal expansion mismatch,
factors. Fortunately, these materials have been the
fracture, abrasion and wear resistance, marginal leakage, and toxicity (Anseth
focus of a great deal of research in recent years
et al., 1995; Lovell et al., 2001a, b; Ferracane, 2005, 2008; Sadowsky, 2006).
with the goal of improving restoration perfor-
Ultimately, these shortcomings reduce a restorations lifetime and represent
mance by changing the initiation system, mono-
the driving force for improvement in dental composites. Clinical evaluations
mers, and fillers and their coupling agents, and
(Bernardo et al., 2007) and laboratory-based studies focused on composite
by developing novel polymerization strategies.
durability (Drummond, 2008) also continue to highlight this need for new
Here, we review the general characteristics of the
materials.
polymerization reaction and recent approaches
The development and implementation of composite dental restorative mate-
that have been taken to improve composite restor-
rials rely on a comprehensive understanding of each component of the com-
ative performance.
posite and consideration of methods for changing each component. Here, we
discuss basic components of composite restoratives and their role in the ulti-
KEY WORDS: polymeric dental composites, mate restoration. Composites are composed of three distinct phases, each with
shrinkage stress, methacrylate, monomers, photo- its own role in dictating material properties: the polymerizable resin, filler, and
polymerization. the filler-resin interface. The resin phase is composed of polymerizable mono-
mers that convert from a liquid to a highly crosslinked polymer upon exposure
to visible light, which catalyzes the formation of active centers, typically radi-
cals, that induce polymerization. The filler has several roles, including enhanc-
ing modulus, radiopacity, altering thermal expansion behavior, and reducing
polymerization shrinkage by reducing the resin fraction. Finally, the filler-resin
interface serves as a bridge by coupling polymerizable moieties to the particle
surface. Each component represents an opportunity for improvements in the over-
all composite and is the target of recent research reviewed here. Specifically, this
article provides background for the general behavior observed in photopoly-
merization, including the origins of polymerization-induced shrinkage stress,
photoinitiation systems used to improve the restoration curing behavior, recent
research on these topics and novel monomers that have been explored, devel-
opment of new photopolymerization mechanisms, and the filler and interface
components of the formulation.
A 2001 review discussed development of polymeric composite restorative
DOI: 10.1177/0022034510381263 materials (Moszner and Salz, 2001). The article focused on methods for
reducing polymerization shrinkage and achieving improvements in biocom-
Received February 3, 2010; Last revision July 1, 2010;
Accepted July 15, 2010 patibility and wear resistance. Here, the focus is on providing general photo-
polymerization background and reviewing advances from the last five years.
International & American Associations for Dental Research The vast research encompassed in this short time is a testament to the difficulty
402
J Dent Res 90(4) 2011 Developments in Composite Dental Restorative Materials 403
associated with successfully

restoring tooth function and
appearance and demonstrates
continued room for advance-
ment. We focus this review on
recent research aimed at
improving one or more attri-
butes of dental restorative mate-
rials. Given the focus on recent
research, only a very few of
these developments have
already been incorporated into
clinical applications.
Photopolymerization of Figure 1. Polymerization kinetic behavior of various methacrylate monomer formulations. (a) Methacrylate
conversion vs. time and (b) storage modulus as a function of polymerization time for BisGMA-based
Multifunctional Monomers resins with various reactive diluents present in different amounts. Samples contain 0.3 wt% Irgacure 819
Generally, the curing reaction in and were irradiated at 7 mW/cm2 with a Demetron Optilux 501 dental curing lamp.
composite restorative materials
involves visible-light-initiated photopolymerization of dimeth- rate significantly, since its presence reduces the crosslinking
acrylate monomers to form a highly crosslinked polymer. This density, which facilitates termination that lowers the polymer-
photopolymerization reaction consists of three stepsinitiation, ization rate. In contrast, the addition of THFMA, a novel mono-
propagation, and terminationand complexities arise in polym- methacrylate (see later section on Ultrarapid Monomethacrylates)
erization kinetics, network evolution, and the material property that has been found to accelerate polymerization, accelerates the
development (Kloosterboer, 1988; Anseth et al., 1995; Lovell polymerization rate and increases the final conversion that is
et al., 2001a, b; Bowman and Kloxin, 2008). achieved. Though these systems were not polymerized at a
With respect to the polymerization kinetics, both the propaga- clinically relevant irradiation intensity, the relative kinetics and
tion and termination reactions are diffusion-controlled. Even at conversions of the different systems can be more accurately
low conversion (Anseth et al., 1994), the termination reaction, i.e., measured and compared at this intensity.
the coming together of two radicals that react to terminate each In addition to complex polymerization kinetics, the polymer
other, is diffusion-controlled and slowed by the network. structure also evolves with numerous complexities. There are
Subsequently, the radical concentration increases and the observed two critical, macroscopic demarcations that occur during polym-
polymerization rate also increases, a phenomenon referred to as erization. The first of these is the gel point conversion and rep-
autoacceleration. This process is important for dental compos- resents the point at which an incipient gel is formed. In the
ites, since it results in rapid curing on clinically acceptable time chain-growth polymerization of dimethacrylates, this conver-
scales. In contrast to termination, the propagation reaction involves sion is generally less than 5-10% and is critical for controlling
the reaction of a polymeric radical and a relatively mobile methac- the shrinkage stress (Kloosterboer, 1988). The second macroscale
rylate moiety. This reactions nature is such that it does not become demarcation is the vitrification point, which represents the con-
diffusion-controlled until significantly higher conversions, gener- version at which the polymer becomes glassy, accompanied by
ally associated with the polymer becoming glassy, a process a dramatic modulus increase. For the same formulations pre-
referred to as vitrification. As the polymer vitrifies, the propaga- sented in Fig. 1a, Fig. 1b presents the storage modulus as a
tion reaction slows and the polymerization ceases, i.e., autodecel- function of polymerization time. The initial modulus measure-
eration occurs. This process is particularly important in dental ments exhibit significant error associated with the liquid nature
composites, where autodeceleration results in residual, unreacted of the resin, though once the system reaches and surpasses the
methacrylates that remain in the composite restoration. gel point, the storage modulus increases by three to four orders
To illustrate these points, we present the polymerization of magnitude in a matter of only a few seconds.
kinetic behavior of various methacrylate monomer formulations Finally, in addition to the macroscopic observations of the
(Fig. 1a). Various dimethacrylate (bisphenol-A-dimethacrylate, network structure and material properties, it is important to
BisGMA, and triethylene glycol dimethacrylate, TEGDMA) understand that these polymer networks are extremely heteroge-
and monomethacrylate (isobornyl methacrylate, IBOMA, and neous. This heterogeneity arises from two issues, the fact that
tetrahydrofurfuryl methacrylate, THFMA) mixtures are polym- microgels form near the sites of initiation, and the fact that pen-
erized, and the methacrylate conversion is plotted as a function of dant methacrylate groups in BisGMA/TEGDMA monomers and
polymerization time. Mobility effects can be readily observed other analogous systems may be more reactive than their mono-
with increasing TEGDMA, where TEGDMA is a reactive diluent meric counterparts (Elliot et al., 2001). This heterogeneity has
that reduces the viscosity, glass transition temperature, and net- significant implications for composite restorative properties
work stiffness, and increases the maximum conversion that is (Kannurpatti et al., 1998; Lovell et al., 1999a, b), contributing
achieved and the rate at which that conversion is achieved. The to the post-cure behavior noted for glassy methacrylate net-
addition of IBOMA, a traditional monomethacrylate, slows the works (Truffier-Boutry et al., 2006) and to the refractive index
404 Cramer et al. J Dent Res 90(4) 2011
variation within the polymer matrix that enhances filler-induced species that complexes with the tertiary amine to promote a
translucency in composites (Howard et al., 2010). sequential electron and proton transfer that creates the active
-aminoalkyl-initiating radical. Additional studies have evaluated
Polymerization-induced Shrinkage Stress alternative co-initiators to the commonly utilized ethyl-4-dimethyl-
aminobenzoate (EDMAB), including N,N-dimethylaminobenzyl
Shrinkage stress is often considered the most significant problem alcohol, 4-(N,N-dimethylamino)phenethyl alcohol (DMPOH),
with current restoratives and a primary contributor to premature and N,N-3,5-tetramethylaniline (TMA) (Schroeder et al., 2007a, b,
failure in composite restorations, since it is capable of deforming 2008; Schroeder and Vallo, 2007) and a variety of aliphatic and
tooth structures and causing microcracks and adhesive failure aromatic amines (Kim, 2005). With the goal of reducing or
(Ferracane, 2005). The stress is dictated by a complex interplay eliminating the amount of potentially toxic amine co-initiator,
among resin viscosity, volume shrinkage, polymerization rate, cyclic acetals and the naturally occurring 1,3-benzodioxole and
degree of conversion, modulus development, and network struc- its derivatives were evaluated as potential replacements for con-
tural evolution, where each of these properties cannot be indi- ventional amine co-initiators and were found to be effective
vidually manipulated and studied without having a significant co-initiators, resulting in kinetics and polymer properties similar
impact on other properties. A great deal of effort has been to those of equivalent systems initiated by CQ/EDMAB (Liu
expended to develop novel monomers and fillers and distinct et al., 2007; Shi and Nie, 2007; Shi et al., 2007). PPD (1-phenyl-
polymerization methods that reduce shrinkage stress while main- 1,2-propanedione) is a non-yellowing photosensitizer that has
taining all other desirable material properties. Several general- been proposed as an alternative to CQ (Ogunyinka et al., 2007;
ized approaches have been attempted, focusing on (i) Schroeder et al., 2007a, b, 2008; Felipe et al., 2008; Schneider
manipulating the curing protocol and timing to allow for relax- et al., 2009a,b), though it does not appear to be as efficient as
ation and flow of the network prior to gelation, (ii) altering the CQ for visible light initiation.
amount of shrinkage that occurs through changes in the mono- One interesting approach for addressing amine co-initiator
mer or functional group density, and (iii) changing the polymer- toxicity has been to develop polymerizable monomers that also
ization mechanism from conventional radical chain-growth function as co-initiators. Therein, the amine component is
polymerization of methacrylates to alter the network structural polymerized into the network via the methacrylate, which sig-
evolution. These approaches are the overarching motivation for nificantly limits the extractable amine. Several methacrylated
much of the research conducted in the dental restorative field. amine co-initiators, such as ethylene glycol 3-diethylamino-
propionate methacrylate, have been synthesized and demon-
Photoinitiation strated to exhibit polymerization kinetics and properties nearly
equivalent to those of traditional BisGMA/TEGDMA systems
Though non-photoinitiated polymerizations are still performed with a CQ/EDMAB initiation system (Nie and Bowman, 2002;
and studied (Achilias and Sideridou, 2004; Sideridou et al., Wu et al., 2006; Wu and Nie, 2007).
2008), photoinitiated polymerizations have enormous value in
controlling the polymerization temporally, allowing adequate Alternatives to Camphorquinone/Amine Systems
time for placement and manipulation of the restorative prior to
curing. Clinically desirable visible light has reduced energy per Phosphine oxide initiators absorb in the visible range and initiate
photon relative to ultraviolet light, which limits the selection of via a cleavage mechanism that does not require a co-initiator.
suitable initiators and often necessitates multicomponent initia- Phosphine oxide initiators exhibit minimal absorption beyond
tors. One such system, composed of camphorquinone and an 420 nm and therefore are not ideal for use in dental material
amine, is well-known and is the most frequently utilized in den- applications where the spectral output of LED curing lamps has
tal materials. Continuing research focuses on understanding and been designed to match the absorption of CQ, which has an
optimization of initiator systems where the goals include absorbance maximum at 468 nm. New initiation systems based
enhanced initiation efficiency, improved coupling of the initia- on benzoylgermanium derivatives have been synthesized and
tor absorption to the desired light sources emission, reduction demonstrated to be efficient visible light photoinitiators (Ganster
of colored by-products, and generation of new active center et al., 2008a,b; Moszner et al., 2008b, 2009). Similar to phosphine
types, including cations for epoxy polymerization. Additionally, oxides, the benzoylgermanium initiators undergo photodecom-
there remain concerns over the toxicity of the amine co-initia- position to form radicals without the need for a co-initiator. The
tors that are used with camphorquinone. Ultimately, these needs benzoylgermanium initiators exhibit strong absorption up to 450
drive the investigation of new photoinitiator systems. nm, which is advantageous for improved initiation efficiency in
dental materials. The novel initiators were demonstrated to
exhibit improved UV stability, comparable shelf stability,
Camphorquinone/Amine
improved bleaching, and increased cure depths and polymeriza-
The camphorquinone/amine initiation system continues to be tion rates relative to those of the CQ/amine systems.
the subject of research in efforts to determine optimum initiator Three-component photoinitiators composed of a photo-sensi-
and co-initiator concentrations for kinetics and polymer mechan- tizer dye, an electron donor photo-reductant, and an electron
ical properties (Viljanen et al., 2005; Musanje et al., 2009). In acceptor photo-oxidant offer enhanced efficiencies in the pro-
this visible-light-activated initiator system, camphorquinone duction of both free-radical and ionic species for photopolymer-
(CQ) absorbs a photon to generate a short-lived excited-state ization. A variety of suitable dyes have been identified, which
allow for variation in the active wavelengths that are considered, Because of conversions importance in dictating material
although dental materials applications continue to require the properties, the development of instrumentation that combines
400- to 500-nm region of the visible light spectrum. Amines are in situ conversion measurements by Fourier transform infrared
primarily used as electron donors, and diphenyl iodonium or (FTIR) spectroscopy with shrinkage or shrinkage stress measure-
triphenyl sulfonium salts are commonly used as electron accep- ments has enabled an effective means by which to study shrink-
tors, although several other examples of practical electron age and shrinkage stress (Lu et al., 2004a; Stansbury et al., 2005).
donors and acceptors are known. In (meth)acrylate-based radi- These experiments demonstrated that the vast majority of stress
cal photopolymerization, the addition of a diphenyl iodonium development arises as the sample nears and ultimately undergoes
salt not only reduces the photon-wasting back electron transfer vitrification. Therefore, stress relaxation can occur prior to vitrifi-
and recombination reactions, but also provides a means to cation; however, the magnitude of the stress reduction is minimal
recycle consumed photosensitizer, which effectively increases with respect to overall stress development (Lu et al., 2004a,b,c).
the photoinitiator concentration (Kim and Stansbury, 2009a,b). These results also indicate that reduced stress that results from
The introduction of a photo-oxidant component in a dental adhe- reduced irradiation intensity (soft-start/pulse-curing techniques)
sive initiator system has been demonstrated to produce enhanced is often the result of changes in the conversion. In addition to the
conversion in the presence of moisture (Guo et al., 2008), with conversion, the sample geometry, initiation and polymerization
analogous results shown in an unrelated system (Gomez et al., rates, and curing protocols can also affect the stress that is
2007). Similar three-component initiator systems are also used achieved by altering the temperature profile that occurs as a result
efficiently in cationically photocurable materials such as epox- of the exothermic nature of the polymerization reaction. The
ides (Oxman et al., 2005; Crivello, 2009). BisGMA/TEGDMA (or similar) resin system has a limited ability
to mitigate shrinkage stress without subsequent reductions in
Soft-start Curing conversion and polymer properties. Extensive research has gone
into and will continue to be devoted toward evaluating curing
One of the methods purported to reduce shrinkage stress without conditions and the subsequent effects on conversion, mechanical
compromising other properties such as conversion or mechanical properties, and shrinkage stress.
properties is to reduce the initiation rate with the use of lower
irradiation intensities, i.e., soft-start curing. The soft-start curing
Methacrylate Monomer Formulations
method originated with work by Unterbrink and Muessner in
1994 (Unterbrink and Muessner, 1994, 1995) and continues to be The resin phase of composite materials presently represents the
the subject of significant study (Braga et al., 2005; Ferracane, area through which the greatest changes in composite practice
2005). Reduced irradiation intensity during the early stages of may be achieved. That said, the requirements for the resin phase
polymerization is hypothesized to allow stress relaxation to of the composite restorative are daunting: These materials must
occur prior to vitrification. Soft-start curing has been adopted be stable on the shelf for years, then rapidly react to form a
clinically and has undergone and continues to undergo signifi- highly crosslinked polymer with high modulus, high hardness,
cant research, due to the benefits of reducing shrinkage stress and high glass transition temperature while matching the ther-
that might occur without compromising other properties (Braga mal expansion of the tooth, limiting extractables, minimizing
and Ferracane, 2002; Lim et al., 2002; Witzel et al., 2005; Pfeifer moisture uptake, being chemically inert, and having minimal
et al., 2006; Cunha et al., 2007, 2008a,b). Though much of the shrinkage and shrinkage stress. Clearly, while the potential
work surrounding soft-start curing has taken conversion into improvements in this area are dramatic and the array of possi-
consideration, a body of evidence supports the notion that reduc- bilities for replacement is also vast, only through careful and
tions in shrinkage stress are often accompanied by subsequent insightful manipulation of the current resin phase will signifi-
reductions in conversion (Gonalves et al., 2008; Pfeifer et al., cant results be realized.
2008) and mechanical properties (Feng and Suh, 2006a,b). In Currently, methacrylate resin formulations dominate both the
addition to soft-start curing, Ferracane and co-workers (Musanje commercial market and research evaluation. The resin phase is
et al., 2009; Pfeifer et al., 2009b) have determined that changes composed primarily of dimethacrylate monomers typically
to the photoinitiator composition and type also alter the polym- selected from BisGMA, BisEMA, and/or UDMA. These base
erization kinetics, polymer structure, final conversion, and monomers result in restorative materials with excellent mechani-
shrinkage stress, and that this factor must be considered in the cal properties, rapid polymerization, and low shrinkage. However,
design of an optimal photopolymerizable composite formulation. resins composed of monomers such as these generally result in
Frequently, shrinkage stress measurements are not coupled with low methacrylate conversion, which leads to significant amounts
in situ kinetic and functional group conversion results. It is inher- of unreacted monomer that may be leached from the restoration
ently difficult to compare results across different specimens and over time, resulting in concerns regarding long-term biocompat-
experimental procedures when very small changes in conditions, ibility. High resin viscosity also limits the ability to incorporate
shape, or conversion produce large changes in stress and material high filler volumes into the resin. To achieve low volume shrink-
properties. Lovell et al. (2001b) demonstrated clearly both that age and high mechanical properties such as modulus and wear
small changes in conversion have a pronounced effect on proper- resistance, filler contents of 60 to 87 wt% (Lohbauer et al., 2006)
ties, especially modulus, and that polymerization conditions had are necessary. To reduce viscosity, enabling high filler content to
little effect on material properties other than through changes in be incorporated, low-viscosity reactive diluents, most commonly
the conversion. TEGDMA, are used. The inclusion of a reactive diluent reduces
Table 1. Several representative methacrylate monomer structures studied without the addition of fillers, and subsequent studies on
utilized in resin based composite restorative materials. optimal resin candidates evaluate the synergistic effects of
changes to both components.
Formulations containing one or more of the base monomers,
2,2-bis[4-(2-hydroxy-3- ethoxylated bisphenol-A BisGMA, EBPADMA, UDMA, and TEGDMA, have been uti-
methacryloyloxypropoxy)phenyl] dimethacrylate (EBPADMA) lized commercially for decades. The monomer interactions,
propane (BisGMA) polymerization kinetics, and polymer properties resulting from
these materials are complex. Numerous investigations are being
and have been conducted to evaluate various combinations of
triethylene glycol dimethacrylate urethane dimethacrylate (UDMA) these dimethacrylate materials, in efforts to understand the inter-
(TEGDMA) relationships among composition, resin viscosity, conversion,
shrinkage, flexural strength, fracture toughness, water sorption
and solubility, and rheology (Sideridou et al., 2003;
Marcinkowska and Andrzejewska, 2006; Charton et al., 2007;
Ellakwa et al., 2007; Gonalves et al., 2008, 2009; Pfeifer et al.,
tert-butylphenoxy BisGMA modified urethane dimethacrylate 2009a). In addition to formulations containing only the tradi-
(MtBDMA) tional base monomers, a vast amount of research has focused on
developing systems with alterations and improvements to these
formulations, including the incorporation of monomethacrylate
amide modified bisphenol-A CH3BisGMA diluents, dimethacrylates, and multimethacrylates. Changes to
the polymerization mechanism, which also involves changes to
the monomers, are reviewed in a later section. An array of
monomer structures for the base dimethacrylate materials as
acidic bisphenol-A dimethacrylate dimethacrylate from cycloaliphatic
epoxide
well as new monomers are given in Table 1.
Multimethacrylates
Because the conventional dimethacrylate monomers have
aromatic urethane dimethacrylate urethane modified BisGMA
worked well in many regards, one target of current research is to
select, synthesize, and evaluate dimethacrylates that preserve
the desirable attributes of the conventional restoratives while
acid aromatic dimethacrylate oxydiphthalic-acid dimethacrylate
simultaneously addressing their shortcomings. As such, a wide
range of dimethacrylate monomers has been synthesized and
evaluated as potential restorative materials. These new mono-
mer systems show promise for maintaining or improving prop-
erties such as conversion, water sorption, volume shrinkage, and
shrinkage stress, with the overarching goal of creating a restor-
ative material with improved performance and service lifetime.
phenyl dihydroxymethacrylate Acidic Bisphenol-A dimethacrylate
diphosphonate The use of a bisphenol-A core, as is contained in BisGMA-
and EBPADMA-based materials, provides both high strength
and toughness to the resulting polymers. Hence, the develop-
ment of dimethacrylate derivatives of bisphenol-A has been an
active research area, where modifications of bisphenol-A-based
morpholine carbonyl phenyl carbonate methacrylate dimethacrylate systems have included the use of pendant bulky
methacrylate (aromatic) constituents (Ge et al., 2005) as well as pendant alkyl
urethanes (Khatri et al., 2003) to increase molecular weight and
thereby decrease volume shrinkage. Oligomeric bisphenol-A
viscosity and increases conversion, but also generally reduces the monomers have also been modified with pendant urethane acry-
modulus and results in higher volume shrinkage and shrinkage lates and exhibited reduced volume shrinkage and improved
stress. Both the resin formulation and filler type and content mechanical properties (Chen et al., 2008). Increasing the ethyl-
affect the final composite curing and mechanical properties. ene oxide chain length between the bisphenol-A core and the
Dental restorative material compositions of dimethacrylates are a methacrylate functional group reduces viscosity and increases
balance between the relative amounts of base materials and reac- conversion, but also increases water sorption and decreases
tive diluents, which results in trade-offs among resin viscosity, flexural strength (Ogliari et al., 2008). Incorporating methylated
polymer properties, and monomer conversion. It is generally not and fluorinated derivatives of BisGMA into BisGMA/TEGDMA
practical to study simultaneously the effects of alterations to the resins has resulted in greater hydrophobicity and reduced water
resin formulation and the effects of fillers on new resin composi- sorption (Pereira et al., 2007), but no significant improvements
tions. Therefore, new resin formulations are most commonly in mechanical properties (Pereira et al., 2005, 2007).
Recent developments regarding public perceptions of bisphe- exhibit a high glass transition temperature. Additionally, the
nol-A toxicity may have a strong influence on steering future mono(meth)acrylates exhibit high conversion, limiting the poten-
monomer development efforts toward bisphenol-A alternatives. tial for leachable monomer. These materials showed great prom-
Numerous other methacrylate monomer types are already being ise when utilized as diluents, and several monomethacrylates
developed and evaluated that would achieve this end. Derivatives were evaluated as alternatives to TEGDMA (Lu et al., 2005;
of urethane dimethacrylate have been synthesized to increase Kilambi et al., 2009). For example, morpholine carbonyl methac-
molecular weight, reduce water sorption, and/or increase rylate with BisGMA exhibited 21% increased conversion, 3.5
mechanical properties by incorporating aromatic or aliphatic times faster polymerization rate, and 30% reduced volume shrink-
groups (Atai et al., 2007; Moszner et al., 2008a; Kerby et al., age as a resin system (Lu et al., 2005) and 13% increased conver-
2009). Bile acids were utilized as starting materials to form sion, 3 times faster polymerization rate, and equivalent or
multimethacrylate monomers (Gauthier et al., 2009). These improved mechanical properties as a composite system relative to
materials showed reduced volume shrinkage and promising a control BisGMA/TEGDMA system (Kilambi et al., 2009).
mechanical properties; however, they exhibited extremely high
viscosities (higher than BisGMA). Polyhedral oligomeric silses- Acidic Monomers
quioxane methacrylates (POSS-MA) were evaluated as alterna-
tives to BisGMA (Fong et al., 2005), and it was found that small Recent developments in methacrylate resins have investigated the
amounts of POSS-MA (2-10 wt%) did indeed improve the incorporation of acidic functional groups into the monomer struc-
mechanical properties of these resins, while dimethacrylates ture. Incorporating acidic monomers in relatively small mole
based on cycloaliphatic epoxides showed kinetics and mechani- fractions into methacrylate resins may enable a separate adhesive
cal properties comparable with those of BisGMA (Shi and Nie, layer to be eliminated and result in improved overall performance.
2008). Methacrylated beta-cyclodextrin derivatives have also Current acidic resins do not exhibit the necessary mechanical
been evaluated as alternatives to BisGMA and were found to properties to function as resin-based composites, and hence
exhibit flexural strength and volume shrinkage comparable with research has focused on developing acidic monomers with
those of BisGMA/TEGDMA (Hussain et al., 2005). improved mechanical properties. Acidic monomers have been
Many previously developed dimethacrylate materials exhibit synthesized from o-hydroxyaryl phosphonates that exhibited
excellent properties with regard to modulus, water sorption, rapid polymerization kinetics (Sahin et al., 2006). Bisphenol-A
conversion, and so forth. When one considers that a dental derivatives have been produced both with carboxylic acid and
restorative material must balance numerous properties, the phosphonic acid functional groups without degradable esters
dimethacrylate materials to date generally result in trade-offs (Sahin et al., 2009) and with carboxylic, amide, and hydroxy
among resin viscosity, polymer properties, and monomer con- functional groups to improve adhesion (Yagci et al., 2006). Other
version. For example, monomers with higher molecular weights derivatives of BisGMA, including carboxylic acid functionalized
often result in low shrinkage and excellent material properties, monomers, exhibit comparable mechanical properties but
but also concomitant increases in resin viscosity (limiting the increased water sorption (Atai et al., 2004). The increased mois-
incorporation of filler) and reduced ultimate conversion. Hence, ture absorption associated with the acid is a common problem,
while numerous dimethacrylate derivatives have shown great since the presence of the acidic group increases the hydrophilicity
promise as dental restorative materials, improvements in overall of the material through increased polarity and charge density.
properties relative to BisGMA/TEGDMA are generally modest, Acidic monomer-containing composites with various aromatic
hence the limited commercial incorporation of these monomers. core structures were evaluated for mechanical properties and
found to exhibit properties similar to those of BisGMA/TEGDMA
(Lpez-Suevos and Dickens, 2008). The use of acidic monomers
Ultrarapid Monomethacrylates
necessitates consideration of hydrolytic stability. Acrylamides
For many years, the inclusion of monomethacrylate monomers in exhibit increased hydrolytic stability compared with esters, and
dental resins was rightly seen as problematic, since inclusion of especially when utilized under acidic conditions, acrylamides
traditional monomers of this type generally slows the polymeriza- present a promising alternative to methacrylates. Bis-acrylamides
tion, reduces the modulus and crosslinking density, increases the showed similar reactivity, flexural strength, and flexural modulus
shrinkage, and leads to an increased amount of extractable materi- when compared with similar dimethacrylate resins (Moszner et al.,
als. The paradigm for inclusion of monovinyl monomers into 2006b). The use of internal amide functional groups has also been
dental resins was changed with the development by Decker of a considered. These monomers are derivatives of bisphenol-A and
novel class of monovinyl (meth)acrylate monomers that exhibited exhibited significant reductions in volume shrinkage, but also
greatly enhanced polymerization kinetics and significantly resulted in increased viscosity and, due to low solubility, are able
improved mechanical properties. These monomers contain sec- to be incorporated only at levels up to 5 mol% in BisGMA/
ondary and tertiary functionalities such as urethanes, carbonates, TEGDMA resins (Yagci et al., 2006).
cyclic acetal, morpholine, cyclic carbonates, hydroxy/carboxy,
oxazolidones, and aromatic rings (Decker and Moussa, 1990,
Novel Polymerization Mechanisms
1991a,b; Jansen et al., 2003; Berchtold et al., 2004, 2008, 2009;
Lu et al., 2005; Kilambi et al., 2007a,b, 2009) that lead to their Conventional radical-mediated chain-growth polymerization of
unique polymerization and polymer property behavior. These dimethacrylates has found incredible utility in composite restoratives;
monomers exhibit rapid polymerizations that rival and often however, it is fundamentally limited in several aspects. The
exceed those of equivalent di(meth)acrylates, and the polymers chain-growth polymerization mechanism leads to early gelation
Table 2. Polymer Properties of Ternary Dimer Acid Dimethacrylate-based Resins and Monomer Structures of Various Dimer Acid Dimethacrylate
Dimethacrylates.
Resin Mass ratio Conversion, % Flexural strength, MPa Volumetric Shrinkage, % PIPS?*
BisGMA/TEGDMA 70/30 64.1 2.8 93.2 8.3 7.26 0.51 -

BisGMA/I/BisEMA 50/30/20 70.4 0.3 100.8 4.3 4.56 0.11 +
UDMA/I/BisEMA 60/20/20 75.1 0.4 65.5 7.9 5.63 0.06 +
BisEMA/II/UDMA 70/20/10 80.1 1.8 73.7 0.8 6.28 0.37 +
BisEMA/III/UDMA 60/25/15 82.9 1.1 85.3 2.3 5.10 0.53 +
Dimer Acid Dimethacrylate Monomer Structures
*Polymerization-induced phase separation
(Kloosterboer, 1988), while the methacrylate consumption is DADMA monomers, with various connecting groups used to
linked to a defined volume reduction associated with the con- attach the C36 dimer acid core to the methacrylates, were formu-
sumption of each methacrylate (Patel et al., 1987). Improvements lated as reactive diluents with BisGMA, UDMA, and/or BisEMA
in the methacrylate monomer structure, as noted previously, have to manipulate comonomer compatibility and polymeric proper-
the potential for addressing many of the shortcomings of current ties. The dimer-acid-derived monomers, DADMA I, II, and III
composites; however, an even greater potential lies in completely (Table 2), were prepared as previously described (Trujillo-Lemon
changing the reaction mechanism, either by changing the active et al., 2006). The DADMA monomers have molecular weights of
center (from radical to cationic), by changing the nature of the 673-849 g/mol, with initial methacrylate group concentrations of
network/molecular-weight evolution (by changing to a step 2.4-2.7 mol/L as compared with the values for TEGDMA of 286
growth reaction or by changing to a covalent adaptable network), g/mol and 7.5 mol/L, respectively. Monomer I has no hydrogen
by changing the nature of the reactive chemistry (by going to ring- bond donor functionality and presents the lowest viscosity of the
opening species), or by changing the physical behavior that arises DADMA series. It has limited miscibility with BisGMA or
during polymerization (by inducing phase separation). Exciting UDMA, but is compatible with BisEMA. Conversely, DADMA
research has focused on bringing each of these developments to monomers II and III, which do form hydrogen bonds through the
dental restorative materials, and their efforts are summarized here. hydroxyl or urethane functionality, respectively, are compatible
with BisGMA or UDMA, but are only partially miscible with
BisEMA. Therefore, ternary compositions that combined one
Polymerization-induced Phase Separation
DADMA monomer with either BisGMA or UDMA and BisEMA
Incomplete polymerization, volumetric shrinkage, and stress allowed formulations to be prepared in which the degree of ther-
are among the primary disadvantages of current resin-based modynamic compatibility could be precisely tuned. Formulations
dental composites. Generally, attempts to increase double-bond near the thermodynamic stability boundary, as monomers, under-
conversion exacerbate polymerization shrinkage and stress. In went polymerization-induced phase separation (PIPS) to generate
one creative approach, specific methacrylate monomers, chosen heterogeneous polymers. The extent of phase separation depends
to be miscible as liquids but phase-separated at higher conver- on the resin composition and reaction conditions, with greater
sions, were incorporated into conventional methacrylate resins sensitivity apparently related to reaction temperature as opposed
and composites. When phase separation occurs, the volume to reaction kinetics.
expands, eliminating a portion of the volume shrinkage that Uniquely, methacrylate conversion values of all the experi-
arises from the methacrylate polymerization. mental resins were significantly greater than those of the control
In particular, the use of dimer-acid-derived dimethacrylate (Table 2), while in appropriate formulations, the flexural strength
(DADMA) monomers in novel dental resin formulations is exam- of the experimental resins was equivalent to that of the BisGMA/
ined as a potential means to address the combined aims of high TEGDMA control. Despite their higher conversion values, the polym-
conversion and low shrinkage and shrinkage stress. A series of erization shrinkage results for all the experimental formulations
were well below those of the control, with several experimental multifunctional monomers that underwent a thiol-ene photopo-
materials demonstrating a modest volume recovery during the lymerization. While the polymerization proceeds, the allyl sul-
post-cure observation interval. This type of novel behavior has fide participates in an addition-fragmentation process that
been reported for other systems involving PIPS associated with allows the forming polymer network to relax throughout the
pre-polymer additives (Velazquez et al., 2004; Schroeder et al., polymerization rather than simply prior to gelation. This net-
2007a). In an analogous fashion, the experimental resins display work adaptation process has been shown to enable polymeriza-
lower polymerization shrinkage stress compared with the con- tion shrinkage stress reductions of up to 75% when compared
trol (unpublished observations). with otherwise identical monomers in which the allyl sulfide is
replaced with a propyl sulfide (Kloxin et al., 2009).
Thiol-Ene Photopolymerization
Work has also focused on utilizing the thiol-ene photopolymer- Hybrid Polymerization Reactions
ization mechanism as a means for circumventing the problems Hybrid polymers are formed from comonomers with different
with conventional methacrylate polymerization. The thiol-ene reactive groups that polymerize via different curing mechanisms
polymerization reaction is ideally suited for dental restorative and are often utilized to synergistically achieve desired proper-
materials, since these reactions are rapid photopolymerizations ties. Typically, polymerizations occur in parallel to form an
that achieve high functional group conversion, are not inhibited interpenetrating polymer network (IPN) or, more generally, a
by oxygen, and proceed via a step-growth polymerization mech- material that is formed from two distinct polymerizations that
anism in which propagation and chain transfer alternate (Cramer generally have significant bonds between the two materials. For
and Bowman, 2001; Hoyle et al., 2004, 2010; Lu et al., 2005; example, the use of methacrylate/vinyl ether systems facilitates
Hoyle and Bowman, 2010). The step-growth nature of the sequential one-step hybrid polymerizations (Lin and Stansbury,
polymerization results in uniform polymer networks with narrow 2003, 2005) where the methacrylate polymerizes via a radical
glass transition regions and reduced brittleness. Also, the gel- reaction and the vinyl ether polymerizes via a cationic mecha-
point conversion is significantly higher in thiol-ene networks as nism. The order of the reactions can be controlled by the selec-
compared with methacrylate networks, because of the step- tive addition of inhibitors of each polymerization type or
growth polymerization. Thus, shrinkage that occurs before gela- through manipulation of the initiating wavelength-initiator com-
tion, which now represents a large fraction of the total shrinkage, bination. Here, the incorporation of vinyl ether monomers is
can be accommodated by flow rather than stress evolution, and desirable, since they exhibit high reactivity, no oxygen inhibi-
hence thiol-ene systems exhibit significant reductions in polym- tion, and low toxicity and irritation properties. An additional
erization shrinkage stress (Carioscia et al., 2005; Lu et al., 2005; benefit of hybrid polymerization is that reduced shrinkage stress
Cramer et al., 2010). Though thiol-ene systems exhibit a number can often be demonstrated, particularly when one polymeriza-
of very attractive properties, including high glass transition tem- tion type largely precedes the second polymerization (Carioscia
perature, results to date have demonstrated that they also exhibit et al., 2007; Lee et al., 2007b). In this manner, the gel-point of
reduced flexural modulus and strength relative to BisGMA/ the entire system is delayed, allowing flow and relaxation to
TEGDMA controls (Carioscia et al., 2005, 2007; Lu et al., 2005; occur and accommodating any shrinkage without stress genera-
Fairbanks et al., 2009; Cramer et al., 2010). tion during the intervening period.
Utilizing thiol-ene systems in combination with methacrylate
systems in methacrylate-thiol-ene systems is one method to
Ring-opening Polymerization
combine the advantages of both the thiol-ene and methacrylate
systems. Methacrylate-thiol-ene systems were demonstrated to The implementation of ring-opening polymerization in dental
exhibit cure time and flexural modulus and strength equivalent restoratives has long been sought, even going back to Bowens
to those of BisGMA/TEGDMA, while achieving increased lev- original work (Bowen, 1956), for many reasons. The primary
els of conversion and exhibiting dramatic reductions in shrink- reason that ring-opening polymerization has received attention
age stress (Cramer et al., 2010). In fact, reductions in shrinkage is underpinned by the unique shrinkage behavior observed in
stress in methacrylate-thiol-ene formulations are greater than for these polymerizations. Whereas methacrylate (and thiol-ene)
bulk thiol-ene systems. The increased reduction in shrinkage photopolymerizations involve the conversion of a carbon-
stress is due to the hybrid nature of the polymerization. The carbon double bond into single bonds, the ring-opening reaction
reaction often proceeds in two relatively distinct stages. The relies on the opening of a cyclic structure to facilitate inter-
first stage is dominated by methacrylate homopolymerization monomer bonding and crosslinking. Inherent to the cyclic struc-
with chain transfer to thiol, while the second stage is dominated tures is that significantly less volume shrinkage occurs when
by thiol-ene polymerization (Lee et al., 2007a,b). rings are opened.
One route to alleviate stress in polymer networks, already A recent exciting development in ring-opening polymeriza-
demonstrated for thiol-ene systems but also applicable to meth- tion is the commercial release of the cationically photopolymer-
acrylates, is the creation of a covalent adaptable network in izable silorane material (Filtek LS) by 3M/ESPE (Weinmann
which the bond structure of the network remains covalent, yet et al., 2005). The resin chemistry relies on the ring-opening
each individual bond can be broken and re-formed (Scott et al., polymerization of a combination of proprietary and readily
2005; Kloxin et al., 2010). In dental materials, this outcome is available cycloaliphatic monomers. The silorane terminology
achieved by the incorporation of allyl sulfide moieties into derives from the novel monomer composed of a cyclic siloxane
core appended with 4 oxirane reactive groups. The cyclohexene radical-assisted cationic polymerizations (Ge et al., 2006). It is
oxide-type oxirane rings are significantly more reactive com- worth noting that new reaction mechanisms, other than free-
pared with a simple epoxy analog, and the very hydrophobic radical methacrylate, must also consider stable adhesion between
siloxane structure effectively balances the potential hydrophilic- the restoration and the tooth.
ity of the polyether backbone generated by the ring-opening
polymerization. The cationic reaction is activated by a visible- Fillers and Filler Modifications
light photoinitiator system with camphorquinone as photosensi-
tizer, a tertiary aromatic amine as a photoreductant, and an In addition to research on the photoinitiation process and the
iodonium salt as an electron donor that creates the active cat- monomers used, research on fillers constitutes a large potential
ionic species. The filler selection, the filler surface treatment, source of improvement in composite-based dental restoratives. In
and the adhesive required for bonding the composite to dentin fact, a significant fraction of the practically implemented improve-
and enamel are also designed to accommodate the cationic cur- ments in composites in recent decades has occurred in the nature,
ing process. A successful, cationically initiated dental restor- type, size distribution, and surface modification of the filler. An
ative material certainly represents a significant challenge, as excellent review (Klapdohr and Moszner, 2005) focused on the
implied by the fact that Bowen initially tried and abandoned inorganic filler component of dental composites and related filler
cationic epoxide materials before developing BisGMA in his composition, morphology, and loading content with properties
seminal work on dental restorative materials (Bowen, 1956). conveyed to composites. This review also examined a variety of
The available literature on silorane physical and mechanical silane surface modifications and sol-gel-based hybrid inorganic/
properties has recently been reviewed (Duarte et al., 2009). A organic materials. Here, we survey continued developments
mechanical property characterization targeting several different related to filled dental polymers, including several recent
length scales has been conducted with the silorane composite approaches that involve the analytical characterization of com-
material along with several commercial composites based on posite materials as well as the implementation of advances in
conventional dimethacrylate resin chemistry (Ilie et al., 2009). filler technology that result in improved composite restoratives.
The cationic silorane and free-radical methacrylate materials
Nanofillers in Dental Composites
provided comparable properties initially and after water storage,
with the silorane demonstrating a better retention of initial Significant attention has been devoted to nanofilled materials,
mechanical properties during extended storage in alcohol. The including improvements realized by the incorporation of nano-
oxirane ring-opening polymerization process is quite exother- fillers into commercial composite materials and research aimed
mic, since it relies on the relief of the substantial ring strain to at the development of new nanofillers. A recent review focused
provide the driving force for the polymerization process. The on nanofilled dental composite materials (Soh et al., 2006), and
advantage of low polymerization shrinkage associated with a separate report centered on how nanofillers affect composite
ring-opening polymerization arises due to an inherently lower mechanical properties and behave distinctly differently com-
molar shrinkage coefficient, as well as greater concentrations of pared with micro- or macro-scale fillers (Crosby and Lee, 2007).
chain ends in comparison with methacrylate polymerizations. Nano-sized fillers can be categorized as either isolated discrete
Monomers containing suitably placed cyclopropyl groups particles, with dimensions of approximately 5 to 100 nm, or
capable of undergoing ring opening based on free-radical fused aggregates of primary nanoparticles, where the cluster size
re-arrangement mechanisms have been developed for dental may significantly exceed 100 nm. The enormous rise in filler
applications (Moszner et al., 2006a; Moszner and Salz, 2007). surface area and the corresponding thickening effect on compos-
Here, a vinyl group next to the highly strained bicyclic structure ite paste consistency associated with decreasing filler size limit
facilitates the re-arrangement that generates a single lower- the content of discrete nanoparticles to relatively low loading
energy ring. Based on this approach, experimental dental com- levels, whereas high contents of nanoparticle clusters are man-
posites that involved free-radical copolymerization of the ageable with appropriate surface treatment. A spatially resolved
ring-opening monomers with conventional dimethacrylates nanoindentation study examined Filtek Supreme XT (A3 Dentin)
were evaluated to demonstrate that composites with good as a nanofilled composite and demonstrated significant differ-
mechanical strength and much-reduced polymerization shrink- ences in the dynamic complex modulus as a function of position-
age compared with control materials were available. Whereas ing within the matrix, within a filler cluster, or at the matrix-filler
the polymerization of monomers with strained small ring struc- interface (Ilie et al., 2009). A study on the influence of mono-,
tures is driven primarily by enthalpy change, the ring-opening bi-, and tri-modal distributions of fillers on the wear properties of
polymerization of monomers with larger ring structures is also composites showed that filler size and shape significantly influ-
possible based on entropy effects. Several bicyclic monomers ence wear resistance, with the inclusion of nano-sized filler a
that engage in either radical or cationic double-ring-opening critical feature, often leading to enhanced properties (Turssi
polymerization have been developed and examined for their et al., 2005). A similar dependence of toothbrush abrasion resis-
potential to reduce polymerization shrinkage in dental materials tance on the presence of nanoparticles in commercial dental
(Miller et al., 2005; Moon et al., 2005; Chappelow et al., 2008). composites has been shown (Cavalcante et al., 2009).
A detailed mechanistic study of 2-methylene-7-phenyl-1,4,6,9- In terms of novel nanofillers, a variety of sol-gel-derived
tetraoxaspiro[4.4]nonane, a bicyclic monomer known to provide hybrid organic/inorganic monomers (ormocers) as well as func-
ring-opened polymer, indicated significant issues, including tional silanes were described in a review of their design for
susceptibility to moisture-induced side-reactions in cationic and dental composite applications (Klapdohr and Moszner, 2005). A
systematic study of the sol-gel synthetic approach was used to composite material with caries inhibition potential and good
produce nearly monodisperse silica particles of adjustable size mechanical properties (Xu et al., 2009). Other composites
from 5 to 450 nm. Silanization conditions were identified that designed to promote remineralization were also examined
yield uniform surface coverage regardless of particle size, and (Mehdawi et al., 2009).
dental composites were formulated by incorporation of the The influence of filler particles on the rheology and handling
nanoparticles alone or in combination with a barium glass filler properties of dental composites has been extensively evaluated.
so that particle dispersion and resin/filler adhesion potential Filler incorporation converts the Newtonian behavior of unfilled
could be examined (Kim et al., 2007). The introduction of resins to composites that exhibit shear-thinning and thixotropic
bonded or non-bonded nanofiller in a hybrid composite was behavior, with micro-sized fillers inducing relatively subtle
evaluated in terms of its effect on abrasion and attrition wear of effects compared with the dramatic changes associated with
the composite. While the use of non-bonded nanofiller does pro- nanofillers (Lee and Bowman, 2006; Beun et al., 2009). One
vide a means to reduce polymerization shrinkage stress in dental investigation of commercial composite materials used an oscilla-
composites, it may also reduce wear resistance. Resin viscosity tory compressive rheometer to highlight the substantial differ-
was a cofactor with composites based on the lower-viscosity ences in viscoelastic behavior of these uncured composite pastes
resins, which achieve higher degrees of conversion, performing (IB Lee et al., 2007). Additional studies correlating the rheologi-
better in wear studies than higher-viscosity resins with the same cal properties of commercial composites with their time-depen-
filler (Musanje and Darvell, 2006). The presence of low to mod- dent slumping resistance have been conducted (Lee et al., 2008).
erate amounts of Montmorillonite clays as a nano-scale layered Related to this, a method to quantify the effects of particle size
silicate filler in a model dental resin was examined, with atten- and morphology on handling properties of experimental compos-
tion given to dispersion and exfoliation potentials dependent on ites was developed. The maximum force and work involved with
loading level and polarity (Discacciati and Orefice, 2007). A the separation of a probe from uncured paste are related to the
method was developed to prepare single-walled carbon nano- stickiness of the composite, with differences noted between
tubes (SWCNT) with suitable compatibility and polymerizability spherical and irregular particulate fillers (Kaleem et al., 2009).
such that they could be introduced into dental composites as a
secondary filler. The SWCNT were oxidized and then silanated Silane Treatment of Inorganic Fillers
in two steps to attach polymerizable surface groups. Addition of
small amounts of the carbon nanotube filler to a commercial Surface modification of most fillers used in dental composites is
composite (Durafill) yielded a material with compromised necessary: (a) to reduce the filler surface energy such that com-
esthetics, but one that was still photocurable. A good dispersion posite paste consistency and hydrophilicity are reduced while
of the SWCNT in the composite was demonstrated, along with a filler dispersion within the resin is enhanced; and (b) to provide
significant increase in flexural strength compared with that of the a functional interface that permits covalent attachment between
unaltered composite material (Zhang et al., 2008). the polymer matrix and the reinforcing higher-modulus filler.
Hydrolyzed trialkyloxysilane groups of the coupling agent react
Additional Dental Fillers and Composite Performance and interact with surface silanols (or other groups, depending on
the filler composition) as well as with themselves to form an
The use of mesoporous silica fillers has been suggested as a imperfect array of covalent and hydrogen-bonded attachment
means to eliminate the silane-mediated interface between filler sites that generally yield a dense, multi-layered interface. While
and matrix, while providing a potentially more stable direct methacryloxypropyltrimethoxysilane (MPS) remains the most
mechanical interlocking. A study evaluating the use of silica widely used surface treatment for the inorganic fillers used in
particles with interconnected pore structures as well as a non- dental composites, several new studies related to either MPS or
porous silanized silica filler showed that optimized filler loading alternative silane surface modifiers have also been reported. A
and mechanical reinforcement were achieved with a mixture of solid-state NMR-based analysis of MPS-treated fillers used in
the two fillers (Samuel et al., 2009). The potential anisotropic model composite materials suggests that the primary silane
effects of fiber-based fillers on polymerization shrinkage have attachment mainly involves CH2SiO2(OH) (T2) structures and
also been demonstrated (Tezvergil et al., 2006), as well as the also used FTIR spectroscopy to verify the conversion restric-
interactions between fibrous and particulate fillers in complex tions imposed by fillers in composite materials (Nunes et al.,
composite materials (Garoushi et al., 2008). Electrospun con- 2008). A study of silane-mediated bonding between a resin com-
tinuous nano-fiber-reinforced dental polymers have also been posite cement and silica-coated titanium evaluated the efficacy
evaluated, with a focus on the fiber-matrix interface being a of a variety of functional silanes, including several lacking
critical feature (Gao et al., 2008; Lin et al., 2008). A composite (meth)acrylate-reactive sites. This result verified the advantages
wear study with bioactive glass-ceramic fillers was conducted, of MPS and its acrylate analog, but also pointed out the potential
and it demonstrated improved performance at low levels of sur- of a mercapto-functionalized silane to serve as a durable cou-
face porosity, but reduced wear resistance in the case of highly pling agent (Matinlinna et al., 2007). In contrast, the addition of
porous filler surfaces (Tan et al., 2010). An examination of mercapto-functionalized silica nanoparticles to a thiol-ene-
nano-fibrillar silicate crystals showed the potential for improved based resin was examined for its effects on photopolymerization
mechanical properties, but also highlighted the difficulties of reaction kinetics. The presence of a stoichiometric thiol to ene
obtaining uniform dispersion of the nano-structures in the imbalance in the vicinity of the nanoparticle interface resulted
matrix (Tian et al., 2008). The combination of calcium phos- in a suppression of the overall thiol-ene reaction rate at low
phate nanoparticles with silicon nitride whiskers produced a filler loading, but at high nanoparticle content, viscosity effects
OCH 3
OCH 3
filler shape and surface modifi-
CH3O Si O
cation relative to the resin
CH3O Si dictate the effects of the filler
OCH 3 on the composite properties.
O OCH 3
These effects of the filler on
3-Methacryloxypropyltrimethoxysilane n-Octyltrimethoxysilane
composite properties are prom-
inent in several investigators
OCH 3 work, where it has been dem-
OCH 2CH3
OCH 3 onstrated that the methacrylate
CH3O Si
CH3 O Si SH
CH3H2CO Si conversion in composite mate-
OCH 3 OCH 2CH3 rials is inversely related to the
OCH 3
filler loading level (Halvorson
3-Mercaptopropyltrimethoxysilane Styrylethyltrimethoxysilane Allyltriethoxysilane
et al., 2003; Tanimoto et al.,
Figure 2. Various silane modifiers used to induce enhanced dispersion, coupling, and copolymerization 2005; Garoushi et al., 2008;
in filled composite restorative materials. Nunes et al., 2008). One study
focused on the effect of varied
MPS coverage (from 0 to 20
associated with the particles produced an enhanced photopoly- wt%), with the finding that increased silane surface treatment on
merization rate (Lee and Bowman, 2006). 0.6 m zirconia glass filler resulted in lower overall conversion,
A neutron scattering analysis of silanized nanoparticles over based on relatively poor reactivity of methacrylate groups
a range of loading levels in a model dental resin showed that within the mobility-restricted interfacial silane layer (Halvorson
dispersion was enhanced, although still not fully achieved, with et al., 2003). Contrary to this, a separate study indicated no
an MPS surface treatment rather than n-octyltrimethoxysilane at significant difference in conversion of composites prepared with
the interface (Wilson et al., 2007). The effect of the silane struc- OX50 silica nanoparticles treated with MPS (from 1 to 10 wt%),
ture applied to a filler surface on the handling properties of although spectroscopic evidence of variations in silane orienta-
uncured composite paste as well as the photopolymerization tion dependent on concentration was provided (Sideridou and
process and the final composite properties were investigated Karabela, 2009). Related to the observations of reduced conver-
(Wilson and Antonucci, 2006). The potential benefits of dual sion in filled resins, several studies concerned with the light
silane treatments were considered where the combination of a attenuation based on absorbance and scattering effects in com-
styryl functionalized silane with MPS demonstrated a higher posites have been presented (Emami et al., 2005; Musanje and
modulus in the photocured composite compared with an MPS- Darvell, 2006; Arikawa et al., 2007; Shortall et al., 2008;
treated control composite, while the combination of MPS with Howard et al., 2010). Clearly, a combination of light attenuation
the non-functional n-octyltrimethoxysilane improved the han- associated with increased scattering as well as decreased mobil-
dling properties of the composite paste without reducing the ity in the interfacial layer may be responsible for the observed
mechanical properties of the cured material. In another study, relationship between filler loading and methacrylate conversion,
allyltriethoxysilane was used to surface-treat titanium dioxide depending on the physical and chemical attributes of the sample.
nanoparticles (< 20 nm). The modified TiO2 particles were dis-
persed in a commercial composite (Z100) at 1 wt%, with a sig- New Analytical Approaches Applied to Filled Materials
nificant increase in hardness and flexural strength observed
compared with the unaltered control (Xia et al., 2008). The One significant need in the composite restorative field relates to
degree of spatial ordering of a 500-nm spherical silica filler in the development of new techniques for determining both the
triethylene glycol dimethacrylate could be enhanced with MPS- properties of filled systems and the fillers impact on material
treated filler or disrupted by the introduction of dimethylamino- properties. In this area, several analytical techniques have
ethyl methacrylate with untreated filler. Compressive testing recently been developed or newly applied to help characterize
demonstrated an improved mechanical strength in the ordered dental composite materials. In one exciting approach with the
materials (Wan et al., 2008). The wear resistance of experimen- potential for rapid evaluation of a wide spectrum of materials, a
tal hybrid composites prepared with filler pre-treated with either combinatorial two-dimensional array was applied to composite
MPS, MPS combined with a non-functional fluorinated silane, specimens with discrete variations in filler composition as well
or a novel aromatic methacrylate-functionalized silane was as continuous gradient variations in the methacrylate conversion
studied. The results showed that the new functional aromatic (Lin-Gibson et al., 2009). Different proportions of a 0.7-m
silane has excellent potential as a hydrophobic, matrix-resin- silanized filler were evaluated with or without the presence of a
compatible coupling agent in terms of wear, in comparison with small amount of nanofiller. A rastering nanoindentation tech-
MPS surface-treated filler (Nihei et al., 2008). The structures of nique was used to obtain the localized hardness and elastic
various silane modifiers for fillers are summarized in Fig. 2. modulus and to assess the viscoelastic response based on a pro-
Surface treatment of particulate and short-fiber fillers based on gressive load scratch test. The filler loading and the presence of
ultra-high-molecular-weight polyethylene (3-6 x 106 g/mol) nanofiller were found to alter the viscoelastic behavior of the
demonstrated improved composite toughness, due to the forma- composite materials as well as macrophage cell adhesion,
tion of a ductile interface; however, composite strength and although variations in the methacrylate conversion produced the
modulus were compromised (Ranade et al., 2006). Ultimately, most significant differences. Related to this issue, filler particle
induction of inflammatory cytokines and chemokines in cells Berchtold KA, Nie J, Stansbury JW, Bowman CN (2008). Reactivity of
was demonstrated (Ansteinsson et al., 2009). Another study monovinyl (meth)acrylates containing cyclic carbonates. Macromolecules
41:9035-9043.
used a micromanipulation technique to examine various repre- Berchtold KA, Haciolu B, Nie J, Cramer NB, Stansbury JW, Bowman CN
sentative fillers used in dental composites. Either spherical or (2009). Rapid solid-state photopolymerization of cyclic acetal-containing
irregular filler particles as well as nanoclustered agglomerates acrylates. Macromolecules 42:2433-2437.
were subjected to compressive testing, which provided force- Bernardo M, Luis H, Martin MD, LeRoux BG, Rue T, Leito J, et al. (2007).
displacement curves on both individual filler particles and nano- Survival and reasons for failure of amalgam versus composite posterior
restorations placed in a randomized clinical trial. J Am Dent Assoc
clusters. Differences in fracture behavior were observed, with 138:775-783.
the nanocluster filler producing multiple fracture events (Curtis Beun S, Bailly C, Dabin A, Vreven J, Devaux J, LeLoup G (2009).
et al., 2009a). The same group also found enhanced damage Rheological properties of experimental Bis-GMA/TEGDMA flowable
tolerance in cyclic fatigue loading of Filtek Supreme, hypothe- resin composites with various macrofiller/microfiller ratio. Dent Mater
25:198-205.
sized to be associated with its nanocluster filler morphology
Bowen RL (1956). Use of epoxy resins in restorative materials. J Dent Res
(Curtis et al., 2009b). Ultimately, a model of filler effects on 35:360-369.
composite properties was developed (Tanimoto et al., 2006). Bowman CN, Kloxin CJ (2008). Toward an enhanced understanding and imple-
The field of composite dental restoratives continues to propose mentation of photopolymerization reactions. AIChE J 54:2775-2795.
and achieve significant and exciting advances in resin formula- Braga RR, Ferracane JL (2002). Contraction stress related to degree of con-
version and reaction kinetics. J Dent Res 81:114-118.
tion, filler loading and modification, and curing methodologies Braga RR, Ballester RY, Ferracane JL (2005). Factors involved in the devel-
and mechanisms. While most of the advances discussed herein opment of polymerization shrinkage stress in resin-composites: a sys-
remain in the research stage, the future both in regards to tematic review. Dent Mater 21:962-970.
research and in clinical practice remains bright with exciting Carioscia JA, Lu H, Stansbury JW, Bowman CN (2005). Thiol-ene oligo-
new developments translated into practice at an ever-increasing mers as dental restorative materials. Dent Mater 21:1137-1143.
Carioscia JA, Schneidewind L, OBrien C, Ely R, Feeser C, Cramer N, et al.
rate. With hundreds of millions of restorations performed each (2007). Thiol-norbornene materials: approaches to develop high T-g
year, continuing research into practical advances and successful thiol-ene polymers. J Polym Sci Part A Polym Chem 45:5686-5696.
clinical implementation of composite restoratives are both criti- Cavalcante LM, Masouras K, Watts DC, Pimenta LA, Silikas N (2009).
cal to oral care, aesthetics, and functional restoration. Effect of nanofillers size on surface properties after toothbrush abra-
sion. Am J Dent 22:60-64.
Charton C, Falk V, Marchal P, Pla F, Colon P (2007). Influence of Tg, vis-
Acknowledgments cosity and chemical structure of monomers on shrinkage stress in light-
cured dimethacrylate-based dental resins. Dent Mater 23:1447-1459.
The authors gratefully acknowledge NSF Grant 0626023, and Chappelow CC, Pinzino CS, Chen SS, Kotha SP, Glaros AG, Eick JD
(2008). Tetraoxaspiroalkanes for polymerization stress reduction of
NIH/NIDCR Grants DE10959 and DE018233. This work is
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Recent Advances and Developments in Composite Dental Restorative Materials

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CRITICAL REVIEWS IN ORAL BIOLOGY & MEDICINE

N.B. Cramer1, J.W. Stansbury1,2,

J Dent Res 90(4):402-416, 2011

associated with successfully

BisGMA/TEGDMA 70/30 64.1 2.8 93.2 8.3 7.26 0.51 -

*Polymerization-induced phase separation

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