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d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 17

Available online at www.sciencedirect.com

ScienceDirect

journal homepage: www.intl.elsevierhealth.com/journals/dema

High-aspect ratio llers: Fiber-reinforced


composites and their anisotropic properties

Pekka K. Vallittu
Department of Biomaterials Science and Turku Clinical Biomaterials Centre TCBC, Institute of Dentistry,
University of Turku, Turku, Finland

a r t i c l e i n f o a b s t r a c t

Article history: Objectives. To present an overview of ber-reinforced composites (FRCs) that are a group of
Received 21 June 2014 non-metallic dental biomaterials used in several elds of dentistry.
Received in revised form Methods. A range of relevant publications from the past half century are surveyed, with
11 July 2014 emphasis upon recent publications.
Accepted 14 July 2014 Results. FRCs vary according to the type of ber llers and orientation of bers, the latter being
responsible for several properties which can vary from isotropic to anisotropic. The length
of the bers, i.e. the aspect ratio of the ller, is another factor or variable that contributes
Keywords: to the properties and the development of new types of composite resins for restorative and
Fiber prosthetic dentistry, as well as to reconstructive medicine.
Composites Signicance. Understanding the anisotropic nature of FRCs from the perspective of dental
Fiber-reinforced composite applications has increased in recent years. This review describes some ber orientation
Polymer related anisotropic properties of FRCs which contribute to the increased use of FRCs in
Anisotropicity clinical dentistry.
2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

produced in 1937 in Russia and since then the anisotropicity


1. Introduction of ber-reinforced materials has been utilized in everyday life
and recently in dentistry and medicine.
Using high aspect ratio llers in composite resins can signif- In natural constructs, reinforcing bers of cellulose can
icantly change the resins physical properties in comparison be found, e.g. in wood, where the length of the oriented
to using particulate llers which provide isotropic properties polysaccharide based cellulose bers and shorter branched
for the material. High aspect ratio llers have a high ratio of hemicellulose bers is between 0.8 and 2.3 mm [2]. Chiral and
the length of the ller to its cross-sectional diameter. In com- crystalline cellulose bers in wood are embedded in the lignin
posites, high aspect ratio llers are bers but shorter lament matrix, which is a natural biopolymer of aromatic alcohols.
like llers of whiskers can be also considered high aspect ratio Other examples of natural systems that contain high aspect
llers [1]. Different types of bers with various orientations ratio components include bone and dentin [3]. Osseous tis-
and lengths have been utilized for decades in engineering sue of bone and dentin is composed of a hard, lightweight
applications to construct devices with high strength and composite, where mineral calcium phosphate in the chemical
fracture toughness. The rst glass ber-reinforced boat was arrangement of hydroxyapatite forms the inorganic matrix for


Correspondence to: Institute of Dentistry, University of Turku, Lemminkisenkatu 2, FI-20520 Turku, Finland. Tel.: +358 2 333 8332.
E-mail address: Pekka.vallittu@utu.
http://dx.doi.org/10.1016/j.dental.2014.07.009
0109-5641/ 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
2 d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 17

the protein origin collagen bers, which are formed from thin-
ner type I brillar collagen. The collagen bers with a diameter
of 20400 nm consist of collagen molecules, which are stabi-
lized by four cross-linking covalent bonds per molecule [4].
The length of collagen ber is around 23 m [5]. High aspect
ratio bers in collagen provide high tensile strength and frac-
ture toughness for bone and dentin, whereas hydroxyapatite
is responsible for the compressive properties. Both collagen
bers and crystals of hydroxyapatite are oriented best to with-
stand physiological loading conditions. Mineralized collagen
bers provide toughness through crack-tip shielding through
osteons, especially with lower strain rates [6].
Man-made high aspect ratio llers have been used since
ancient times to reinforce bricks and buildings [1]. Modern Fig. 1 Inuence of the aspect ratio (l/d) of bers and their
ber-reinforced composites (FRCs) are used in applications orientation to the tensile stress ( t ) and modulus of
where high static and dynamic strength and fracture tough- elasticity (E) with the same volume fraction of bers (Vf )
ness, especially in relation to weight, are desired properties. [34].
For example, dental and medical devices are typically sub-
jected to hundreds of thousands of loading cycles by the
masticatory system or the weight of the body during physical
exercise [7]. FRCs are typically designed to have the highest classied as short discontinuous and long continuous FRCs;
possible reinforcing efciency against the direction of stress, which have different mechanical properties although the ber
and thus, they often represent anisotropic material in terms volume fraction could remain the same [34]. By changing
of mechanical properties. However, some other properties, continuous unidirectional bers to longitudinally oriented dis-
such as optical properties, surface physical properties, ther- continuous short bers of lower aspect ratio, ultimate tensile
mal properties and polymerization contraction properties are strength of the composite is reduced (Fig. 1). In this case both
related to the orientation of the bers in the FRC. From the continuous and discontinuous FRCs are anisotropic. Changing
point of view of high fatigue resistance and toughness, FRC the orientation of short bers so they lay randomly causes the
is part of a group of choice materials for dental and medi- tensile strength to reduce even more, and the FRC material
cal needs. FRCs in dentistry were rst developed in the early becomes isotropic. Consequently, strength, unlike stiffness of
1960s but an increase in the number of published scientic continuous FRCs, cannot be attained by discontinuous short
papers occurred in the early 1990s [815]. Currently, FRCs ber systems even with high aspect ratios [34]. Failure types
are used in xed prosthodontics, restorative dentistry, peri- of discontinuous short FRCs including cracking of the polymer
odontology, orthodontics and in repairs of prosthetic devices matrix, debonding of the ber and fracture of the ber (Fig. 2).
[1626]. There are also cranial implants made of glass FRCs and Depending on the length of the ber, aspect ratio of the ber,
attempts to develop oral and orthopedic implants are ongoing interfacial fracture energy (adhesion of bers to the matrix)
[27,26,28,29]. This is a review of the current status of knowl- and ber volume fraction, some of the failure types are more
edge of some anisotropic properties of FRCs used in dentistry. common. Dependence between the orientation and length
of the bers is also described by Krenchels factor, in which
the reinforcing efciency factor for ber reinforcement goes
2. Reinforcing efciency of bers
against the known direction of stress [35]. Reinforcing bers
in the direction of the stress provides the highest reinforcing
The majority of dental FRCs are presently produced from glass efciency and nally axial failure of the bers and polymer
bers due to their surface chemistry, which allows for their
adhesion to the resin matrix via silane coupling agents, and
to the transparency of their bers [3032]. Glass bers do
not cause severe problems related to the appearance of the
restoration. Out of the several different types of bers (car-
bon/graphite, aramid, polyethylene), glass bers have been
adopted for use in dentistry and medicine. The most com-
mon glasses, namely E-glass and S-glass, and their behavior
as components of dental FRCs were recently reviewed in more
detail in another publication [33].
FRC is a material which contains at least two phases, one
of which is characterized by its high aspect ratio, i.e. ratio Fig. 2 Schematic presentation of the types of failures
between the length and diameter (l/d). Among many parame- (crack of the matrix, debonding of the ber, fracture of the
ters (interfacial adhesion, elongation of bers, ber volume ber) of discontinuous short ber-reinforced composite
fraction) which contribute to the reinforcing efciency of (Xo = embedded ber length which as debonded,
bers, length and orientation of bers are important in terms d = diameter of ber, L on ber length, f = volume fraction of
of the isotropicityanisotropicity of the material [1]. FRCs are bers). Arrows show the direction of load.
d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 17 3

Fig. 4 Schematic presentation of alternatives to bond


particulate ller composite resin (PFC) to the surface of
ber-reinforced composite (FRC) (upper row) and bonding
ber-reinforced composite (FRC(bidir)) = bidirectional bers,
FRC (rand) = randomly oriented bers, FRC(vert) = vertical
unidirectional bers) to the surface of enamel (E) and
dentin (D). Bonding values are shown in Fig. 5.

Fig. 3 Schematic presentation of types of failures (from top


to bottom: axial tensile failure, transverse tensile failure,
shear failure) of a continuous unidirectional ber-reinforced dentures) [17,19,40,41]. In these applications, the orientation
composite. Arrows show the direction of force. of bers in the load-bearing part of the construction is selected
according to the loading conditions of an FRC system, which
can best resist the mechanical stresses of the masticatory sys-
tem. The surface of the substrate onto the adhesive resin,
matrix will occur (Fig. 3). If stress is applied perpendicular to
luting cement or veneering composite resin is adhered and
the bers, the bers do not reinforce the FRC, and transverse
can have different orientations of bers as shown in Fig. 4.
failure of the polymer matrix occurs.
In the case that the surface of the substrate is ground, and
The effect of the aspect ratio of bers is also related to
the reinforcing glass bers are exposed, an average of 50% of
critical ber length, which can be dened as the minimum
the surface area of the substrate is composed of the polymer
length of the ber. It allows for the development of sufcient
matrix and 50% are glass bers. The exposed glass bers are
stress to cause the ber to fail at its midpoint. Interfacial frac-
those which have lost the surface silanation due to the grind-
ture energy of the adhesive interface between the bers and
ing. This can occur with prefabricated FRC root canal posts
polymer matrix versus the tensile strength of the ber has
and frameworks in xed dental prostheses, which are poly-
an impact on the critical ber length. It has been concluded
merized and mechanically shaped before veneering. Repairs
that for advanced FRCs, the critical ber length could be as
to FRC constructs also expose the bers to the surface. Bonding
much as 50 times the diameter of the ber. To eliminate ber
mechanisms and bonding efciency to the cross-linked poly-
debonding under tensile stress, FRCs with longer bers could
mer matrix and interpenetrating polymer matrix have been
exhibit strength similar to the corresponding continuous FRC
reported [42]. When the orientation of exposed bers is con-
[36]. The diameter of glass bers presently used in dental FRCs
sidered, the highest bonding strength to the FRC surface is
is 1518 m and the critical ber length should be, therefore,
obtained with perpendicularly exposed bers (Fig. 5). Fibers in-
between 750 and 900 m [37]. A recently introduced short ber-
a-plane, which were along the direction of debonding stress,
reinforced composite for lling applications has ber lengths
reached almost the same value of bonding strength as perpen-
within this range [38,39].
dicularly oriented bers, whereas the in-a-plane bers, which
were opposite to the debonding stress, gave the lowest bond-
3. Fiber-reinforced composite as an ing strength [43] (Figs. 4 and 5). Discontinuous short bers can
adhesive substrate be used to reinforce dental llings [39]. A layer of discontin-
uous short FRC, which replaces the missing part of dentin,
Use of FRCs in dental applications requires covering the is covered with a layer of particulate ller composite resin to
ber-rich part of the construction by some other resin sys- achieve a wear resistant and polishable surface. FRC layer sub-
tem in order to adhere (adhesives and luting cements) structures and the particulate ller composite resins form a
the ber-rich FRC to the dental tissues. This also protects bilayered composite structure in which randomly oriented and
the bers and provides a polishable surface for the FRC slightly protruded discontinuous bers reinforce the interface
device (veneering composites, lling composites, removable of the composite layers.
4 d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 17

Fig. 5 Shear bond strength (MPa) of material combinations Fig. 6 Anisotropic linear polymerization contraction strain
described in Fig. 4 [4345]. (microstrain) of ber-reinforced composites (FRC) with
various orientations of bers and the direction of
measuring the strain in relation to the long axis of the ber.
In direct applications of FRCs, e.g. during fabrication of Control material is isotropic particulate ller composite
direct xed dental prostheses or periodontal splints, the bers resin [53].
are adhered directly to the surface of the dentin or enamel.
In direct applications, the orientation of bers can vary from
bidirectional weaves to veils of randomly oriented bers to
continuous longitudinal bers (Fig. 5). Bonding efciency of
FRCs with different orientations of bers varies only slightly
from each other (Fig. 5) [44,45].

4. Polymerization contraction

Polymerization contraction is one of the shortcomings related


to dental composite resins, which contributes to the longevity
of restorations [4648,50,51]. Reinforcing bers not only
improve mechanical properties of the composites but can also
control the polymerization contraction. Polymerization con- Fig. 7 Anisotropic hygroscopic expansion of the
traction strain of FRCs has been measured by conventional ber-reinforced composite (FRC) compared to isotropic
strain gauges and optical Bragg grating sensors [49,52]. Both expansion of particulate ller composite resin and unlled
strain gauges and Bragg sensors have shown the depend- resin [49].
ence of the polymerization contraction on the direction of the
reinforcing bers. Fig. 6 summarizes isotropic polymerization
contraction strains of particulate ller composite resin and the opposite: direct polymerization of the FRC in the root
FRCs with varied orientations of bers. Hygroscopic expansion canal with the composite resin luting cement demonstrated
of resin composites is also dependent to the ber orienta- better adaptation and sealing between the post and root
tion (Fig. 7) [49,53]. FRCs with longitudinal ber orientation canal compared to the posts, which were polymerized chair-
demonstrate no contraction in the direction of bers; minor side before cementation. This was explained by the elastic
thermal expansion can be found, which is caused by an properties of the FRC post interpenetrating polymer net-
increase in temperature due to exothermic polymerization work (IPN) polymer matrix. The lower modulus of elasticity
reactions. Anisotropicity in polymerization contractions can of the IPN polymer matrix was assumed to be able to
be benecial in tailoring the properties of lling composite absorb polymerization contraction stress during polymeriza-
resins in order to minimize gaps between llings and tooth tion and cause less stress to the cementtooth interface
substances. [42,56].
An observation was published recently on the use of
individually formed FRC root canal posts, i.e. FRC mate-
rial, which is directly polymerized in a root canal with a 5. Effect of ber orientation on optical
high conguration factor (c-factor = 953) [54]. It was expected properties
that the higher polymerization contraction in the trans-
verse direction to the bers of the FRC could have caused Optical properties of FRCs are also ber direction related; they
debonding and gap formation between the FRC material are utilized in ber optics of communication systems and
and root canal dentin [55]. However, the results showed in transmission of light in illumination applications. Fiber
d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 17 5

optics can also be used in sensor technology, for instance


in Braggs grating sensors to measure dimensional changes
with high precision [57]. Optical bers have a transparent
core, which is covered with a transparent cladding material
with a lower index of refraction in order to keep the light in
the core by total internal reection. Applications in dentistry,
which are utilizing optical properties of bers can be found in
restorations of root canal treated teeth [5861]. There are some
prefabricated FRC root canal posts available which transmit
the polymerization light through the post and enables light-
initiated polymerization to occur in the composite resin luting
cement [59,60]. In the case of individually formed FRC root
canal posts, the resin matrix of the post needs to be polyme-
rized as well as the resin based luting cement. Transmission
of light to the resin system surrounding the bers and to the Fig. 8 Index of refraction and extinction coefcient of a
ber-rich area in general is based on reectance and the scat- monomer system of bisGMATEGDMA in volume ratios of
tering of the light. Scattering of light includes the deection of 50:50 and 99:1 plotted against the light curing time. The
a ray of the light from a straight path. The deection of light gray area demonstrates the refraction index of E-glass
can be caused by irregularities in the propagation medium, at bers with different compositions [62,63].
the interface between two media, or from differences in the
refraction indices of light transmitting bers in the surround-
ing resin system. Scattering of this type is referred to as diffuse
reection.
There are studies related to the optical properties of ller composite resin with a thickness of more than 2 mm
dimethacrylate resin systems in the context of light- in order to eliminate the risk of color shade mismatch [65]
initiated polymerization of resin systems. It has been shown (Fig. 8).
that polymerization reactions of bisphenol-A-dimethacrylate
(bisGMA)triethylene glycol dimethacrylate (TEGDMA) resin
systems increase the refraction index from 1.515 to 1.550 6. Other anisotropic properties and
with a bisGMATEGDMA ratio of 50:50, and to 1.580 with conclusions
bisGMATEGDMA ratio of 99:1 (Fig. 7) [62]. This is due to the
reorganization of the molecular structure during polymeriza- Research on man-made FRCs demonstrates that they
tion. At the same time, the extinction coefcient at the 470 nm mimic structurally constructs of biological systems. Natural
wavelength of the resin system decreases due to reducing anisotropic systems are not only anisotropic in their nal
the amount of initiator camphorquinone until the extinction constructs. Natural systems function anisotropically during
coefcient is dominated by the copolymer only. Simultaneous the creation of tissues and structures from cellular activity.
changes in the refraction index and extinction coefcient of Anisotropic substrates for cells can direct cell morphology
the resin system, and the refractive index of E-glass ber and growth. Studies related to continuous unidirectional E-
(1.556) and boron free E-glass ber (1.547) [63], enhance light glass FRC in implant applications have shown that surface
to scatter out from the glass bers once the polymerization wettability, surface energy and cellular responses are also
of the resin system has started and proceeded to a particular dependent on the direction of the exposed glass bers [66,67].
stage (Fig. 7). This is according to the Snells law of relation- Microscopic investigation has shown broblast cells to ori-
ship between the angles of incidence and refraction of light ent themselves parallel to the direction of E-glass bers.
passing through a boundary between two isotropic media; E- This was likely due to the hydrophilic surface of the glass
glass and resin system of bisGMATEGDMA. In practice, this ber when compared to the polymer matrix. Approaches
phenomenon is utilized in the polymerization of continuous of tailoring ber-containing scaffolds for tissue engineering
unidirectional E-glass ber composite prepreg with an opti- applications are ongoing. One promising alternative could be
mized bisGMATEGDMA ratio inside the root canal when an to add brous scaffold to the surface of the implant con-
individually formed root canal post is prepared. It is known struction in order to enable anisotropic tissue growth to the
that surface irregularities of the bers enhance scattering. implant.
It has been demonstrated in vitro that the depth of light- It can be concluded that FRCs with high-aspect-
initiated polymerization of the bisGMATEGDMA resin matrix ratio llers have several properties which relate to the
of FRC root canal post is 18 mm for the degree of monomer direction of the bers. In the case of unidirectional
conversion of 55%. This exceeds the length of the suggested bers, both continuous and discontinuous bers provide
individual FRC post (ca. 5 mm), which has shown to provide anisotropic properties for the composite. Dependent on
the highest load-bearing capacity for a root-post-crown sys- the application, anisotropicity should be carefully con-
tem [64]. Optical properties of glass FRCs also play a role in sidered when designing FRC devices. More research is
the appearance of FRC-reinforced restorations. A recent study needed for detailed information on anisotropicity and
showed that continuous unidirectional and bidirectional E- its inuence on the function of FRC devices in clinical
glass bers should be veneered with a layer of particulate applications.
6 d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 17

[18] Vallittu PK. The effect of glass ber reinforcement on the


Acknowledgements fracture resistance of a provisional xed partial denture. J
Prosthet Dent 1998;79:12530.
Author expresses gratitude to the researcher team [19] Narva K, Vallittu PK, Yli-Urpo A. Clinical survey of acrylic
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(www.biomaterials.utu.) and principal nancing part-
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Glass-bre-reinforced composite xed partial dentures on
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Commission (Grant: NEWBONE NMP3-CT-006-026279-2). 902.
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