Dental Biomaterials: Where Are We and

Where Are We Going?

Stephen C. Bayne, M.S., Ph.D., F.A.D.M.
Abstract: This article reviews the current state of the art for restorative biomaterials by examining the roles of 1) truly biological
biomaterials, with respect to the “near-future” of five to ten years, 2) traditional synthetic biomaterials, and 3) performance
outcomes for biomaterials. Biological biomaterials are discussed in terms of tissue engineering and stem cell research, self-
assembling system opportunities, and nanotechniques or technologies. Future developments for major areas of synthetic
biomaterials are considered for bonding systems, composites, VLC curing, ceramics, and cements. Performance outcomes are
discussed for all biomaterials in terms of safety, efficacy, and longevity of materials.
Dr. Stephen C. Bayne is a Distinguished Professor, Department of Operative Dentistry, University of North Carolina School of
Dentistry. Direct correspondence to him at the UNC School of Dentistry, CB#7450, University of North Carolina, Chapel Hill,
NC 27599-7450; 919-966-2776 phone; stephen_bayne@dentistry.unc.edu.
Key words: dental biomaterials, tissue engineering, restorative dentistry, bonding materials, dental ceramics

B
iomaterials science is in the midst of the larg- shifting emphases from traditional synthetic
est transition in its history in terms of refo- biomaterials toward a time when the routine options
cusing and embracing new and exciting tech- involve truly biological materials.
nologies. For older academics or clinicians, this The purpose here is to examine the near-future
change might be viewed as the death of conventional or the next five-to-ten-year period (see Figure 1 for
dental materials, but for most others, this is the birth impacts of this transition). This state-of-the-
of true biomaterials. biomaterials report will be examined in terms of bio-
For many years, one of the in-house questions logical materials fabrication (tissue engineering,
among biomaterials teachers1 was if or when any- nanoengineering, self-assembling systems), leading
one would move the field of biomaterials from the edge synthetic biomaterials utilized in chairside den-
materials engineering side (materials) more toward tal applications (bonding, composites, curing, ce-
the biological engineering side (biology). The earli- ments, and ceramics), and assessment of the perfor-
est dental materials science began in the laboratory mance outcomes of these strategies (longevity).
of G.V. Black at Northwestern University in 1900 It is easy to list the large number of doors now
with the first controlled experiments on dental amal- open for biomaterials research, but it is much more
gam. The field vaulted forward when the excellent complicated to define an accurate timeline for the
textbooks in the field became available (e.g., EW future. Most of the crucial steps for biological mate-
Skinner, The Science of Dental Materials, 19362). In rials success have yet to become well defined. It may
those earlier times, dental materials were focused be possible now to demonstrate the production of a
exclusively on synthetic restorative dental materi- biologically new tooth using stem cell pathways, but
als. By the early 1970s, the term “biomaterials” be- it is very hard to imagine the moment in the future
came more prominent with the formation of the So- when practical and low-impact methods will exist
ciety for Biomaterials, yet even its focus remained for placing these entities into full function in patients
primarily on orthopedic applications that utilized by general practitioners. In the excitement of the
existing dental materials for the next thirty years. moment, we dream of those possibilities. However,
Despite continual discussions about refocusing the at the moment, a safer guess about translation of bio-
field of biomaterials, the greatest impetus for change logical materials into routine practice is twenty years.
did not arrive until the decoding of the human ge- Any impact of truly biological materials de-
nome at the end of the last century. Suddenly, the pends on a combination of both technology and cost.
real potential for biological engineering of tissues If replacement teeth were available today from a
and organ systems was revealed. The question for us hypothetical personal tissue bank, would this be a
today is how to paint the future for biomaterials. practical option for most restorative circumstances?
Perhaps the correct image is that we are now im- Would a patient with pit-and-fissure caries be better
mersed in a twenty- to twenty-five-year transition of served with a minimal composite restoration or an

May 2005 ■ Journal of Dental Education 571

 entire tooth replacement? When would one draw the Regenerative treatments require the three key
line between discontinuing synthetic biomaterials elements: an extracellular matrix scaffold (which can
approaches for restoring teeth and shifting to bio- be synthetic), progenitor/stem cells, and inductive
logical materials approaches? A substantial window morphogenetic signals. The oral cavity offers spe-
remains for developing much better synthetic mate- cial advantages over other parts of the body for tis-
rials. Most likely there will be a mixture of both strat- sue engineering because there is ready access and
egies in general practice for at least two decades. ease of observation. At the present time, the signal-
ing processes that control the development of dis-
crete dental morphologies for incisors, canines,
New Biomaterials premolars, and molars are not clear. Successful
bioengineering of recognizable tooth structures has
True biological biomaterials are ones that lead been reported using cells from dissociated porcine
to natural tissue restoration. At the moment, tissue third molar tooth buds seeded on biodegradable poly-
engineering approaches rely on synthetic scaffolds mer scaffolds that were grown in rat hosts for twenty
that are generally resorbable as a means of manag- to thirty weeks.7 Successful bioengineering has dem-
ing tissue development, but that need not always be onstrated that mature tooth structures form single-
the case. The paragraphs that follow consider the cell suspensions of four-day postnatal cultured rat
impacts of tissue-engineered systems seeded with tooth bud cells on polylactic acid scaffolds grown as
stem cells, biologic and non-biologic self-assembling implants in the omenta of adult rat hosts over twelve
systems, and nanotechniques and technologies. weeks.8 Murine teeth have been produced recently
using stem cell-based engineering techniques.9
Tissue Engineering and Stem Cell The developmental capacity of embryonic stem
cells (ESCs) and the tissue repair potential for adult
Research stem cells (ASCs) make their use truly exciting.10 At
An excellent summary of tissue engineering for the present time, the politics of collecting ESCs has
dentistry and the role of bone morphogenic proteins severely restricted research in this arena.11 However,
(BMPs) has been presented by Nakashima and Reddi3 if ASCs turn out to have potential similar to ESCs,
and is summarized in Figure 2. There is significant then this political hurdle may be circumvented. For
potential in the orofacial complex for fracture heal- dentistry, the transplantation of dental pulp stem cells
ing, bone augmentation, TMJ cartilage repair or re- may some day be used to repair bone or regenerate
generation, pulpal repair, periodontal ligament regen- teeth. Using a patient’s own stem cells avoids issues
eration,4-5 and osseointegration6 for implants. of histocompatability. There is strong evidence for

Synthetic Dental Biomaterials

Biological Biomaterials

N ear F ar
FU T URE FU T URE

1980 1990 2000 2010 2020 2030 2040

5 years 20 years

Tissue Engineering and Stem Cells

Nano-Engineering and Self-Assembly

Figure 1. Timeline of the recent past, near future, and far future for the use of synthetic dental biomaterials versus
truly biological materials

572 Journal of Dental Education ■ Volume 69, Number 5

Figure 2. Summary of the opportunities for tissue engineering to develop scaffolds, cells, and signals to create
substitute or replacement dental tissues in the future
Potential applications include fracture replacement, alveolar ridge augmentation, TMJ reconstruction, dentin replacement,
PDL replacement, and pre-osseointegration of dental implants.
Source: Nakashima M, Reddi H. The application of bone morphogenic proteins to dental tissue engineering. Nature Biotech
2003;21:1025-32. Reprinted with permission.

this potential in regeneration experiments conducted can be biological assemblies (e.g., viruses, cells, tis-
in animal models. However, significant technical sues, organisms) or nonbiological ones (e.g., crys-
hurdles still exist. tals).13 These can produce domains at nano-, micro-,
Scaffolds, cells, and signals have been com- milli-, and macro “scales.” Assemblies can be made
bined without much elegant control until relatively from metals, ceramics, polymers, or complex con-
recently. The same lithography and printing tech- structions of several materials. However, at the mo-
niques discussed for ceramics are also available to ment, the most intriguing systems are nanoscale ob-
lay down scaffolds, cells, and signals in a well-con- jects involving organic or ceramic construction.
trolled three-dimensional architecture.12 Printing is Production of assemblies occurs in orchestrated
a special tissue engineering tool for the future. stages of initiation, propagation, and termination.
Numerous surfaces of nonbiological materials Control systems for initiation and/or propagation may
such as implants could benefit by pre-treatment (pre- be templates (e.g., template polymerization of pro-
integration) with those tissues that would normally teins, patterning for silica templates for electrical
result from healing or osseointegration. This has al- circuits), or they might depend simply on natural rules
ready been evaluated with existing implant systems.6 corresponding to energetically favorable physical,
This may make possible a much more biologically chemical, mechanical, and/or biological events (e.g.,
and physiologically stable, immediately loaded im- capillary forces,14 heterogeneous nucleation of
plant. Eliminating long healing phases is desirable crystallization, surface energy reduction, phase sepa-
for dental implant acceptance by patients. ration, micelle formation, steric probabilities for mo-
lecular folding). The intrigue for current engineers
Self-Assembling Systems is that self-assembling nanoscale objects can become
nanoscopic pharmaceuticals, nanosensors, nano-
Self-assembling systems are ones that auto-
domains, or nanophases with special properties,
matically construct prespecified assemblies. These
nanobuilding blocks,15 nanocontrol systems, nano-

May 2005 ■ Journal of Dental Education 573

 devices,16 and many other functional entities. The conceivable that the same events could be managed
potential is infinite. on a nanoscale within the body and with the proper
At the moment, the challenge is to learn how self-assembling nanoscaffolds this process could be
to take advantage of natural rule systems (e.g., mi- highly targeted.
celle formation, energy minimization, crystallization)
and learn to build geometries of interest that will have Nanotechniques or Technologies
useful functions. For example, it is possible to con-
Not only has the scale of research changed for
struct a nanocage, but not be able to control trans-
the design of new biomaterials, but so have the re-
port in and out of the cage. It is possible to construct
search tools. At UCSF, Dr. Sally Marshall’s team has
a nanoswitch but have no systems that it can switch
been conducting an in-depth investigation of dentin
on. Perhaps a more sophisticated way of envision-
structure for more than ten years,17-22 utilizing a
ing the potential of self-assembling systems is in
unique set of nanoscopic tools. They have collected
terms of multistage constructions with complex func-
evidence for a nanoscopic view of normal and ab-
tions. One of the great advantages for individuals
normal dentin. The UCSF team was first to take ad-
involved with this emerging field is that the science
vantage of unique x-ray scanning tomography (XTM)
of biomaterials (or materials) is the same science as-
to profile in three-dimensional micro-architecture of
sociated with natural rule systems for self-assembling
1x1x1µm cube of normal and carious dentin.23 Their
processes.
team built the first fully functioning atomic force
Presently, tissue engineering relies heavily on
microscope (AFM) to explore dentin and modified
systems outside the body to create scaffolds, pro-
dentin nanostructure (see Figure 3)24 while measur-
vide cells, and create signaling systems. It is certainly

Figure 3. Nano-AFM image of collagen fibrils in dentin after decalcification in preparation for hybrid layer formation
Top: Mixed-mode surface plots of tapping and phase mode AFM images of dentin collagen fibrils, obtained a) in liquid and
b) in air. The axial repeat pattern is still present after dehydration.
Bottom: AFM images of dentin collagen fibrils obtained in liquid: a) tapping mode image: gap and overlap zones of adjacent
fibrils interlock; b) phase mode image reveals the presence of mineral particles attached to fibrils.

Source: Habelitz S et al. In situ atomic force microscopy of partially demineralized human dentin collagen fibrils. J Struct
Biol 2002;138:227-36. Reprinted with permission.

574 Journal of Dental Education ■ Volume 69, Number 5

ing nanohardness and nanomodulus (modulus map- cient to guarantee that decalcification occurs in five
ping)25 information to assess the true mechanical to eight seconds. Priming materials are optimized to
properties of nanodomains of tooth structure. That ensure wetting and flow occur on substrates. They
instrumentation has been further refined to permit usually are optimized for the surface characteristics
pico-measurements of some features. of dentin rather than enamel. Primers are hydrophilic
and low viscosity. Solvent typically is added to ad-
just primer viscosity and improve its wetting. Thus,
State of the Art of Key it is crucial that multiple layers of primer be applied
to ensure that it simply does not soak into and below
Synthetic Dental the surface of dentin. It must fill up the outer dentin
surface and be available for contact with the bond-
Biomaterials ing agent. Since almost all restorative filling materi-
als (e.g., composite) are hydrophobic, a bonding
Where are we at this moment in the adoption agent must chemically bridge between the more hy-
of newer and better biomaterials? What is the imme- drophilic primer and hydrophobic restorative mate-
diate or near future? Despite the protestations of rial. If a bonding agent were not present, then the
many older practitioners about the serviceability of two surfaces would not wet and could not effectively
amalgam restorations, that is not the future. Amal- bond together. Thus, a standard or traditional three-
gam will not disappear, but it is not the future for component bonding system is represented as
restorative dentistry.26-27 Clearly, the major research E+nP+B. The “n” is used to remind one that mul-
efforts of the last decade have been heavily focused tiple applications of primer are required to adequately
on bonding systems, composites, ceramics, and es- fill the surface.
thetics (and bleaching). The following paragraphs In response to concerns by practitioners that
consider their status and potential over the next five bonding procedures were too complicated and
years. seemed time consuming, there was a movement to
reduce the number of steps. Two principal approaches
Bonding Systems arose. Early the 1990s, Japanese scientists began uti-
Bonding systems have been in continual de- lizing acidic monomers to combine the etching and
velopment for dentistry for fifty-five years since acid priming steps. A few years later, North American
etching was introduced.28 We have cycled through scientists were pushing to combine the priming and
times when there were no bonding systems, enamel- bonding steps, while retaining the traditional etch-
only bonding systems, separate enamel bonding and ing process. We will consider these in the opposite
dentin bonding systems, and now to combined order.
enamel/dentin bonding systems.29 Current bonding If one retains the etching (E) step but combines
systems now are optimized to work well on dentin. the priming and bonding steps (nPB), then the bond-
For many years, there was a popular classification ing system is purportedly simpler and faster (E+nPB).
system that suggested that bonding systems evolved Normally, this would be described as a two-compo-
in generations,30 but finally that concept has fallen nent total-etch system on the basis that two bottles
out of vogue. New bonding systems come in many (phosphoric acid solution and primer-bonding ma-
different flavors. A better approach for classifying terial) are in the commercial kit. The etchant is the
bonding systems is in terms of the number of compo- traditional phosphoric acid solution or gel (15 per-
nents, their actions, and/or the type of acid being used. cent, 35 percent, or 37 percent H3PO4 in water) that
All focus on formation of a hybrid layer in dentin.31 works quickly and allows preservation of a hydrated
Kanca32 introduced a simple shorthand years dentin surface. Any system that combines primer-
ago that is very instructive in this regard (see Figure bonding materials generally has a high concentra-
4). Conventional three-component systems can be tion of solvent to keep the two components comis-
represented in terms of their etching (E), priming (P), cible. An extreme case is the 90 percent acetone
and bonding (B) operations. Etching is required to utilized in Prime&Bond (Dentsply, York, PA). Most
remove the smear layer and decalcify intertubular others are at least 65 percent solvent and might in-
zones of dentin or decalcify portions of rods in clude water/alcohol combinations or acetone.33 There
enamel. Etchants must be relatively strong and effi- are different advantages for each choice.

May 2005 ■ Journal of Dental Education 575

 mers that must both dissolve the
smear layer and decalcify the in-
tertubular dentin while penetrat-
ing to embed superficial collagen
and produce an effective hybrid
layer. Many complicated events
must occur in this zone of the in-
tertubular dentin. Etchant-primer
(nEP) must dissolve the smear
layer or, at least, produce suffi-
cient dissolution to penetrate the
smear layer and surround any re-
maining pieces. Decalcification
must occur while this solution
penetrates into the dentin. Once
the hybrid layer is formed and
acidic monomers are polymer-
ized, new polymer must not allow
continuing decalcification by its
acidic side groups that might del-
Figure 4. Simple classification scheme for dentin bonding systems using a eteriously affect dentin below the
formula method first proposed by John Kanca (2004) to remind users of the
smear layer. All of these steps
functions and proper use of the components for dentin bonding systems.
(E=etching, P=priming, B=bonding) must occur in a uniform and pre-
dictable way over the widely
ranging microstructure of dentin
along the walls of a tooth prepa-
As one moves away from phosphoric acid to- ration. At the same time, similar events must pre-
ward acidic organic monomers, the challenges in- pare any enamel surfaces for micromechanical bond-
crease. No option that has yet been tested is as effi- ing. These bonding systems are called “self-etching”
cient and as effective as phosphoric acid for etching primers (SEPs). These systems do not involve “total
tooth structure. Phosphoric acid has the advantage etching” (TE) typical of phosphoric acid-based sys-
of being very acidic (37 percent solutions in water tems.
has pH=0.2). Remember that pH is the negative loga- It is possible to go further and combine all three
rithm of the hydrogen ion concentration. So if one functions into a single package (nEPB), producing
defines pH=7 as neutral, values decrease with in- one-component systems called self-etching adhesives
creasing acidity. pH=6 is ten times more acidic than (SEAs). These have all the challenges discussed for
neutral. pH=1 is 1,000,000 times more acidic than SEPs but additionally must create a surface compat-
neutral. The scale is continuous and actually goes ible to hydrophobic restorative materials. SEAs ac-
below zero. Phosphoric acid is only partially disso- tually are not formulated to work independently as a
ciated. Therefore, as it reacts on tooth structure, the single bottle. Rather, they use novel packaging meth-
pH is effectively buffered, and the solution main- ods to allow a critical component for the setting re-
tains its acid strength for a long time. This is crucial action to come into contact with the main portion of
for good etching. Organic acids, however, suffer from the SEA during the procedure. 3M ESPE’s Adper
the fact that most are not very acidic (pH=1-3) and Prompt L-Pop37 uses an intriguing triple pouch (ad-
do not have the extraordinary buffering capacity of hesive, initiator, and applicator compartments) to mix
phosphoric acid solutions. Therefore, they must work two components and load the applicator brush. AQ
quickly. These solutions become less acidic as the Bond (Sun Medical, but marketed under the trade
etching proceeds. name of Touch & Bond in the United States by Parkell,
34-36
Japanese scientists have examined a wide Farmingdale, NY) places the initiator species within
range of self-etching monomers. The two-component the foam applicator tips, so that final mixing occurs at
systems they have developed involve acidic mono- the time of dipping prior to application.

576 Journal of Dental Education ■ Volume 69, Number 5

 For both SEPs and SEAs, the composition be- component systems. They require mixing regardless
comes a chemical milieu of competing reactions of their curing mechanism.
when so many different things are combined. These Since the goal is clearly to move toward sim-
systems tend not to be very stable. It is common to pler and more predictable bonding results, bonding
recommend cold storage and rapid use since the shelf- systems for enamel and dentin may someday disap-
life is very short. These systems principally include pear. Up to this point, we have ignored the fact that
water as a solvent. While gentle air-drying may be bonding is required for other substrates such as amal-
recommended, air-thinning is not. It tends to displace gam and ceramic. In those cases, traditional designs
unset materials from tooth surface and prevent fu- for dentin do not work as well. Modified bonding
ture contact with the restorative material. Since one systems are required; this will probably continue to
major challenge for SEAs and SEPs is to dissolve be true.
the smear layer quickly, agitation with the applica-
tor or brush is recommended to allow mechanical Composites
disruption of the smear layer as well. Smear layers
Despite the rich history associated with devel-
can be slightly different in properties depending on
opment of dental composites (see the chronology
the type of rotary instrumentation used. Typically,
presented in Figure 5) and their prominent position
smear layers produced by diamond burs are more
in dentistry today, their future is even more promis-
compact and difficult to dissolve. In the case of SEPs
ing for a number of reasons. Non-shrink prototypes
and SEAs, some have argued that, for the present
will reach the market in the short term, solving some
time, it may be better to use carbide burs for final
of the problems related to premature bonding sys-
tooth preparation to ensure the smear layer will be
tem stresses. This will also reduce internal porosity
less resistant to dissolution. In addition, if complex
that may have contributed to higher than desired
clinical conditions further hamper effective etching,
water absorption. Silanes, while used for almost the
manufacturers recommend total etching in advance.
entire history of formulation of composites, have
Since these bonding materials are designed to be
never been optimized or well controlled to produce
hydrophilic, they absorb water from the layers be-
potentially excellent interphase bonding. More at-
low the hybrid layer. They actually wick water to-
tention is being focused on this problem.39 Filler tech-
ward the tooth preparation side of the bonding agent
nologies, which directly affect most composite prop-
film. One must anticipate this as a potential problem
erties including wear resistance, now include more
and work quickly to complete the restorative mate-
and more nanofiller use. Nanofillers permit substan-
rial placement. Otherwise, the bonded surface may
tially smaller interparticle distances and shelter the
become contaminated with water droplets arriving
resin matrix from wear.40 Certain types of nanofillers
from below the film.38
may allow better coloration and radiopacification
Despite our enthusiasm for these newer sys-
systems.
tems, for many clinicians it is not yet practical to
There also is interest in moving away from
rely on these systems for complex bonding situations.
light-curing methods and toward homogeneous cur-
A common conservative stance is to remain with to-
ing options. Despite the dental profession’s enchant-
tal-etch systems to guarantee predictable bonding be-
ment with light-curing methodology, that approach
havior. At the same time and despite pleas for cau-
does not allow consistent depth of curing or degree
tion, there is commercial pressure to carry bonding
of conversion in cavity locations that are poorly ac-
further down the path to what has been called “no
cessible. Therefore, there is a reconsideration of
steps.” The presumption here is that the materials in
chemical curing strategies and new investigations
the one-component systems or SEAs can become part
into other curing strategies.
of the matrix of the restorative material. During res-
All potential improvements, taken together,
toration placement, it is assumed that the matrix phase
mean that composites may become substantially bet-
would start etching and priming on its own. During
ter in the future. These points, and other important
subsequent polymerization, the restoration would be
questions, are considered in depth in the following
locked onto a hybrid layer mimicking traditional
paragraphs.
bonding systems. At the moment, it may be practical
Shrinkage in composites is fickle. Levels are
to make self-etching restoratives or cements, but it
relatively low but occur quickly and affect many pro-
is not practical yet to supply them as truly single-
cesses during the setting process. The most domi-

May 2005 ■ Journal of Dental Education 577

 Figure 5. Simple chronology of the development of dental composites based on their filler technologies and textures
in comparison to curing systems and available bonding system technologies. Topics of interest reviewed in this article
are highlighted.

nant point of view is that, during shrinkage, com- equate or ineffective, then interfacial failures may
posite restorations place high levels of stress on rela- occur. At the same time, other key interfaces between
tively immature dentin bonding films. A simple ex- the matrix and filler phases may be affected. Incom-
ample follows. For a composite formulated with 75 plete or non-uniform silane bonding to the filler par-
weight percent filler (~50 volume percent filler), half ticles prevents appropriate coupling, and local shrink-
of the restoration is resin undergoing shrinkage. age may result in either separation or porosity along
Bisphenol-A-glycidyldimethacrylate (BIS-GMA) or the filler interfaces. In addition to these porosity ef-
similar monomers shrink about 10-12 volume per- fects on fracture resistance, the same sites act as water
cent.41 Polymerization only produces about 65 per- absorption reservoirs.
cent reaction conversion because steric hindrance Low shrinkage or no shrinkage composites
limits the extent of reaction of monomers. Actual have already been demonstrated42-43 as prototypes
polymerization shrinkages of about 3-3.5 percent are using varying chemical approaches. The first evi-
typical. With adjustments in filler levels or mono- dence of these systems was revealed by 3M44 and
mer combinations, this level can be controlled down- ESPE45 during conferences in 2000. In this particu-
ward. During curing, the majority of the reaction (and lar case, prototypes utilized ring-opening reactions
shrinkage) occurs literally in five to ten seconds. With typical of epoxy systems to compensate for the
the emphasis on chairside speed during dental pro- double-bond reaction shrinkage.43,46 These particu-
cedures, the push is toward even faster curing pro- lar systems are not entirely trouble-free. The reac-
cedures. Polymerization stresses occur quickly and tion chemistry is tainted by contact with other dental
unevenly. After a few minutes, stresses relax for a materials and requires some accommodation in for-
variety of reasons, but they potentially have done mulation of other dental materials products. How-
some damage. Despite the fact that newer genera- ever, this was a valuable demonstration that shrink-
tions of dentin bonding systems produce better hy- age could be managed with existing technologies.
brid layers, they are not necessarily any stronger at Silane chemistry has been part of the polymer
the start and can be dislodged by early stresses. If chemistry and composite fields for almost seventy
polymerization of dentin bonding systems is inad- years. These systems work only with Si-O based sub-

578 Journal of Dental Education ■ Volume 69, Number 5

strates, and since so much filler use in dentistry is characteristics. The last point deserves special atten-
silica, they have been very popular. However, tion. Strength alone does not explain the relation-
silanation has never been optimized. Theoretically, ship of filler to wear resistance. Intraoral wear oc-
A174 silane (3-methacryloxy-propyl-trimethoxy si- curs via several different mechanisms,51 but most
lane) acts as a good coupling agent. One end con- occlusal wear is caused by ~0.1 m diameter abrasive
tains three methoxy sites that potentially etherify with particles52 that exist within food that are suspected
hydroxyls on the hydrated surface of silica to pro- to be silica. The matrix phase of a composite is sub-
duce one to three possible ether bridges and chemi- ject to wear, but the much harder filler phase is not.
cally bond to that surface. The opposite end is a Therefore, sheltering of the matrix is possible by
double-bond functional methacrylate, which be- designing the filler particles to be close enough to-
comes co-polymerized with the resin matrix to com- gether to protect the matrix phase from contact with
plete the chemical coupling. By chemically bridg- abrasive food particles. This process is called “mi-
ing the matrix and filler phases, interfaces effectively cro-protection”40 and had strong support based on
can transfer stresses and also drive future cracks to- evidence from long-term clinical trials.53 The pro-
ward the stronger reinforcing filler phase. Yet, there tective capacity was obvious from the excellent wear
is evidence of several problems in this hypothetical behavior observed anecdotally for microfill compos-
chain of events.39 It is difficult, if not impossible, to ites. It is particularly obvious in the newer micro-
produce a monomolecular film of silane on the sur- hybrid and now nanohybrid formulations that are
face of filler particles. Silane does produce outstand- being sold. One might expect that a purely nano-
ing wetting of the filler and may primarily function composite might someday be the ideal composite
in helping matrix monomers to adapt very closely to design.
the filler at a microscopic level. However, silane has Nanofillers are not all the same. A variety of
a propensity to dimerize or trimerize creating meth- nanofillers have already been demonstrated. 3M uses
acrylate moieties that no longer can act as coupling sol-gel technology to produce tiny nanospheres they
agents. Thus, coupled surfaces might be poor at best. call nanomers.54 These can be agglomerated into
Long term, the coupling reaction, which is a con- nanoclusters, and either the spheres or clusters can
densation reaction that eliminates water as a by-prod- become filler particles for composite formulations.
uct, may be reversed by hydrolysis when water pen- 3M ESPE Filtek Supreme55 uses primarily nano-
etrates into the resin matrix.47 This is particularly true clusters in combination with submicron fillers to pro-
under basic conditions.48-49 Due to the nanoscale of duce a hybrid. Pentron has had excellent success with
these interactions, it has been impossible to date to Simile utilizing POSS technology borrowed from
measure the extent of actual chemical interaction Hybrid Plastics.56 In this case, molecular-sized sili-
along filler particles. Finally, when shrinkage does cate cages are produced from silane and
occur, it produces stresses at external interfaces with functionalized for co-reaction with matrix monomers.
tooth structure and internal interfaces with filler par- This technology has great potential that is still being
ticles. Shrinkage leads to phase separation or poros- explored. Still others have designed nanoscale fill-
ity. Porosity in composites is typically at the level of ers using tantalum nanoparticles.57,58
2-5 percent. While this seems like a low level, it may For several years now, the use of the term
be concentrated at critical interfaces and have an even “nanofiller” has been tainted by everyone wanting
greater effect than predicted. If these shortcomings to be on the nanotechnology bandwagon. Typically,
can be managed, there is a strong indication that the nanoscale is reserved for things that are on the order
mechanical properties of today’s composites could of magnitude of 10-9 meters. It is standard for scien-
be substantially improved. tists to use those units to refer to dimensions that are
For many years,50 the potential of nanofillers one to ten units in that size range. Materials with
has been touted. Dentistry is one of the latecomers domain sizes of 1-10 nm do have very special prop-
to adopt this technology. Nanofiller is a part of many erties.
other commercial composite formulations. Mechani- Suddenly, it is in vogue to report even conven-
cal properties of composites depend critically on the tional fillers in terms of nanoscale units. Normally,
filler levels within the formulations. Generally, in- one would not report these sizes as nanoscale enti-
creased filler leads to greater stiffness, higher elastic ties. 1 mm is actually 1000 nm. Microfiller particles
limits, better fracture resistance, and improved wear have diameters of 20-40 nm. It would be more accu-

May 2005 ■ Journal of Dental Education 579

 rate to describe these as “near-nanoscale” phases about 65 percent, then many portions may only be
rather than actual nanoscale ones. In a positive light, cured to 45-55 percent conversion, thereby affecting
this means that we still have yet to realize the poten- the resulting properties of the restorative material.
tial advantages of true nanoscale phases in new com- Actual degrees of conversion depend on the type of
posite formulations. monomers involved. In composites, the monomers
are predominantly difunctional ones, and so these
Visible-Light Curing values are typical. For many of the newer bonding
systems, monofunctional monomers dominate and
Light curing of composite formulations arose
so undercured systems would be represented as 90
during the late 1960s with the adoption of ultravio-
percent conversion.
let (UV) light polymerized systems. In just a few
Best estimates are that, in clinical practice at the
years, it became obvious that visible-light cured
moment, ~85 percent of the VLC units are quartz-
(VLC) had many advantages over UV-light cured
tungsten-halogen (QTH) types and that LEDs domi-
composites, and practitioners made the shift. Den-
nate the remaining 15 percent. Clearly, the shift is
tistry has been wed to VLC systems ever since. De-
under way toward LED units. They have many ad-
spite the apparent chairside advantage for command
vantages. They often do not require fans, have fewer
curing, these systems have a significant number of
parts, and are much more lightweight and often por-
shortcomings. By contrast, chemically cured systems
table; most are rechargeable battery-operated; output
polymerize much more uniformly throughout the
intensities for second-generation units are excellent;
entire composite.
and they have excellent reliability characteristics.
VLC systems depend on available access to
Some units include more than one type of LED (e.g.,
provide high-intensity visible light. VLC suffers from
UltraLume 5, Ultradent, Provo, UT) but most are de-
three major categories of problems.51 First, VLC
signed to provide light to cure camphorquinone ini-
lights have technical shortcomings. This was exem-
tiators (e.g., Elipar Freelight 2, 3M ESPE, St. Paul,
plified by quartz-tungsten-halogen lights that have
MN; Allegro, LEDemetron, Kerr, Orange, CA;
been so popular over the last thirty years. Fluctua-
Denmat, Santa Maria, CA; SmartLite iQ, Dentsply,
tions in line voltage, problems with light reflectors,
York, PA). Despite early sales at relatively high prices,
degradation of filters, non-uniform fiberoptic trans-
excellent units are now available for under $500 (e.g.,
port properties, and many other effects have led to
the CURE, Spring Health Products, Philadelphia, PA).
variable outputs. Second, light intensity depends on
While they do not solve access and depth-of-cure prob-
several technical operations by the dentist such as
lems, they do represent an improvement in equipment
close approximation to the material to be cured, use
operation and design. Thus, LED curing units are ex-
of thin enough increments to ensure sufficient light
pected to dominate the near-future period.
penetration, proper light angles, and overlapping light
exposures, all of which are necessary to ensure proper
opportunities for adequate light curing. Third, com- Ceramics
posite formulations affect the depth of penetration Ceramics have noteworthy advantages of es-
of visible light. Darker shade composites may have thetics, biocompatibility, and mimicry of natural
as little as .05-1.0 mm effective depth of cure. Cer- enamel properties. However, most are custom fabri-
tain filler particles are in the visible light spectrum cated into dental restorations and contain porosity
range (e.g., 0.474 m filler particle diameters corre- and/or stress risers that lead to cracks. More robust
spond exactly to 474 nm light wavelengths) and can ceramics are on the way. Until relatively recently,
interact with key wavelengths of light. Monomers dentistry had not employed ceramic technology at a
do not all react equivalently to VLC photoinitiation. very sophisticated level. Restorations are still cus-
Monomers have different copolymerization tenden- tom made using either all-ceramic or porcelain-fused-
cies. While newer VLC approaches such as light to-metal systems without much underlying control
emitting diode (LED) systems have helped to solve or engineering of the microstructures. Dental ceram-
some of the first category of problems, they do noth- ics have relied primarily on the presence of reinforc-
ing to manage the other two sets of challenges. It is ing second phases as a crack controlling mechanism.
becoming increasingly obvious that most VLC sys- A wide range of all-ceramic materials have been
tems tend to have some portion undercured. If one employed (feldspathic porcelains, leucite-reinforced
considers that an effective degree of conversion is porcelains, alumina-reinforced porcelains, high-den-

580 Journal of Dental Education ■ Volume 69, Number 5

sity alumina ceramics, high-density zirconia ceram- ever, as the complexity, sophistication, and expense
ics, glass-infiltrated ceramics, glass ceramics), but of the CAD/CAM design and milling operations ex-
not much elegance has been applied to local control panded, this technology has moved back into the den-
of domain properties within ceramic. tal laboratory. Despite the fact that the original goal
There still is a clear need for more crack-resis- for CAD/CAM generated restorations was to provide
tant or crack-tolerant designs in dental ceramic en- a low-cost alternative to dental amalgam, all the re-
gineering. Both pathways are being explored. Crack- search has evolved in quite a different direction.
resistant materials include zirconia and alumina The key challenges for improved dental ce-
cores. Both have interesting potential. Yet, these ap- ramic systems seem to be crack-tolerance, low cost,
proaches introduce other problems such as alloying bondability, and excellent esthetic characterization.
esthetic ceramic veneers or creating strong attach- These goals involve materials design more than fab-
ment opportunities for dental cements or bonding rication limitations. Major dental laboratories now
systems. provide full-service ceramic processing options, so
There is ever-increasing interest and research many cost concerns for expensive processing equip-
on options for crack-tolerant designs. This involves ment have disappeared when considering the poten-
identification of new mechanisms to arrest cracks or tial for new processing technologies for dental res-
slow down their propagation rates. Layered ceram- torations. Novel ceramic textures and microstructural
ics have potential because different layers can be control can be produced by rapid prototyping,
designed to have different properties (moduli) that stereolithography, and other printing techniques.
produce crack blunting.59 Textured ceramics (woven Their potential has not yet been realized.
ceramic microstructure motifs) create local variations
in properties that discourage crack formation and Cements
make growth very difficult. Surface film modifica-
While dental cements do not represent much
tions60-64 or surface retreatments such as sandblast-
volume of dental material, they are involved in a cru-
ing65 also may be used to eliminate fabrication de-
cial step of luting and bonding restorations. The pref-
fects that otherwise might generate cracks.
erences of U.S. clinicians have been slowly shifting
Ceramics are difficult to form into complicated
away from traditional cements (e.g., zinc phosphate)
geometries using high-temperature processes in a
toward resin-based cements (e.g., resin-modified
cost-effective manner in small dental laboratories.
glass ionomers). In 199069 there was already some
Other processes are well suited for custom opera-
evidence of this shift in usage (zinc phosphate=22
tions. Hot-isostatic-pressing (HIP) has great advan-
percent, polycarboxylate=33 percent, glass
tages for creating standard shapes in a reusable mold,
ionomer=42 percent, resin=2 percent). It was esti-
such as prepable zirconia abutments for implants. Yet,
mated in 200170 that the shift toward glass ionomer
for custom prostheses (crowns and bridges), it is
types was dramatic (zinc phosphate=10 percent,
currently more practical to rely on milling operations
polycarboxylate=5 percent, glass ionomer types=75
or molding operations to form dental shapes.
percent, resin=10 percent). For metal alloy substruc-
CAD/CAM ceramic materials provide a unique
tures (e.g., gold alloy crowns and bridges, PFMs),
option to start with almost defect-free materials, but
resin-modified glass ionomer cements have been far
they don’t provide flexibility to regionally custom-
and away the most popular choice. However, resin
ize esthetics or other properties for a restoration. That
(i.e., composite) cements are ideal for all-ceramic
is a large part of the reason that CAD/CAM has not
restorations since they much more effectively trans-
replaced much of traditional ceramic fabrication tech-
fer stresses.71 For almost fifteen years, the need for
nology. No alternative yet competes with the esthetic
these two types of cements was emphasized. Since
result of dental porcelain being layered by an artistic
2002, there has been a new class called “universal
ceramic technician to fully characterize a restoration.
cements” (e.g., Unicem, 3M ESPE, St. Paul, MN;
While one can speculate that this is possible, this is
MaxCem, Kerr, Orange, CA) which are a hybrid of
not currently an option. When this is true, then CAD/
the properties of resin-modified glass ionomers and
CAM might have much grander appeal.
composites that purport to replace the two types with
When CAD/CAM first became commercially
one. They are designed to be self-etching. In 2004,
available in dentistry in 1989,66-68 one of the initial
universal cements seem to be the popular choice for
appeals was the generation of an all-ceramic bond-
young clinicians.
able restoration chairside in just a few minutes. How-

May 2005 ■ Journal of Dental Education 581

 are more traumatic than others. An esthetic failure
Performance Outcomes for might be easy to manage by resurfacing or a repair.
A fracture would require replacement of the restora-
Synthetic and Biological tion in most cases. Regardless of the definition or
Biomaterials complexity, it is important to know the distribution
of values for longevity associated with a procedure.
Stepping back from the glitter of technologies Amalgam is normally chosen as the standard for com-
involved with new biomaterial engineering, fabrica- parison of all other longevities. In a controlled long-
tion, and investigation, one is still confronted by an- term clinical trial, amalgam longevity was around
other important core question. What are the safety twenty-four years.86
and efficacy of these options? Concerns for safety Longevity must be defined in relative and not
include the procedure, materials, and risks posed by absolute terms, as is explained by the following. For
failure. This type of information has been very lim- any procedure, there are many possible variables that
ited in scientific depth. Efficacy is concerned with influence outcomes, including the clinician and the
the comparative longevity. True long-term estimates patient, and many possible failure modes. A minor
of efficacy depend on longitudinal clinical trial in- failure in one mode might not require repair or re-
formation, and that is just starting to be emphasized placement. Longevity is the average survivability for
in biomaterials research. a pool of restorations taking into account all pos-
Biocompatibility of biomaterials has never sible outcomes. For example, consider examining
been investigated from a truly scientific base. Most procedures involving Class II composites in maxil-
tests have been crude screening procedures. Even tra- lary first molars being monitored for several years
ditional guideposts for screening tests, such as the in terms of a wide range of clinical performance cri-
Ames Test, have been withdrawn by its own author teria. Overall, the performance for the pool of resto-
as ineffective.72 Practical substitutes have not yet rations can be summarized as a success (or failure)
emerged. More times than not, we depend on the curve (see Figure 6). With time, the success level
clinical record of reported problems to discern the decreases from 100 percent. Over relatively long
relative biocompatibility of a biomaterial. Yet that periods, ten to twenty years, it becomes obvious that
record remains incomplete because we refuse to look the overall curve is shaped like an inverted “S.” It
closely. The Dental Biomaterials Adverse Reaction may never fall all the way to 0 percent, but is still
Unit73 at the University of Bergen in Norway has been quite symmetrical in shape. For convenience, the
studying posttreatment reactions to dental materials curve can be described by the point at which 50 per-
for several years and reports a much higher level of cent or half of the pool of restorations has failed as a
patient problems than is routinely acknowledged in definition of longevity. In other words, the half-life
the United States. Clinical trials of a biomaterial’s is the number-average longevity for the pool. This
performance are short-term and ignore important has been called the “clinical longevity for 50 per-
changes that may occur later and take ten to forty cent” or CL50 for the pool.51 In dentistry, the practi-
years to surface. There are concerns that the poly- cal goal for the CL50 might be ten years. Shifting the
mer matrix of dental composites may undergo deg- entire curve to the right represents a positive situa-
radation reactions in the presence of esterases com- tion of improved longevity. Shifting the curve to the
monly found in saliva.74-85 While the effects may seem left represents a poorer longevity.
minor in the near term, should we classify a com- Factors influencing the curve are a combina-
posite as biologically safe? Do these changes affect tion of effects including 1) operator factors, 2) de-
restoration properties such as wear? Surface changes sign factors (such as resistance and retention form,
can dramatically alter the receptivity toward biofilms. cavosurface margin bevels), 3) restoration material
This entire area clearly deserves a much closer look factors, 4) intraoral location factors (maxillary ver-
and more careful scientific review. sus mandibular, anterior versus posterior, premolar
Longevity, on the other hand, has been studied versus molar), and 5) patient factors (fluoride his-
in terms of cross-sectional and longitudinal clinical tory, diet, dental IQ, genetic predisposition to dental
trials. Concern for longevity arises from pressures disease).87-88 Risk factors are not equal. Generally,
for evidence-based dentistry. For any dental proce- operator factors are suspected to be the most impor-
dure, there are clearly a number of events that could tant and may represent >50 percent of the risk. Ma-
lead to a pronouncement of clinical failure. Some terials factors may be very minor and could be the

582 Journal of Dental Education ■ Volume 69, Number 5

smallest effect. Thus, design of new dental materials
is concentrated on eliminating, as much as possible,
operator’s effects on performance and shifting the
focus to the material’s effects. In recent years, mix-
ing of dental materials has almost been entirely elimi-
nated from the armamentarium to prevent errors in
proportioning and technique.
A CL50 of ten years is certainly not ideal. One
would like to shift this substantially to the right.
However, the practicality of a restorative material
lasting a real lifetime is far off. Consider the follow-
ing two thoughts. First, the current middle-aged
population generally has a relatively low caries ex-
perience and an ever-increasing longevity. To last a
lifetime, a cemented restoration in a woman who is
around sixty years old might require survival for up Figure 6. Schematic summary of the key parts of a
to forty years. Normal mechanical stresses in the oral survival (failure) curve for a restorative dental
environment are estimated to provide about 1 mil- material
lion loading cycles per year. Typically, we have de- The half-life for a population of restorations is typically
signed engineering materials that do not survive be- reported as the “clinical longevity for 50% of the
restorations” or CL50. If only a small portion of the curve
yond ten to twenty million cycles of loading (or ten has been defined, then it is more convenient to report the
to twenty dental years). Therefore, newer survival level at a certain time period. The dashed curve
biomaterials will have to become much more dam- is the hypothetical curve. The solid curve is more typical,
where a few restorations appear to survive forever.
age-tolerant to provide longer service lifetimes. For
this same reason, one might argue that true biologi-
cal replacements (tissue engineered or cloned teeth)
would be a better choice for treatment. However, this 8. Duailibi MT, Dualilibi SE, Young CS, Bartlett JD, Vacanti
argument presupposes that there is sufficient bone, JP, Yelick PC. Bioengineered teeth from cultured rat tooth
normal healing processes, and good health for the bud cells. J Dent Res 2004;83:523-8.
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synthetic biomaterials still may be employed for a cell-based tissue engineering of murine teeth. J Dent Res
2004;83:518-22.
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potential cellular therapeutics for craniofacial regenera-
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