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2 DENTAL APPLICATIONS 171

DENTAL APPLICATIONS
Introduction

The dental industry has taken great advantage of polymer science to design ma-
terials. Materials used in the oral cavity or external prostheses have very specific
requirements, ie, these materials must have physical, chemical, biological, and
aesthetic requirements, not always fulfilled by currently available materials. A
host of requirements must often be met, including adequate strength, resilience,
wear or abrasion resistance, dimensional stability for both fabrication and use,
translucency or transparency to provide a match of the natural tissue replaced,
good color stability, resistance to the oral environment, show tissue tolerance and
low toxicity, and exhibit ease of fabrication into a needed dental device. Since
few resins fulfill all the mentioned requirements, the search for improved dental
materials has been limited to a few classes of polymeric materials. The various
types of monomers and polymers used in dentistry are discussed, along with brief
attention given to new areas of promise for preparing better materials.
The largest volume of polymeric materials used in dentistry is in prosthetic
applications. Polymeric materials are also important in operative dentistry, being
used to produce composite resins, dental cements, adhesives, cavity liners, and as
a protective sealant for pits and fissures. Elastomers are employed as impression
materials. Resilient prosthetic devices are often fabricated to restore external soft-
tissue defects. Mouth protectors are fabricated to prevent injury to teeth, as well as
prevent head and neck injuries. Other polymer applications include fabricating
patterns for metal castings and partial denture frameworks, impression trays,
orthodontic and periodontal devices, space maintainers, bite plates, cleft palate
obdurators, and oral implants. Polymeric materials may also be used to fabricate
an artificial tongue, when disease results in its loss.

Encyclopedia of Polymer Science and Technology. Copyright John Wiley & Sons, Inc. All rights reserved.
172 DENTAL APPLICATIONS Vol. 2

The discovery of vulcanized rubber in 1839 gave rise to the first polymeric
dentures, followed by celluloid dentures about 1870, and subsequent use of vinyl
chloride copolymers, phenol–formaldehyde resins, and polystyrene. Acrylic-based
resins gained rapid acceptance after 1937, and are being greatly used today. Their
main disadvantages are related to shrinkage because of the free-radical polymer-
ization of methyl methacrylate, poor abrasion resistance, and fracture toughness.
Other polymers, such as epoxy resins, polystyrene, polyesters, polycarbonates,
polysulfones, vinyls, silicones, polysulfides, and polyethers, have been explored or
used to some degree.
The various dental polymers discussed in this article include impression
materials, dentures and denture liners, artificial teeth, crown and bridge mate-
rials, mouth protectors, maxillofacial materials, restoratives (consisting of glass
polyalkenoates or glass-ionomers and composites), adhesives, and sealants. Spec-
ifications and standards for dental materials are also briefly mentioned in the
text.

Impression/Duplicating Materials

Impressions must accurately show the dimensions, surface detail, and relation-
ship of teeth and soft oral tissues. Materials used to accomplish this task include
rigid gels of the reversible hydrogen-bonding type, irreversible alginate hydrocol-
loids, and elastomers such as silicones, polysulfides, and polyethers. Duplicates
of original casts, used to fabricate partial or complete dentures, are made from
duplicating materials.
Agar (Reversible Hydrocolloids). Agar, a galactose sulfate or muco-
polysaccharide (sulfonic acid ester of a galactan complex), is a long-chain polymer
having a molecular weight of about 150,000. The material forms a colloid with
water, with the solutions being liquid at ≥70◦ C and setting to a gel at 30–50◦ C.
Strong hydrogen bonding causes the molecule to form a helical structure, which
uncoils on heating. On cooling, the gel forms and reproduces the shape of the
oral tissues. These materials can be used several times, but prolonged heating
causes degradation. While agar is the main constituent, it is by no means the
main constitutent by weight. For example, a typical formulation consists of about
85.5% water, 12.5% agar, 1.7% potassium sulfate, 0.1% alkyl benzoate, and trace
amount of pigments. Fillers, such as zinc oxide and a hard wax or clay, are of-
ten used to modify the formulations. Borax or calcium metaborate may be used to
control the pH, increase viscosity, toughness, and resiliency. These materials were
developed to make accurate impressions, even of undercut areas. The agar used
in duplicating uses has a composition similar to the agar impression material, but
with a higher water content. ANSI/ADA Specifications No. 11 (1997) applies to
agar-based impression materials.
Alginates (Irreversible Hydrocolloids). The reactive component in
these materials is the sodium or potassium salt of anhydro-o-D-mannuronic acid
(alginic acid), isolated from brown seaweed (algae). A typical formulation consists
of about 18% sodium or potassium alginate, 14% calcium sulfate dihydrate, 2%
sodium phosphate, 10% potassium sulfate, 56% diatomaceous earth filler, and 4%
sodium silicofluoride. When mixed with controlled amounts of water, the soluble
Vol. 2 DENTAL APPLICATIONS 173

hydrocolloid is converted to insoluble calcium alginate, ie, and an acid–base reac-


tion leads to matrix cross-linking. In the sol–gel conversion, calcium cations form
salt-bridges with the carboxylate anions, forming ionic cross-linking. The material
can only be used once. The addition of sodium tripolyphosphate or tetrasodium
pyrophosphate retards rapid precipitation of gel. Addition of a fluorosilicate com-
pletes the precipitation of the insoluble alginate, after adequate working time
has elapsed. Besides diatomaceous earth filler, zinc oxide may be used to improve
strength and yield a material with a smooth, nontacky surface. Alginates, used
most frequently to make impressions, are inexpensive, easy to manipulate, and
comfortable for the patient. But, alginates deteriorate rapidly on storage at ≥50◦ C
and once set they must be kept in 100% relative humidity to prevent shrinkage. In
addition, they are the least accurate of the impression materials. Both reversible
and irreversible hydrocolloids have been used at the same time in a laminating
technique. ANSI/ADA Specification No. 18 (1992) sets the requirements for fast
and slow setting alginate impression materials.
Synthetic Elastomers. Synthetic elastomers, such as polysulfides, sili-
cone, and polyethers, exhibit much better dimensional stability than the hydro-
colloids. They are mainly used in crown and bridge applications or for impressions
of dentate patients. These polymers are used at a temperature above their glass-
transition temperature (T g ). The viscosity of the materials used is influenced by
both the working temperature above T g and the length of the polymer chains,
as well as by fillers and other additives. The formulated materials are liquids or
pastes at room temperature, which transform into a solid by covalent bonding
between the long-chain molecules. The process of forming chemical bonds creates
a three-dimensional organic matrix. The chemistry of the impression materials is
described separately, followed by a brief comparison of their properties. ANSI/ADA
Specification No. 19 (1982) sets requirements for the elastomeric-type impression
materials.
Polysulfides. The starting materials have molecular weights of about
2000–4000 and can be formulated to yield a wide range of physical and chemi-
cal properties. In the two-component (paste) system, the base material is a vis-
cous polysulfide liquid prepolymer having terminal and pendant mercaptan (SH)
groups, such as a Thiokol LP-2 rubber, commonly called thiols (see Fig. 1). Tita-
nium dioxide (TiO2 ), calcium sulfate, calcium carbonate, silica, or alumina is used
as fillers, to extend, reinforce, or harden the product. Dibutyl phthalate, tricresyl
phosphate, or tributyl citrate is added as modifiers or diluents to improve mixing
and flow properties. The paste may also contain sulfur and oleic or stearic acid,
which act as a retarder to control the set. The SH groups are oxidized by lead
dioxide or copper hydroxide supplied as a separate part of the formulation. When
the accelerator (oxidizer) is added to the base (polysulfide) paste an exothermic
reaction occurs, bringing about a 3–5◦ C rise in temperature, depending on the

Fig. 1. Polysulfide oligomer.


174 DENTAL APPLICATIONS Vol. 2

Fig. 2. Polyether impression material reaction.

amount of sulfur used. The exothermic reaction is accompanied by a rapid in-


crease of molecular weight and elimination of water, caused by formation of the
chain-extending and cross-linking S S bonds. Besides being sticky and having
a disagreeable odor, polysulfides [R(SH)x ] are difficult to mix and exhibit relatively
poor elastic recovery when stressed. In undercut areas, they may not provide ac-
curate reproduction of oral structures. When properly used they exhibit good tear
resistance and acceptable stability.
Polyethers. These impression materials were developed in Germany
in the 1960s. The reactive oligomer used is a polyether having cyclic imine
(ethyleneimine) residues, which undergo ring opening and subsequent cross-
linking via a cationic initiator, as shown in Figure 2. The two-part formulation
contains the imine functionalized polyether, silicate filler, and a glycol ether plas-
ticizer as one paste, and the cationic initiator (such as an alkylester of benzene
sulfonic acid), a silicate filler, and a plasticizer as the second paste (1). Adding
a polyester diluent or thinner controls the rheological properties and working
time. Mixing is moderately easy and dimensional changes in air are low (<0.1%)
over several hours, as no products are released during curing. The elastic recov-
ery and reproduction of detail are excellent. These materials have a much higher
modulus of elasticity than silicones or polysulfides, making them more difficult to
remove from the mouth. Polyether impression materials tear readily and have an
equilibrium water sorption of about 14%. Dimensional stability in water is poor,
necessitating storage in a dry environment.
Silicones. Two types of silicones are used in impression materials: addi-
tion (Fig. 3) and condensation (hydrosilylation) (Fig. 4). Both are based on using
poly(dimethylsiloxane), with the two having different end groups and different
curing mechanisms. Addition siloxanes are a two-paste system, with one paste

Fig. 3. Addition silicone structure/reaction.


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Fig. 4. Condensation silicone structure/reaction.

containing a low molecular weight silicone having terminal vinyl groups (Fig. 3)
and reinforcing filler and the other paste consisting of the hydrogen-terminated
silanol oligomer, filler, and chloroplatinic acid catalyst. Mixing the pastes gives
a cross-linked elastomer. No volatiles are given off during polymerization—a
definite advantage—compared to the condensation type, which eliminates ethyl
alcohol.
The condensation-type silicone impression materials are based on hydroxyl-
terminated poly(dimethylsiloxane), ie, viscous liquids of structure (Fig. 4). Col-
loidal silica or micronized metal oxides, having 5–10 µm particle size, are added
to prepare a paste which is cross-linked with an alkyl silicate containing 50%
ethoxy groups, such as tetraethyl orthosilicate (TEOS). Organic tin activators,
such as stannous octoate or dibutyltin dilaurate (2), are used at the 1–2% level.
The chief uses of silicone impression materials are for crown and fixed partial
dentures. These systems may be used in a wide range of impression techniques.
They are relatively easy to mix, producing high tensile strength materials having
good elastic properties, along with permanent-set values of about 1% at 40% strain.
But, they tear at relatively low extension.
Communicable diseases have caused concern in handling of impression ma-
terials, meaning impressions are not generally accepted by dental laboratories
unless they are disinfected. However, disinfection must be accomplished with-
out distorting the impression. Reversible and irreversible hydrocolloids, as well
as polyether impressions, should be avoided if they are to be disinfected, since
they lack the required stability. A guide for disinfecting impression materials may
be found in the ADA Council on Dental Materials, Equipment and Instruments
(COMEI, 1988 and 1992).
Impression Materials Merits. Elastomeric impression materials repro-
duce surface details very accurately, provided low viscosity formulations are used.
Since these materials are generally hydrophobic, they will not properly wet out
the surface of the tooth with saliva present. Contact angle studies of water on the
elastomeric impression surfaces for polyether, polysulfide, and addition silicones
show angles of 49.3◦ , 82.1◦ , and 98.2◦ , respectively, indicating that polyethers
work best where saliva cannot be excluded. The setting process for polysulfides
is highly susceptible to temperature and humidity, influencing working and set-
ting times. Condensation silicones may also show erratic setting, because of in-
adequate mixing and possibly some hydrolysis of TEOS. The setting behavior of
addition silicones and polyethers is the most consistent. Condensation silicones
are dimensionally less stable than polysulfides, addition silicones, or polyethers.
The contraction or shrinkage of condensation silicones, upon cooling from mouth
temperature (37◦ C) to room temperature, is ca 0.35%, compared to 0.20% for the
polysulfides. This shrinkage is essentially caused by release of alcohol generated
176 DENTAL APPLICATIONS Vol. 2

during the condensation reaction. However, condensation silicones are cleaner to


handle than polysulfides (3).
Elastomer Thermal and Mechanical Properties. Comparing stiffness
of the polysulfide (PS), condensation silicone (CS), addition silicone (AS), and the
polyether (PE) elastomeric impressions, the ranking would be as follows: PS < CS
< AS < PE. The permanent set or resistance to deformation on removal would be
as follows: PS > PE > CS > AS. Tear strength would be approximated as follows:
PS ≫ PE > AS and CS. Polymerization shrinkage for the elastomers is of the
order PE = AS < PS < CS. The materials may thermally contract on removal
from the oral cavity, with PE = 320, PS = 270, and AS = CS = 200 ppm/◦ C.

Denture Resins/Prosthetic Materials

A variety of polymeric materials have been studied or used for preparing den-
tures, including epoxy resins, cellulose nitrate, rubber or vulcanite, phenol–
formaldehyde, vinyl acrylics, polystyrene, polycarbonates, and polysulfones, but
acrylics have become the materials of choice. It happens that compression-molded,
cross-linked acrylic dentures are as dimensionally stable and useful as the den-
tures made with special resins (4).
Denture wearers demand an accurate fit and natural appearance. The fit
is very important, since chewing efficiency of artificial dentures is substantially
lower than that of natural teeth. Besides being easy to fabricate, an ideal den-
ture material would have high strength, stiffness, hardness, and toughness, ie, be
fracture resistant, have low density, good dimensional stability, show resistance
to oral fluids, have an absence of odor or taste, be resistant to bacterial growth,
have good thermal conductivity, show good retention to other polymers, porcelain,
and metals, be radiopaque, be easy to repair, easy to clean, have good storage life,
and be inexpensive to make. Significant challenges remain to produce the ideal
denture material.
To achieve needed comfort, dentures must be custom-made. To form the cus-
tomized denture, in which the artificial teeth are embedded, a wax pattern is used.
The wax pattern is inserted in a plaster or dental stone in a split mold flask. After
removal of the wax, the surface of the resulting mold cavity is painted with a sep-
arating medium, usually an aqueous alginate solution, followed by the addition
of the acrylic resin. The separating medium aids in removal of the cured acrylic
from the mold.
Acrylic denture materials are made by free-radical (addition) polymerization,
using methyl methacrylate (MMA) monomer. In the process, the MMA becomes
poly(methyl methacrylate) (PMMA). The resins are available in either heat- or
cold-cured formulations. A cross-linking monomer, such as ethylene glycol (Fig. 5)

Fig. 5. Dimethacrylate monomers/reactive diluents. EGDMA (R = CH2 CH2 ); DEGDMA


(R = CH2 CH2 OCH2 CH2 ); TEGDMA (R = CH2 CH2 OCH2 CH2 OCH2 CH2 ).
Vol. 2 DENTAL APPLICATIONS 177

or diethylene glycol dimethacrylate (Fig. 5), is included with the MMA mixture
to improve the mechanical properties. The dimethacrylates are covalently bonded
at various points along the PMMA chains, forming a cross-linked matrix. Visible
light-cured versions have also become available, with the chemistry akin to that
of composite restoratives.
Heat-Cured Methacrylate Formulations. These resins consist of granu-
lar PMMA powder blended with liquid MMA, along with a cross-linking monomer,
as shown in Figure 5 (EGDMA or DEGDMA). After mixing and heating, the
monomer–polymer dough forms a rigid plastic. The powder component is mostly
granules of PMMA, along with benzoyl peroxide initiator (BPO, 0.5–1%), tita-
nium/zinc oxide pigments and opacifiers, dibutyl phthalate plasticizer, and acrylic-
or nylon-type reinforcing fibers. The liquid component contains the inhibited
MMA, along with a cross-linker (Fig. 5, DEGDMA). The blends, normally con-
sisting of about two to three parts of PMMA and one part of monomer by volume,
are packed with pressure into the mold, having the properly positioned teeth.
The MMA is normally inhibited with the methyl ether of hydroquinone (MEHQ)
or butylated hydroxytoluene (BHT). Small amounts of other acrylic monomers,
plasticizers, and 1–5% of a cross-linking agent may be employed. The polymeric
granules may also have methyl acrylate in the backbone or be plasticized by ethyl
or butyl methacrylate or ethyl acrylate to increase solubility in the monomer
syrup. Particle size and molecular weight distribution of the PMMA controls the
solubility of the polymer and the working consistency of the mixture. Traces of
poly(acrylic acid) or soluble starch suspension agents may remain in the polymer,
preventing wetting of the beads by the monomer. The residual initiator content
of the polymer beads may be at the level to obviate the need of further BPO to be
added to the mix.
Most dentures are fabricated from the heat-cured formulations with the poly-
merization rate increasing directly with temperature, proportional to the square
root of the initiator concentration. The half-life temperature (t1/2 , ◦ C) for BPO at
72◦ C is 10 h (5). The customary curing cycle of the fully mixed powder/liquid blend
is about 90 min at 65◦ C. Post-curing is usually done at 100◦ C for 60 min so as to
produce a more fully cured denture with low porosity. After cooling, the denture
is separated from the embedding material, trimmed, and polished. Red fibrous
materials and beads of varying translucency are added in small amounts prior to
curing so as to simulate the appearance fo natural oral-tissue.
Autopolymerizing Resins. Room temperature (RT) curing, initiated by a
suitable redox (oxidizer–reducer) combination, is a simple modification of the heat-
cured formulations. In such formulations tertiary aromatic amines, such as N,N-
dihydroxyethyl-p-toluidine or p-N,N-dimethylaminophenethanol (6), are added at
about the 0.3–0.8% level to the monomer, which is subsequently blended with a
polymer containing 2% BPO. The rate and degree of polymerization depends on
both the type and concentration of initiator (BPO) and activator (amine), as well as
the particle size of the PMMA powder. Techniques for preparing the molding are
very similar to the procedure described for heat-cured dentures. In this procedure,
the freshly mixed monomer–polymer blends are more limited in use because of
the handling characteristics of the formulations, ie, the polymerization is slightly
delayed upon mixing. The rise in temperature depends on the mass of material
and the powder/liquid (P/L) ratio used. Since polymerization occurs from inner to
178 DENTAL APPLICATIONS Vol. 2

outer portions of the mass, temperatures within the bulk portion of the casting
are higher than those at the surface. The cured dentures are usually not very
porous, since monomer evaporation is limited. The bulk of the polymerization
takes place within 30–45 min, but may continue for hours. The denture flask is
therefore held under pressure for several hours so as to ensure complete curing.
Room-temperature cured materials usually contains about 3–5% free monomer,
compared with only 0.2–0.5% found in heat-cured materials. Thus, this method of
curing is not as efficient as the heat-cured process, since the product produced has
less cross-linking density and a lower T g than the heat-cured materials. The latter
factors also make these RT-cured materials more susceptible to creep, eventually
creating distortion in the denture. The larger the amounts of free monomer present
in the final product, the greater the propensity for warpage to occur. Materials
generated by using amines in the curing have poorer color stability upon aging.
Blue dye, a ultraviolet absorber (7), may be added to the formulation to mask color
shift. Production of high dimensional accuracy is one of the main advantages of
RT-cured resins, resulting from lower curing temperature leading to reduction
of stresses in the matrix. Differences between thermal expansion of the denture
resin and the plaster mold may result in undesired dimensional changes when the
mold is subjected to a wide temperature range during processing. Dentures cured
at RT have better dimensional accuracy (8,9) than heat-cured dentures. However,
both are clinically acceptable.
Low Viscosity, Chemically Cured Resins. The pour and cure acrylic
resins are blends of high molecular weight polymer powder mixed with monomer
and other additives to achieve a pourable viscosity. The mixture is usually poured
through sprues into a hydrocolloid-based mold, with polymerization conducted
under pressure for about 30 min at RT (10). This procedure for preparing dentures
is inferior to heat- and cold-cured acrylics. However, it is an excellent technique for
denture duplication. Polymerization shrinkage is a problem for this type of system,
possibly causing posterior teeth to be displaced in the resilient mold and out of the
desired occlusal pattern (11). Methods have been developed to improve the latter,
by increasing the bond of acrylics to denture teeth (12). This technique requires
great attention to detail in order to produce clinically acceptable prostheses.
Visible Light-cured Resins. Employing high intensity visible (blue) light
to bring about free-radical polymerization (curing) of the denture resins holds
great promise (13). A photopolymerizable formulation in this case could consist of
a urethane dimethacrylate–acrylic polymer combination, reinforced with a micro-
fine silica filler. Thus, the materials produced have more in common with a com-
posite restorative material than with the commonly used denture-based resins.
The matrix produced is a highly cross-linked acrylic, having an interpenetrat-
ing polymer network (IPN)-type structure. MMA is not used in the urethane
dimethacrylate (Fig. 8) cross-linked IPN matrix, filled with colloidal silica and
acrylic polymer beads. Akin to composite restoratives, the formulation makes use
of the camphorquinone–tert-amine initiator system. With the exception of brittle-
ness, the cured materials have properties as good or better as the denture mate-
rials made by the methods described earlier. This technique shows good potential
for expanded use.
Mixing/Working Properties. For denture resins certain aspects are im-
portant to note. First, great care needs to be taken to use the correct P/L ratios,
Vol. 2 DENTAL APPLICATIONS 179

usually about 2.0/1.0 wt% or 1.6:1.0 vol%. Too much powder will result in under-
wetting of the beads, leading to production of a weak structure. Conversely, too
much monomer will produce excessive shrinkage. All ingredients must be thor-
oughly mixed to achieve the best results. A separating medium must be used to
prevent adhesion of the resin to the mold surface. Control of porosity and preven-
tion of processing stress are also two areas of concern. Polymerization shrinkage
and escape of volatiles can generate porosity.
Concerning shrinkage, volume reduction of about 20% for the monomer is
minimized by using polymer (PMMA) powder, cutting shrinkage to about 5–8%. It
is very important that this contraction is not translated into the high linear-type
contraction, which on the basis of volumetric shrinkage should be about 1.5–2.0%,
but is actually in the range of about 0.20–0.5%. The observed change is probably
due to thermal contraction, caused by temperature changes, and not to actual
polymerization shrinkage. The resin becomes very rigid once the temperature of
the reaction descends below the T g of the material, at which point the curing con-
traction will have essentially been completed. From this point onwards thermal
contraction contributes to dimensional changes of the denture material. Because
of the latter, cold-cured dentures should have a better fit, since the processing
temperature is considerably lower, ca 60◦ C, compared to heat-cured dentures at
ca 100◦ C. Thus, it is very important to pack the viscous mix in the mold in suffi-
cient quantity to create pressure, facilitating removal of voids and helping to cut
down on curing contraction. In all systems, polymerization generates an exotherm,
which might elevate to the point of causing monomer vaporization and creating
porosity. Thus, temperatures of cure should be controlled to avoid gaseous porosity
and pressure maintained to eliminate contraction porosity. Dimensional changes
also give rise to internal stress, which if allowed to relax may lead to warpage, craz-
ing, and distortion of the denture. The use of acrylic teeth, rather than porcelain
teeth, eliminates differential shrinkage, helping to reduce strain. Craze develop-
ment is another problem that may develop in dentures as a result of strain relief,
polishing, presence of alcohol, and differential contraction due to the type of teeth
used. Cross-linking helps reduce craze formation. A brief summary of the denture
materials’ properties is shown in Table 1.
Biocompatability. PMMA is highly biocompatible, with very few patients
showing any type of allergic reaction. Adverse reactions are usually caused by
leachable monomers. Cold-cured formulations may be a problem, since they tend
to have more residual, free monomer. Post-curing of the denture helps lower free
monomer content, but may also cause some denture distortion.
Dimensional and Mechanical Properties. Even though the denture is
placed on soft tissues, there is still great need for the denture to have dimensional
stability. The denture must fit as accurately as possible to promote retention of
the denture to the mucosa. As shown in Table 1, there is a considerable variation
in mechanical properties, depending on composition, processing technique, and
environment factors. Room-temperature cured resins have lower strength and
stiffness, with about the same elastic modulus as heat-cured materials. Polymer-
ization shrinkage of the monomer–polymer dough is about 6–7%. Linear shrink-
age is about 0.5% across the posterior aspect, under normal denture processing.
Water sorption, about 1–2 wt%, partially compensates for the shrinkage. Linear
shrinkage of 0.3–0.4% is clinically insignificant, since the tissue on which the
180 DENTAL APPLICATIONS Vol. 2

Table 1. Physical Properties of Denture-Based Materialsa


Property Poly(methyl methacrylate) Vinyl acrylics
b
Compressive strength MPa 76 70–76
Tensile strength, MPab 48–62 51–60
Flexural strength, MPab 83–117 69–110
Elastic modulus, MPab 3.8 × 103 2.3 × 103
Elongation, % 1–2 7–10
Impact strength, N·mc 1050 3150
Transverse strength, MPab 41–55 41–55
Knoop hardness (KHN) 15–23 14–20
Coefficient of linear thermal 81 × 10 − 6 71 × 10 − 6
expansion per ◦ C
Heat-distortion temp., ◦ C 160–195 130–170
Polymerization shrinkaged , % 6–7 6–7
Water sorption, 24 h, % 0.3–0.4 0.07–0.4
a Partiallytaken from Ref. 14.
b To convert MPa to psi, multiply by 145.
c To convert N·m to ft·lbf, multiply by 0.74.
d Linear shrinkage of commercial dentures is ca. 0. 12–0.97%.

denture rests adjusts to such changes (14,15). Some cross-linked resins contain 2-
hydroxyethyl methacrylate (HEMA), which promotes higher water sorption, low-
ering dimensional stability. Fillers reduce the thermal expansion of the dentures,
providing higher impact strength. However, they are difficult to polish, tend to
stain, and may collect debris and imbibe bacteria at the surface.
It has been clearly shown that radiopaque materials are needed (16,17) for
visualization of aspirated or swallowed denture fragments. This is accomplished
with additives such as barium sulfate, barium fluoride, barium or bismuth glasses,
and halogenated organic compounds. The physical properties of the materials are
significantly affected by large quantities of these additives. ANSI/ADA specifica-
tions or requirements for radiopaque materials for denture-based polymers have
been described (18).
While commercial denture materials are reasonably strong and show good
flexibility, improved fracture resistance and fatigue strength are still sought. Seek-
ing to improve such things as fracture toughness, impact and transverse strength,
tensile strength, etc, various types of fiber (glass, carbon, Kevlar, and polyethy-
lene) reinforcement have been found to significantly improve many of the afore-
mentioned properties (19). Glass fiber reinforced composite resins have also been
introduced as a replacement for metal framework in crown and bridges or fixed
partial dentures as per recent clinical studies (20). Yet, research is still needed
to develop improved materials, pointed toward reducing the need for denture re-
pair (21). ANSI/ADA Specification No. 12 sets the requirements for denture-based
Resins.
Polymeric Teeth for Dentures. Acrylic resin denture teeth were intro-
duced in the late 1930s. About 60% of all preformed artificial teeth used in den-
tures, at least in the United States are produced from acrylics or vinyl acrylic
resins. The chemistry used is based on the well-known MMA polymerization
Vol. 2 DENTAL APPLICATIONS 181

technology. Poor wear, crazing, blanching, fracturing, etc, found in earlier acrylic
teeth, has been overcome by better methods of fabrication, improved formula-
tions, and use of higher cross-linking density. The molding technique for prepar-
ing the teeth must be highly controlled, with respect to particle size, molecu-
lar weight, and residual initiator. Further, the mix flow properties and curing
cycle must be highly controlled. Mechanical retention serves, to some degree,
to anchor the teeth in the chemically activated denture-based resins. However,
a combination of mechanical and chemical bonding is used to retain the teeth
(22).
Polycarbonates and polyslfones have also been explored for producing molded
teeth. Compositions containing very finely dispersed spheres of pyrogenic silica
as reinforcing fillers, urethane dimethacrylate (Fig. 8) resin, highly cross-linked
IPNs, and the fabrication of layered teeth with an exterior made up of a 2,2-
bis-p(2 -hydroxy-3 -methacryloxypropoxy)-phenylpropane (BisGMA)-based resin
have also been explored (23). All formulations employ pigments to provide a natu-
ral appearance. Other additives/modifiers are also used to achieve a more natural
appearance.
Acrylic teeth, with compressive strength of 76 MPa (11,000 psi), abrasion
resistance, elastic modulus of 2700 MPa (3.9×105 in. − 2 ), elastic limit of 55 MPa
(8000 psi), Knoop hardness (KHN) range of 18–20 kg/mm2 , and good abrasion
resistance, have physical properties which are lower than those of metal alloys
used for dentures and those of human enamel or dentin. For example, dentin and
enamel have an ultimate compressive strength of 297 and 384 MPa, respectively,
and ultimate tensile strength of 105.5 and 10.3 MPa, respectively. Furthermore,
the low modulus of elasticity in plastic teeth reduces the clicking sound often
exhibited by denture wearers. Compared to porcelain teeth, acrylic teeth have
less resistance to creep, higher water sorption, greater fracture toughness, better
resistance to thermal shock, and bond to the denture base. In contrast, porcelain
teeth display better dimensional stability and increased wear resistance. A study
of plastic teeth opposite plastic teeth or opposite smooth porcelain teeth has been
published (24). Plastic teeth are covered by ANSI/ADA Specification No. 15.
Denture Repair Resins. Fractured dentures are readily repaired with
materials similar to the RT- or cold-cured denture resins. Repairs are achieved
with little to no dimensional change. However, the strength of the repaired den-
ture may be substantially less than the original prosthesis (25). ANSI/ADA Spec-
ification No. 13 (1999) sets the requirements for cold-cured repair resins.
Denture Liner Materials. There are three groups of these materials: hard
and soft liners and tissue conditioners. It is often necessary to refit the denture
because of the changes in the denture-bearing tissue. To meet this need a hard
relining material can be employed, using an RT- or cold-cured acrylic resin at the
dentist’s office, or by sending the denture to a laboratory to be repaired with a
heat-cured acrylic resin. Soft liners weaken the strength of the heat-cured resins,
since they can reduce the thickness of the denture base and allow diffusion of
monomer or solvent into the base. The cold-cured formulations are basically of
two types: a two part PMMA powder blended with MMA monomer, containing
the plasticizer di-n-butyl phthalate or poly(ethyl methacrylate), PEMA powder,
blended with liquid butyl methacrylate (BMA) monomer. The BPO–amine redox
initiator system is used for curing. The use of PEMA and BMA works best where
182 DENTAL APPLICATIONS Vol. 2

the patients may be sensitive to PMMA or MMA. However, the use of PEMA and
BMA creates a liner with a lower T g , which may create dimensional problems. The
liners must show good adhesion to the denture, allow recovery from deformation,
provide a good cushioning effect, have good wetability, be relatively resistant to
oral fluids, not support bacterial growth, not impair denture function, and be
easily cleaned. At present, a material awaits discovery for fulfilling all of these
requirements. Polyphosphazine fluoroelastomers have been formulated and cured
with peroxides (26), showing that systems may be found to eliminate some of the
deficiencies found in currently available liners.
Soft liners were developed to eliminate the use of MMA directly against soft
tissue. Also, there are patients who are not able to tolerate a hard relining surface,
even though the denture fits well. The soft liner is more comfortable and provides
a means of absorbing masticatory forces via the highly resilient material placed
between the denture and the soft oral tissue. In addition, soft liners may be used
to reduce tissue inflammation caused by worn out or ill-fitting dentures. Polymers
with a T g slightly above the mouth temperature exhibit a rubbery behavior in the
oral cavity. A variety of materials have a T g low enough to be useful as soft liners,
including silicones and acrylics. PMMA is also useful when plasticized to obtain
the required T g . Fortunately, acrylic monomers are available which produce poly-
mers with a wide range of T g , starting with PMMA at 105◦ C, PEMA at 65◦ C, and
poly(n-butyl methacrylate) (PBMA) at 20◦ C. They are all useful for producing soft
liners. The soft liners are generally supplied as powder-liquid kits or ready-to-use
sheets. Materials currently available are usually plasticized acrylics. All formu-
lations contain fairly high molecular weight acrylate or methacrylate polymers or
copolymers, derived from ethyl, n-propyl, n-butyl, etc, monomers and a liquid or
solvent, such as ethyl alcohol or ethyl acetate, a plasticizer, such as dibutyl phtha-
late, and a polymerizable monomer. The T g of the material is set to ≤47◦ C. The
materials adhere well to denture-based resins. But, they have poor elasticity and
harden upon aging because of the loss of the plasticizer (27–30). More hydrophilic
liners have been formulated by using HEMA or other copolymers (28). However,
HEMA-based resins may soften and swell excessively due to water sorption, lead-
ing to undersirable functional changes.
Silicone liners are similar in composition to the previously described elas-
tomeric impression materials, which are produced by condensation polymeriza-
tion. Systems for the relining application may be either a one-component system,
which cures in the presence of moisture or heat, or a two-component system, con-
taining base and catalyst. Both types generally have poor adhesion to the denture
surface, and can readily support bacterial growth.
Tissue Conditioners. These products alleviate discomfort from soft-
tissue injury or inflammation. Tissue conditioners are soft materials applied tem-
porarily to the denture fitting surface, allowing better distribution of stress. They
exhibit viscous flow under pressure, forming a very soft cushion between the hard
denture and the soft tissue. In terms of softness, the material must not be too soft
or flow to the extent that it will be displaced from between the denture and the mu-
cosa. These materials may consist of PEMA powder mixed with a solvent (such as
ethyl alcohol) and a plazticizer (such as n-butyl phthalate and n-butyl glycolate)
(31,32). The alcohol swells the PEMA beads, rapidly promoting diffusion of the
plasticizer into the polymer, yielding a plasticized gel. Alcohol and plasticizer are
Vol. 2 DENTAL APPLICATIONS 183

slowly leached out from the applied gel, which may cause the material to become
too rigid. The liner must be replaced every few days to retain properties, until the
patients supporting tissues return to normal state.
Crown and Bridge Temporary Resins. Materials used in this area are
usually based on methyl or ethyl methacrylates and BisGMA-acrylics mixtures
(20), or even an ethyleneimine-terminated monomer (33). The formulations are
supplied as a two-component paste, composed of monomers and polymerization
initiator. Used for interim tooth coverage, these materials are not as strong as
other acrylics. However, they exhibit good flow, low exotherm, and low curing
shrinkage. They maintain the correct biting relationship, stop teeth drifting, and
protect the prepared tooth against fracture, while waiting for the permanent pros-
thesis to be delivered.
Polymeric materials are also used for fixing veneers on crown and bridges.
Polymers used for this application include acrylics, vinyl acrylics, and dimethacry-
lates, as well as silica- or quartz-microfilled composites. After placing on the metal-
lic substrates of the prostheses, the materials are heat or light cured. These ma-
terials are easy to fabricate, and can be readily matched to the color of the tooth
structure. The acrylic facings have poor adhesion to the metals, being retained only
by curing the monomers into mechanical undercuts designed into the metal sub-
strate. They have less mechanical strength, less color stability, poorer abrasion,
etc, than normal dental composites, along with deforming more under bruxism.
With the advent of porcelain fused to metal crowns and bridges, restoratives with
polymeric veneers are less frequently used.
Mouth Protectors. The widespread growth of contact sports has acceler-
ated the use of mouth guards (34,35). Guards may be produced from natural rub-
ber, poly(vinyl chloride), poly(vinyl acetate-co-ethylene), or polyurethane materi-
als. Customized guards are often fabricated from poly(vinyl acetate-co-ethylene)
blanks, soft acrylic dough, liquid rubber latex, polyurethane, and laminated ther-
moplastic (36,37). Over the counter protectors usually fit poorly, in contrast to
dimensionally stable and comfortable, customized mouth protectors.

Maxillofacial Prosthetic Materials

A large number of polymers, including latexes, vinyl plastisols, silicone elastomers


(heat or RT vulcanized), and polyurethanes, may be formulated into materials for
facial prostheses (38–41). The materials should be biocompatible, easy to fabricate,
easy to clean, feel like real skin, translucent, stable to heat, light, and cleaning so-
lutions, and sufficiently resilient to prevent tearing. It should be possible to modify
the formulation to match skin color. No material meets all these requirements.
Latexes. These materials do not have the strength and color stability to be
very useful for this application. In addition, they may cause an allergic reaction.
However, a recent terpolymer derived from n-butyl acrylate, MMA, and methyl
methacrylamide, can be formulated with colorants to provide a superior latex,
compared to earlier materials.
Vinyl Plastisols. These materials have some utility in maxillofacial pros-
theses. The formulations are viscous liquids, made up of small vinyl particles
dispersed in a plasticizer, along with colorants. They are heated to generate the
184 DENTAL APPLICATIONS Vol. 2

Fig. 6. Gutta-percha structure.

desired materials. The loss of plasticizer and lack of stability decreases the use of
these materials.
Silicones. These materials have some only recently been used to produce
maxillofacial prostheses. Both the RT- and heat-vulcanized materials may be used.
Heat-vulcanized formulations are supplied as a semisolid or putty-like material,
which requires the addition of colorants. The molded material is cured under
pressure at 180◦ C/30 min. The heat-cured materials exhibit better strength and
color stability than the RT-cured materials.
Polyurethanes. This is the most recent material used in maxillofacial ap-
plications. Fabrication requires accurate proportioning of the components. The
isocyanate and polyol are blended, placed in a suitable mold, and allowed to cure
at room temperature. Colorants and other additives are also used in the formula-
tions. Even though the fabricated prosthesis has a natural feel and appearance,
the final product is still relatively unstable.

Root-Canal Sealants

A variety of materials have been used to hermetically seal the root canal, prevent-
ing ingression of oral fluids into the canal. One natural material used is gutta-
percha (Fig. 6), a rubber obtained from the Taban tree. This material has been
used in endodontics for over a hundred years. Rubbers are polymers of 2-methyl-
1,3-butadiene (isoprene), having two possible conformations, ie, a cis and trans
form, with the trans form being gutta-percha. These rubbers are hardened by vul-
canization, achieved by blending and heating with a few percent of sulfur, which
causes cross-linking. A typical formulation used in a root canal has about 19–22%
gutta-percha, 59–75% zinc oxide filler, 1–17% heavy metal salts, and 14% wax
plasticizer. The material softens at about 60–65◦ C and melts in the vicinity of
100◦ C, providing a temperature range to soften, deform, and condense the mate-
rial into the prepared root-canal space. Other materials used for endodontically
treated, fractured teeth are based on zinc oxide-eugenol, epoxy resin, polyvinyl
resin, calcium hydroxide resin based formulations, and glass-ionomers formula-
tions.

Other Uses

Patterns for gold-inlay castings can be prepared from acrylics. Castings made
this way are not superior to castings produced from a wax pattern, accounting
for the lack of interest in this technique. Some dental laboratories use epoxy die
Vol. 2 DENTAL APPLICATIONS 185

materials for fabrication of casts. Autopolymerizing resin formulations are used to


make custom impression trays, with such resins containing substantial quantities
of fillers to increase the rigidity of the materials. PMMA or other thermoplastics
are used to prepare occlusal night guards. Other areas of dentistry make extensive
use of polymers in retainers, splints, temporary space maintainers, and bite plates.

Restorative Materials

Filling Materials. Resins used to formulate dental composites/restoratives


were initially derived from the free-radical polymerization of doughs made from
PMMA beads blended with MMA monomer (42–46). Many studies have focused
on improving these materials, by addition of cross-linking monomers and rein-
forcing fillers (45), with much of the early work done at the National Bureau of
Standards. Earlier, the polymer industry had previously shown that epoxy resins,
based on bisphenol A, were excellent matrix resins for a variety of composites.
However, epoxies exhibited poor ambient polymerization characteristics under
conditions useful in the oral cavity. Knowing the latter, as well as the need to have
a new monomer which would be both free-radical polymerizable with less shrink-
age in composites, Bowen (47,48) made the discovery that the diepoxide derived
from bisphenol A and epichlorohydrin could be treated with methacrylic acid to
form a unique hybrid monomer, well known today as BisGMA (45,47,48). Alter-
natively, the BisGMA monomer may also be produced by reaction of bisphenol A
with 2 mol of glycidyl methacrylate. The synthetic path to the bulky, thermosetting
dimethacrylate, BisGMA, launched a new era for development of composites used
in dentistry. BisGMA (Fig. 7) has two chiral carbon atoms (denoted by an asterisk)
with the dimethacrylate diastereomers helping to make the BisGMA mixture a
viscous syrup. Compared with the PMMA–MMA doughs, the BisGMA-based for-
mulations, combined with inorganic reinforcing fillers and suitable polymerization
initiators, made available composite fillings with lower polymerization shrink-
age, improved mechanical properties, reduced water sorption, a more attractive
coefficient of thermal expansion, better esthetics, and more acceptable biocom-
patibility (44,45). A good review of dental composite resins has been published
(49).
Dental Composite Restoratives. Polymeric restoratives have three ma-
jor components: an organic resin matrix, an inorganic filler modified with a cou-
pling agent, and a suitable polymerization initiator system. The formulation used
to produce the organic matrix, or continuous phase, is made up of free-radical
polymerizable monomers. The monomer mostly used in the formulations for both
anterior and posterior resins is BisGMA (Fig. 7), or alternatively formulated with

Fig. 7. BisGMA structure(s).


186 DENTAL APPLICATIONS Vol. 2

Fig. 8. Monomers structures in urethane dimethacrylate mixture.

a urethane dimethacrylate monomer (Fig. 8). A variety of fillers may be used to


make up the reinforcing phase. Fillers may consist of silanized quartz, glass or
various ceramics, with silanization affording the coupling mechanism. A prepoly-
merized resin containing pyrogenic silica may also be used to reduce polymeriza-
tion shrinkage. Various polymerization initiators or activator–initiator combina-
tions are known to be useful to achieve curing. Inhibitors are required to prevent
polymerization during storage. Sealants used in dentistry have similar composi-
tions, but are more lightly filled or possibly unfilled. Composites used in dentistry
can come in various forms, ie, a one- or two-part formulation, a uniform paste, a
powder–liquid, a paste–liquid, or a paste–paste formulation.
Polymerization. Methacrylate-based restoratives are free radical not rad-
icals polymerized by redox systems or photochemically by visible light, using
photoinitiators or photoinitiator–photosensitizer combinations with only the vis-
ible light range (400–500 nm) allowed for curing. Redox initiation systems may
consist of such things as BPO/tert-amines, hydroperoxides-thioureas, peroxides
with ascorbic acid or derivatives, and BPO/tert-amine with synergistic promot-
ers, eg, polythiols (4,50–52). A commonly used combination for redox use is the
BPO/N,N-dihydroxyethoxy-p-toluidine system. The combination of α-diketones,
such as camphorquinone (CQ), with a tertiary amine, such as N,N-dimethyl-
aminoethyl methacrylate (DMAEMA) (52), are particularly useful for visible light-
curing (VLC) (53,54). With light activation, CQ and DMAEMA form an “exciplex”
with the “exciplex” subsequently producing a DMAEMA-based radical, which ini-
tiates the polymerization. VLC resins provide the dentist a significant control over
the restorative hardening process. Further, the porosity and surface tackiness, ow-
ing to air inhibition, are lower in the VLC-cured materials compared with that of
the redox formulations. But, properly mixed redox formulations polymerize much
more uniformly, especially in areas of great bulk, compared to the VLC formula-
tions. When using VLC systems to fill deep cavities, a layering technique must be
used to ensure adequate polymerization.
Monomers or Matrix Phase. Although BisGMA is widely used in com-
mercial dental composites, other types of dimethacrylates have also been stud-
ied or developed for use as alternatives to BisGMA (55–76). Because of the high
viscosity of BisGMA, a variety of dimethacrylates have been found to be useful
as reactive diluents or polymerizable modifiers to provide suitable viscosities for
high filler loading, with diethylene glycol and triethylene glycol dimethacrylates
(Fig. 5) being good examples. Studies on the kinetics and the nature of the network
Vol. 2 DENTAL APPLICATIONS 187

formation in the dimethacrylate polymerizations have been given significant at-


tention (77–83), with the types of monomers used and the degree of carbon–carbon
double bond conversion achieved determining the T g obtained (49). There is grow-
ing interest in varying the polymerization stages, ie, using a “soft start” stage, as
a way to improve the resin properties.
Resins have also been designed to utilize multifunctional methacrylate
prepolymers, derived from the chain-extending reaction of BisGMA with a di-
isocyanate, such as 1,6-hexamethylene diisocyanate, combined with a diluent
monomer (64,65). Incorporating urethane residues in the matrix, which en-
hances toughness, gained great acceptance in Europe, with an example being
the monomer derived from the reaction of HEMA with a branched aliphatic diiso-
cyanate (Fig. 8).
Many experimental dimethacrylates have been explored for reduction of
shrinkage and water sorption in composites, seeking to improve such things as di-
mensional stability, creep resistance, fracture toughness, wear resistance (66,84–
95). The goal is to formulate a better alternative to the commonly used amal-
gam. Some of these have been prepared from nonhydroxylated homologues of
BisGMA, having lower viscosity (66). In one case, a multimethacrylate prepared
from esterification of a low molecular weight styrene–allyl alcohol copolymer was
shown useful in reducing shrinkage or polymerization contraction stress in Bis-
GMA/TEGDMA neat resin blends (96,97).
A variety of fluorine-containing monomers and polymers have been prepared
and examined to produce hydrophobic dental composites with low water sorption,
high contact angles, reduced margin leakage, and resistance to surface staining
(67–73). One such formulation consisted of 75 wt% octafluoro-1,1,5-trihydropentyl
methacrylate and 25 wt% of a nonhydroxylated homologue of BisGMA (66–68).
But, the polymerization shrinkage and strength deficiencies were not improved.
Also, the volatility of the nonbulky fluorinated-monomer component was a prob-
lem. In contrast, a stronger hydrophobic composite was prepared from a low
surface-energy matrix resin consisting mainly of a highly fluorinated multifunc-
tional methacrylate prepolymer, ie, PFMA (70–73,98). The viscosity of this for-
mulation was comparable to that of BisGMA, along with solubility in a variety
of diluent monomers. The dimethacrylate derivative of a fluorinated triethylene
glycol, having low viscosity, was recently examined as a reactive diluent, showing
some promise to improve the performance properties of an ethoxylated bisphenol
A dimethacrylate (BisEMA)-based composite (99–101).
Elimination of polymerization shrinkage has been under study for some time
(74,75). In the early work, a blend of a BisGMA-based resin and a solid spiroortho-
carbonate (SOC), which also polymerizes by a free-radical, ring-opening mecha-
nism, was cured to give thermosets with very low volume shrinkage (75). Following
the latter study, a great variety of compositions have been designed for ring open-
ing, expanding polymerizations, focused on eliminating or reducing the shrinkage
as well as improving the physical and mechanical properties of composites. The
focus has mainly been on SOC and SOC-type monomers with epoxy resins (102–
113). This concept has not, to date, produced marketable dental restoratives.
More recently, the possible use of liquid crystalline monomers (114), hy-
perbranched polymers (115,116), inorganic–organic hybrid monomers (117–120),
and sol–gel technology (121) has started to be examined for preparing improved
188 DENTAL APPLICATIONS Vol. 2

composites. The use of multimethacrylate substituted hyperbranched polymers


looks to be a particular attractive path to explore for generating composites with
significantly lower shrinkage, since low viscosity, high molecular weight entities
can be formulated into the monomer–polymer mixture. Also, the in situ gener-
ation of a nanocomposite, where the inorganic component is truly distributed
at the molecular level in the cured composite, may satisfy the great need for
preparing restoratives with both low shrinkage and significantly improved wear
resistance.
Reinforcement Phases. After introduction of quartz filler in the late
1950s, many types of reinforcing fillers have been studied or used in dental
composites. In addition to quartz, fused or colloidal silica, and other inorganic
fillers, finely divided, organic prepolymenized composite particles are also useful
as a dispersed phase. This is especially true for microfilled and hybrid compos-
ites (122–124). Fillers serve to increase hardness and compressive strength, and
significantly reduce shrinkage of the restoratives. Filler technology has brought
many improvements to currently used composites. But, in order for the compos-
ites to have acceptable mechanical properties, it is critical for the resin matrix and
filler to have a strong interfacial bond. A breakdown at the interface, followed by
load application, will not allow the stresses developed to be effectively distributed
throughout the material. Bonding is achieved by the use of coupling agents, in-
corporated into the formulation at the surface of the filler. Vigorous efforts have
been focused on maximizing filler volume or obtaining highly loaded composites,
which exhibit much better stress-bearing capability.
Physical Properties. Table 2 shows some physical properties of unfilled
(neat) resins and filled composites. Microfilled composites generally have inferior
properties compared to conventional or the more recent hybrid restoratives, with

Table 2. Physical Properties of Resin Restoratives


Conventional and
Unfilled Microfilled filled hybrid
Property PMMA composite composite
Inorganic contenta , wt% 33–51 70–80
Compressive strength, MPab 55–78 225–350 250–400
Knoop hardness (KHN) 15 5–30 50–60
Tensile strength, MPab 14–28 30–55 50–90
Modulus of elasticity, GPac 1.9–2.3 3.2–6.0 8.0–20.0
Linear coefficient of thermal 92 50–70 20–40
expansion, 10 − 6 ◦ C
Water sorption, mg/cm2 1.70–2.03 0.94–2.20 0.50–0.70
Polymerization shrinkage, vol% 5.2–8.0 1.0–1.8 1.2–5.3
Thermal conductivityd,e W/(m·K) 2.4 6.3–8.4 1.5–4.0
a The volume (weight) of the filled systems varies from about 30 to 77% (50–85%). Traditional, small
particle filled, micro-filled, and hybrid composites have fillers ranging in size, respectively, from 8–12,
1–5, 0.04–0.4, to 0.6–1.0 µm.
b To convert MPa to psi, multiply by 145.
c To convert GPa to psi, multiply by 145,000.
d Thermal conductivity of enamel and dentin, respectively, is 0.87 and 0.59 W/(m·K).
e Composite restoratives are good insulators.
Vol. 2 DENTAL APPLICATIONS 189

the exception of polishability. By definition, hybrids (blends) have a combination


of colloidal and fine particles as filler, at approximately 60–65 vol% with the fillers
ranging in size from 8–12, 1–5, 0.04–0.4, to 0.6–1.0 µm. The higher volume ratio
of polymer to inorganic filler, ie, low filler content, of the microfilled resins leads to
lower modulus of elasticity, greater thermal dimensional changes, less resistance
to indentation, and higher water sorption. Requirements for dental composites
are covered by ANSI/ADA Specification No. 27.
Dental Cements. Polymeric matrices used in formulating cements are
similar to those used in methacrylate-based composites and sealants. BisGMA or
some other dimethacrylate is blended with monomers such as MMA, along with
fillers and other additives, to make the formulated adhesive useful in the oral
cavity. They may be of the VLC type and/or chemically cured type. They may also
contain additives such as inorganic fluoride salts, which may result in reducing
recurrent decay.
Polyelectrolyte-Based Restoratives. Alginates, previously described
under Impression Materials, were the first ionic polymers to be employed in dental
applications. But, polyelectrolytes derived from poly(acrylic acid), various co- and
terpolymers of acrylic acid, and other alkenoic acids (ie, itaconic acid and maleic
acid) are used in aqueous solutions for formulating polyelectrolyte-based cements.
These materials are also known as glass polyalkenoates or more commonly glass-
ionomers (GIs) (125–135). Several articles present the chemistry associated with
GIs (136–139). Cements based on glass ionomers adhere well to enamel but only
weakly to dentin.
Glass Polyalkenoate Cements. Polyalkenoate cements, which evolved
from the zinc phosphate cements, were formulated with an organic polyacid and
subsequently called zinc polyacrylate cements (127). Zinc oxide was the basic pow-
der component, with smaller amounts of magnesium or tin oxide and, optionally,
small quantities of silica, calcium hydroxide, stannous fluoride, and other salts.
The acid component was an aqueous solution of poly(acrylic acid), having about
30–50% solids, with the polymer having an average molecular weight of 30,000–
50,000. Copolymers of acrylic and other alkenoic acids, eg, itaconic, maleic, and
aconitic acids, were subsequently used to make shelf stable aqueous solutions
with lower viscosity, providing a cement with better properties. A series of acid–
base reactions brings about hardening or setting of the cements, with ionic-type
cross-linking achieved by the ionized carboxylate groups forming a complex (salt-
bridge) with the divalent metal cations, producing a highly, ionically cross-linked,
hydrophilic matrix. Free powder embedded in the stiff polymeric hydrogel or ma-
trix acts as a normal reinforcing agent. Other types of additives are incorporated
into the formulations to improve certain properties. Cements of this type, which
have an opaque appearance due to the high concentration of zinc oxide, adhere
well to tooth structure and base metals, enabling them to be used as bases un-
der permanent fillings and to cement prefabricated restorations and orthodontic
appliances. The properties of various cements are given in Table 2. A family of non-
aqueous polycarboxylate cements may also be formulated, with such systems dis-
playing excellent hydrophobic and energy-absorbing properties. Chain-extending,
acid-base reactions of dimer and trimer acids with various basic powders may
be used (140). The water-based cements are covered by ANSI/ADA Specification
No. 96 (1994).
190 DENTAL APPLICATIONS Vol. 2

Table 3. Physical Properties of Resin Restoratives


Conventional and
Unfilled Microfilled filled hybrid
Property PMMA composite composite
Inorganic content, wt% 33.2–50.9 70.4–80.2
Compressive strength, MPaa 55–76 221–330 127–350
Tensile strength, MPaa 14–28 28–56 28–63
Modulus of elasticity, GPab 2.3 3.2–5.0 7.1–16.2
Linear coefficient of thermal 92 46–70 25–40
expansion, 10 − 6 ◦ C
Water sorption, mg/cm2 2.03 0.94–2.20 0.13–0.74
Polymerization shrinkage, vol% 5.2–8.0 1.9–5.8 1.2–5.3
Thermal conductivity, W/(m·K) 2.4 6.3–8.4 10.5–13.8
a To convert MPa to psi, multiply by 145.
b To convert GPa to psi, multiply by 145,000.

More translucent glass polyalkenoate- or polyelectrolyte-based cements


(GI) were developed by using similar aqueous solutions of polyacids, such as
poly(acrylic acid), poly(acrylic acid-co-itaconic acid), poly(acrylic acid-co-maleic
acid), etc, and ion-leachable calcium fluoro aluminosilicate type glass powders
(126,128,135). The matrix in this conventional-type GI is formed by acid-base re-
actions involving the di- (Ca2+ ) and trivalent (A13+ ) cations, binding carboxylate
groups in ionic cross-links (salt-bridges), producing a stiff hydrogel into which
partially reacted glass particles are embedded (136–138). Glass-ionomers, simi-
lar to the zinc polycarboxylate cements, exhibit good adhesion properties. Glass-
ionomer cements may be used as a cosmetic filling materials and for the repair
of cervical erosions because of good adhesion and semitranslucent nature. In the
area of mechanical strength, GI-based cements are superior to zinc phosphate
and zinc polycarboxylate, approaching the dental silicate cements in compres-
sive strength and modulus of elasticity (Table 3). Other polyelectrolytes have also
been explored as polymeric acids for formulating GIs, with poly(vinyl phosphonic
acid) being an example (141,142). The vinyl phosphonic acid polymer formula-
tions were too acidic to allow suitable working and setting times (142). Experi-
mental cements have also been described for taking advantage of the reaction of
an aqueous solution of phytic acid and myoinositol hexakisphosphate with zinc
oxide or alumino-silicate glass powders (143). In such a formulation, a polyelec-
trolyte network matrix is formed by ionic chain extension and cross-linking re-
actions involving leachable multivalent cations and the organophosphoric acid
groups.
Acrylic acid copolymers were recently modified with N-acryloyl- or N-
methacryl-oylamino acids, such as N-methacryloyl-glutamic acid (MGA), provid-
ing a possible path to improved, conventional GIs (144–148). The copolymers stud-
ied had the carboxylic acid groups tethered at various distance off the copolymer
backbone, with the acid groups having a range of pK a or dissociation constants
(149,150). The AA IA MGA copolymer having an 8:1:1 monomers ratio looked
particularly attractive to use in formulating conventional GIs, as shown by sta-
tistically designed experiments. The study showed that an 8:1:1 (AA:IA:MGA)
Vol. 2 DENTAL APPLICATIONS 191

copolymer gave the highest compressive strength (148). Raman spectroscopy


studies showed that tethering the acid groups various distances off the copoly-
mer backbone influences the level of salt-bridge formation (149). This type of
modification was also shown to enhance the adhesion of the GI to tooth structure,
improve fracture toughness, and enhance fluoride release. All the improvements
were attributed to greater availability of the carboxylic acid groups to ionize and
form salt-bridges. The copolymers with pendant amino acid residues have also
been developed for preparing VLC formulations (146,150).
The monomer N-vinylpyrrolidinone (NVP), 1-vinyl-2pyrrolidinone, has been
explored for modification of poly(acrylic acid-co-itaconic acid), providing a path to
new polyelectrolytes for formulating GIs (151–155). For these copolymers, the opti-
mum monomer ratios and molecular weights, to give good mechanical properties,
were determined by statistical design of experiments. Formulations containing
NVP residues were also developed for VLC applications. Clearly, new polyelec-
trolytes can be prepared for formulating improved GIs.
VLC Glass-Ionomers. Presently, the GI formulations used in the United
States are either the free-radical, VLC, redox initiated, or a combination of VLC
and redox initiation types (128,136–139). These are water-soluble polylectrolytes
having both pendant carboxylic acid groups and free-radical polymerizable moi-
eties, such as methacrylate residues. These hybrid-type formulations, which are
more composite-like, are also referred to as resin modified glass-ionomers (RMGIs)
(138,156–158). The two-component formulations, with one being an aqueous solu-
tion of the polyelectrolyte (acidic polymer), initiators, and reactive monomers and
the second the basic glass powder consisting of calcium fluoro-aluminosilicate, are
mixed, placed in the cavity, and exposed to visible light. Hardening occurs in two
ways: formation of a free-radically cross-linked organic matrix and salt-bridge for-
mation. A combined VLC, redox, and salt-bridge reaction in the same formulation
appears to work best (157,158). The VLC GIs are less technique sensitive, cure in
shorter time, may be finished at the time of placement, are more plastic in nature,
have better adhesion to tooth structure, and reduce microleakage better than the
conventional GI formulations (159). All in all, the RMGI modifications made the
GI family of restoratives significantly stronger than the conventional GIs, leading
to recommendations that these materials could be used in Class V and Classes I
and II restorations in primary teeth.
Compomers. Glass-ionomers have evolved along with composite resin
technology to produce a new family of materials for restoratives, now commonly
called compomers (160–166). To some degree, compomers offer the advantages
of both GI and composites in one material. Starting from the first resin modi-
fied cements (160,161) work, compomers were first introduced to the market in
1995. The term polyacid modified composite more readily describes the chemistry
of compomers. These formulations consist of an organic and an inorganic phase,
with the inorganic phase having some level of fluoride-containing, basic or reac-
tive glass particles. The organic phase also contains carboxylic acid functionalized
monomers and initiators. On exposure to light, free-radical polymerization occurs
to give the cured resins. Water sorption of the cured organic matrix facilitates
an acid-base reaction, bringing about further hardening due to formation of some
ionic-type cross-linking. Water diffusion also facilitates the release of fluoride ions
to the tooth structure. The physico-mechanical properties of GIs, compomers, and
192 DENTAL APPLICATIONS Vol. 2

composite restoratives have recently been compared (167), with this and other
efforts showing that the mechanical properties of compomers, as well as their re-
sistance to wear, are significantly better than both conventional- and VLC-type
GIs. The compressive strength and diametral tensile strength for compomers is in
the range 280–460 MPa and 52–62 MPa, respectively, with polymerization shrink-
age in the range of 2.0–3.0%, and the coefficient of thermal expansion (ppm/◦ C)
being in the range 12–41. The reported coefficient of thermal expansion for coro-
nal tooth structure is about 11 ppm/◦ C. Clearly, research on compomers suggests
that there are still others ways to be discovered for improving the handling char-
acteristics and compensating for polymerization shrinkage in the design of dental
restoratives.

Sealants

A variety of sealants have been explored or developed (168), with many people
having one or more applications of a sealant. Sealants are vital for promotion of
adhesion, which significantly reduces caries formation (169–177). Pit and fissure
sealants are covered under the American Dental Association (ADA) Acceptance
Program. These materials are used to seal high caries-susceptible pits and fissures
of the deciduous and permanent molars, and also to seal microspaces between
the tooth and restorative materials, enabling these materials to adhere firmly
both to prepared cavity walls and to other restoratives. They provide dental pulp
protection and protection from secondary caries formation.
Most dental sealants are resinous materials derived from free-radical poly-
merizable monomers, but GI dental cements (discussed earlier) also have some use
as sealants. Sealing with resinous materials or GIs is part of modern preventive
technology, where the sealants used for this purpose are called preventive dental
sealants (PDS). Dental caries that occur around restorations are called secondary
caries. Sealing the microspaces with adhesive resinous materials is effective in
controlling secondary caries; here we call these adhesive materials the restorative
dental sealants.
A brief history and state-of-the-art ion enamel and dentin bonding was pub-
lished in 1995 (178). Recent advancements in synthetic chemistry and polymer
science of dental sealants are now briefly reviewed or discussed, including those
designed for various clinical uses, directed toward prolonging the lifetime service
of natural teeth.
Preventive dental sealants, used to seal the susceptible areas of teeth, are
classified into pit and fissure sealants and smooth surface sealants. From a ma-
terial science perspective, pit and fissure sealants can be further classified into
resin sealants and GI cements. Preventive dental sealants are usually placed
onto molar teeth of young children who are at high risk for caries develop-
ment.
Pit and Fissure Sealants. Resin sealants consist of a free-radical poly-
merizable monomer mixture, having a viscosity low enough to penetrate easily
into narrow pits and fissures, capable of being cured to a hard and durable sealing
material. BisGMA, urethane dimethacrylate, and other methacrylates are very
popular as monomers for resin sealants, along with other monomers, to lower
Vol. 2 DENTAL APPLICATIONS 193

mixture viscosity to enhance penetration ability, which is interesting to note.


The highly active, anerobically cured cyanoacrylate monomers have also been
evaluated for sealant applications (179). Etchants, such as phosphoric acid, citric
acid, or other acidic solutions, are applied to the enamel pit or fissure area prior
to application of the sealant, to provide the required tooth bonding to the nonad-
hesive resin (179–181). This so-called acid etching changes the enamel surface to
a microrugged structure, which fosters better penetration of the sealant into the
fissure and results in stronger adhesion between the sealant and the tooth surface
(182). Acidic monomers have been developed for use in the sealant formulations to
further enhance the penetration and adhesion. Polymerization of the sealants is
initiated chemically with BPO/amine or sulfinate (redox combinations) or visible
(blue) light irradiation, where the formulation contains CQ as the photosensitizer.
These sealants may be one- or two-component formulations. One-component, pho-
topolymerizable sealants can be cured very rapidly (<60s) by exposure to visible
light, with two-component, self-curing sealants taking significantly longer time to
harden or cure after mixing (183).
Glass-ionomer cements, where the chemistry was described earlier in the
text, are widely used as sealants. Uses of this type of hydrogel (184) vary with the
dental treatment, where low viscosity pastes, which exhibit fast setting, charac-
terize the cements for pit and fissure sealing. In this process a glass powder and
an aqueous polymer solution are mixed in given proportions and packed into pits
and fissures without prior acid etching of the tooth surfaces. The cement paste
cures within a short time through the salt-bridge formation between poly(acrylic
acid) (185), or acrylic acid copolymers with maleic and itaconic acids (6), and Ca2+
and Al3+ cations leaching out from the glass powder. Poly(acrylic acid) under-
goes ionic interaction with calcium ions on the enamel surface, producing bond
strengths of 2–4 MPa. Fluoride ion released from these compositions helps pre-
vent caries formation, improving the acid resistance of surrounding dental enamel
(186).
Smooth surface sealants are used to prevent bacteria, staining, and phys-
ical damage to susceptible teeth. Cured sealants are directly exposed to the
oral conditions, and therefore strong adhesion to enamel and dentin, good
physical properties, good wear resistance, chemical stability, biological sta-
bility, and thin-film formation are required. Glass-ionomer cements fail to
meet these requirements because of insufficient physical properties. Instead,
highly cross-linked resin sealants, reinforced with ultrafine silica particles, are
used.
Shear bond strengths of composite restoratives on enamel, etched with 30–
40% phosphoric acid solutions are typically in the range of 18–25 MPa (182). In
comparison, bonding to dentin is a much tougher challenge because of its organic
constituents, fluid-filled tubules, and intrinsic compositional variation (187). How-
ever, substantial progress has been made to facilitate minimal invasive restora-
tive therapy, by design of new bonding techniques/agents. First, it was discov-
ered that resin penetration into the acid etched (conditioned) dentin, which is
critical to achieve good bonding, is influenced by dentinal conditions (moist or
dry) and by the type of solution used (188,189). There is great correlation of the
bond strength received with the permeability and dentin penetration depth (189–
191). The elusive goal, not yet totally reached, is to have a simplified application
194 DENTAL APPLICATIONS Vol. 2

method for a dentin bonding system which will produce a very durable bond with
total elimination of future microleakage (192–194). Composite resin polymeriza-
tion shrinkage is the main reason for marginal gaps and stress at interfaces,
leading to microleakage (192,195). Thermo- and load-cycling studies are essen-
tial for determining or predicting the dentin-restoration bond longevity (196,197).
Apart from using simple acid etching, the evolutionary development of surface-
active comonomers with both hydrophilic and hydrophobic moieties, as part of
the primer system, has made a very significant impact on improving bonding to
dentin (198–201). The work on self-etching primers, to improve the understand-
ing of what it takes to bond well to dentin, also played a very important role
in the design of improved dentin bonding systems (202–206). For specific infor-
mation on some of the most recent, commercial enamel and dentin bonding sys-
tems, see literature on Excite (Ivoclar AG or Vivident), Single Bond (3M Dental
Products), One Step (BISCO), Prime Bond (Dentsply/DeTrey), and Optibond Solo
(Kerr Sybron).
Dental Restorative Sealants. Dental amalgams are mixed and con-
densed into molar teeth cavities, hardened by the amalgamation process. The
amalgam has no chemical interaction with the cavity wall, and irregular mi-
crospaces are produced along the interface between them. Amalgam sealant and
amalgam bonding agents are used to seal the microspace and control the inci-
dence of secondary caries around the amalgam restoration. Chemical composition
of this sealant or bonding agent may be as follows: a monomer such as diethylene
glycol dimethacrylate (Fig. 5) or a comonomer such as methacryloxyethyl phtha-
late (MEP). Other formulation additives may be tert-butyl hydroperoxide initiator,
o-sulfobenzimide accelerator, and hydroquinone inhibitor.
This sealant is composed of only one liquid, which remains uncured before
application, but cures quickly once applied to amalgam. Because of tert-butyl hy-
droperoxide and o-sulfobenzimide, polymerization occurs anaerobically when it is
cut off from air and it contacts the copper in the amalgam. When placed between
two glass plates at 25◦ C, it takes more than 10 min to cure. However curing occurs
within 2 min between a glass plate and the amalgam. The MEP (207) monomer
is used to enhance penetration of the sealant into micro spaces and achieve adhe-
sion to both arnalgam and tooth surface. This sealant achieves amalgam–enamel
bonding by about 1.0 MPa and bonds amalgam–dentin by about 2.6 MPa without
acid etching. Examples of two amalgam bonding agents illustrate the latter, brief
discussion.
Amalgam Restorative Sealants. These adhesives are of two types: adhe-
sive resin cements and bonding agents originally developed for composite restora-
tions. One commonly used adhesive resin cement is Amalgambond (Sun Medical
Co., Japan), which consists of PMMA powder and MMA monomer, containing
4-methacryloxyethyl trimellitate anhydride (4-META) and tributylborane oxide
(TBB-O) as a catalyst. TBB-O is activated by the water on the surface of adher-
ents and promotes graft polymerization of MMA onto collagen in dentin, promoting
strong adhesion (201,207,208).
Panavia 21 (Kuraray Co., Japan) is an adhesive cement, characterized by
the use of 10-methacryloyloxydecyl dihydrogen phosphate (MDP). This cement
consists of a primer and a composite paste. The primer is a monomer solution
containing MDP, which develops strong adhesion to enamel and dentin. The
Vol. 2 DENTAL APPLICATIONS 195

cement paste is a mixture of polymerizable monomers, including MDP, and


inorganic filler, with polymerization/curing caused by the catalyst BPO/text-
amine/sulfinate. Strong adhesion to tooth substances and amalgam is achieved.
Panavia has a shearbond strength, in MPa, of 20 to dentin, 37 to enamel, 15 to
amalgam, and 47 to Ni–Cr alloy.
Composite Restoration Sealants. Systems used in this case consist es-
sentially of dimethacrylate mononers, such as BisGMA, homologues of BisGMA,
urethane dimethacrylate, and silanated inorganic fillers, as discussed in the sec-
tion on Composite Resins. The sealants used for restorations (called bonding
agents) are applied onto the cavity walls prior to the placement of composites
and bond the two substances tightly.
Bonding Agent Chemistry. Composite bonding agents are a mixture of
polymerizable monomers or a solution of monomers in volatile solvents, which
cures through free-radical polymerization on the cavity walls or between cav-
ity walls and composite restorations. Liquid monomers, such as MMA, HEMA
(207,209,210), other erythritol methacrylates, and ethylene glycol dimethacry-
late, exhibit strong adhesion to dry teeth. The well-known Gluma adhesive sys-
tem is made up of water, HEMA, and glutaraldehyde (211). When the teeth cav-
ity walls are wet, application of acidic monomers is common for getting reliable
adhesion, even when using a water-free adhesive primer (189). Monomer com-
position is selected for a balance of hydrophilicity and hydrophobicity, physical
properties of the cured polymers, adhesion to composite restorations, curing time,
and so on. Polymerization catalysts used are similar to those for pit and fissure
sealants.
Pretreatment of cavity walls with bonding agents is a must for composite
restorations. A typical procedure for restoration with composites, using a light-
cured bonding agent and a light-cured composite is as follows: (1) cavity prepara-
tion, (2) washing and air drying, (3) acid etching of the cavity wall, (4) application
of the bonding agent and visible light irradiation, (5) composite restoration filling
and visible light irradiation, and (6) finishing and polishing. Researchers have
improved this procedure by using acidic monomer in the bonding agent as the
acid for etching. Combining the etching and bonding agents reduces the number
of steps and gives higher bonding strength to the dentin.

Dental Adhesives (For Alloys and Ceramics)

Various materials such as polymers, alloys, ceramics, and composites are used to
restore or replace tooth structure. It is vitally important for these materials to
be bonded securely to the tooth surface. Lack of bonding between the materials
and tooth will induce secondary dental caries or restoration detachments. Recent
dental adhesive techniques are based on chemo-mechanical bonding between the
adhesive and adherend.
Surface conditioning before applying adhesives effectively increases the sur-
face bonding area and enhances the strength of the bonding agent. The enamel is
commonly etched with an aqueous solution of phosphoric acid or other acids. Most
current enamel bonding systems employ phosphoric acid in various concentrations
and viscosities as an etchant (169,170).
196 DENTAL APPLICATIONS Vol. 2

Casting alloys in dentistry are categorized into base metals and noble metals.
Base metals include cobalt–chromium (Co–Cr), nickel–chromium (Ni–Cr), and ti-
tanium (Ti) alloys, while noble metals include gold (Au), silver (Ag), and palladium
(Pd) alloys. Mechanical methods, such as air-abrading with 50–200 µm alumina,
are the most common way to prepare the alloy surface. Electrolytic etching creates
micro-mechanical retention on the alloy surface. Other types of surface modifica-
tion include electroplating, silica coating, and ion-coating.
Dental ceramics consist mainly of metal oxides of silicon, aluminum, potas-
sium, and sodium. Etching with an aqueous solution of hydrofluoric acid roughens
the ceramic surface.
The roughened, adherend surface is treated with a primer for chemical
bonding. Because the composition of dental adhesives is based on methacrylate
monomers, the primers for chemical bonding also contain functional monomers.
The functional monomer usually consists of a polymerizable methacrylate or vinyl
group, a hydrophobic intermediate spacer, and a functional group capable of bond-
ing to the adherend surface. Functional groups effective for bonding base metal
alloys are the acid anhydride, carboxylic acid, and phosphoric acid groups. Thiol
derivatives are used to prime noble metal alloys. The dental ceramic surface is
primed with silane couplers activated in acids, such as carboxylic acid monomers,
ferric chloride, and/or a tri-n-butylborane derivative (TBB) (212,213). Silane cou-
plers are also used for surface modification of filler particles included in dental
composites (214).
After surface preparation, the restorative material is bonded to the tooth
structure with auto-polymerizing adhesive resin. One prerequisite for dental ad-
hesives is an ability to cure in the mouth; that is why methacrylate-based polymer
materials are used in dentistry. Initiation systems are BPO–t amine or TBB (201).
Monomers used are MMA or bifunctional methacrylate monomers. The needed
optical opacity (215,216) is achieved by various inorganic and metal compounds
incorporated into the formulations.
Acid anhydride or acidic monomers, such as 4-methacryloxyethyl trimel-
litate anhydride (4-META), 4-methacryloxyethyl trimellate (4-MET), 4-(3-
methacryloyloxypropoxy carbonyl) phthalic anhydride (MPRPA), and 4-(4-
methacryloyloxybutoxycarbonyl) phthalic anhydride (MBPA), prepared by
condensing hydroxyalkyl methacrylates and trimellitic anhydride acid chloride,
are very important coupling agents. The phosphoric acid derivative, MDP is
synthesized from methacrylic acid, 1,10-decanediol, and phosphorus oxychloride.
These very useful, functional (polymerizable) monomers are added to the primer
or liquid part of the adhesive.
The MMA-based adhesive system, 4-META/MMA–TBB resin formulation,
has three components: initiator, monomer liquid, and powder. The initiator is par-
tially oxidized TBB (TBB-O). The monomer liquid contains 5% 4-META in MMA.
The powder is finely pulverized PMMA, with a number-average molecular weight
of about 100,000. The original MMA–TBB resin without 4-META is a transparent,
unfilled resin. Bonding to enamel and base metal alloys is improved by addition of
4-META monomers to the liquid part. A primer containing 0.5% 6-(4-vinylbenzyl-
n-propyl)amino-1,3,5-triazine-2,4-dithol (VBATDT) in acetone is used to bond no-
ble metal alloys. Mercaptan (SH) groups on the VBATDT monomer bond to noble
metals and copper on the alloy surface. The ceramic surface is treated with a
Vol. 2 DENTAL APPLICATIONS 197

two-part liquid primer before applying 4-META resin. One liquid contains 4% γ -
methacryloxypropyl trimethoxysilane (γ -MPTS), while the other liquid contains
5% 4-META (or 4-MET) in MMA or 0.5% ferric chloride in ethanol. The γ -MPTS
is activated by mixing with 4-META (or 4-MET) or ferric chloride to silanate the
dental ceramic surface. The use of MMA polymer (PMMA)-coated titanium oxide
(217) makes 4-META/MMA–TBB-O resin optically opaque.
Shear bond or tensile tests determine the dental adhesive bond strength,
with thermocycling in water effectively evaluating the bond durability. The
monomer VBATDT is effective for bonding Ag–Pd alloy, while 4-META is suit-
able for Ni–Cr alloy and titanium. For Ni–Cr alloys, the chromium content influ-
ences bond durability. Ferric chloride combined with a silane coupler significantly
improves the bond strength of 4-META/MMA–TBB-O resin joined to dental porce-
lain.
Ceramic restoratives are often bonded directly to the tooth surface with ad-
hesive resins, reducing the amount of healthy tooth reduction needed in clinical
treatment. Resin-bonded fixed partial denture or resin-bonded ceramic restoration
methods are often employed. Adhesive resins are also used for bonding orthodontic
brackets, amalgam restoratives, and many other metal and ceramic materials.

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GENERAL REFERENCES

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Applications, Cambridge University, Cambridge, 1993.

BILL M. CULBERTSON
RONALD E. KERBY
The Ohio State University