COMPOSITE RESINS AND

BONDING AGENTS

A BRIEF HISTORY OF TOOTH COLORED RESTORATIVE MATERIALS

Silicates

The earliest tooth colored restorative materials were the silicate cements. These were used extensively
in the early 20th

century. Though they had a fluoride release mechanism but eroded quickly and had a problem of
marginal discoloration.

Acrylic resin restorations

Silicates were subsequently replaced by the tooth colored acrylic resins. These were basically
polymethyl methacrylate

(PMMA) resins similar to those used in dentures. They were widely welcomed at the time because of
their superior

esthetics, ease of manipulation, low cost and insolubility in oral fluids.

Bowen’s resin

The material was supplied as a powder and liquid (in brown bottles). With time however, many
restorations began to fail,

due to microleakage, staining and caries. This happened primarily because these materials shrink on
setting causing

them to pull away from the cavity walls. Their high thermal expansion and contraction caused further
stresses at the

margins. In addition, they had poor wear resistance. The monomer within was also implicated in pulpal
irritation especially

in deep restorations. Manufacturers tried to offset these problems by adding quartz filler particles. This
greatly reduced

the shrinkage by reducing the proportion of resin in the mix. It also reduced the thermal expansion.
However, the quartz

did not bond to the resin which resulted in staining and poor wear resistance.

The real breakthrough came with the discovery by Ray L Bowen in 1962 of a new type of resin called
bisphenol A glycidyl
methacrylate (popularly called bis-GMA or Bowen’s resin). In addition to this he also developed a
process by which the

resin was bonded to the filler particles within the composite (silane coupling). The acrylic resin
restorative materials soon

became obsolete and were replaced by the composite resins. Today composite resins are widely used
for both posterior

and anterior restorations.

COMPOSITE RESINS

Essentially, it is a resin which has been strengthened by adding silica particles

called fillers. The pioneering research of Bowen together with the development

of the acid etching technique and bonding agents, revolutionized restorative

dentistry. It largely replaced the earlier silicate and restorative acrylics.

The composite is a system composed of a mixture of two or more macromolecules

which are essentially insoluble in each other and differ in form. The composite

material’s properties are superior to those of its individual components, e.g.,

fiberglass has a resin matrix which is reinforced by glass fibers. The resulting

composite is harder and stiffer than the resin matrix material, but less brittle

than glass. Examples of natural composite materials are tooth enamel and

dentin. Matrix is made of collagen, with hydroxyapatite crystals acting as fillers.

Though the early composites were developed for restorative purposes their uses

subsequently expanded to include provisional, restorations, luting, etc.

Basic DENTAL MATERIALS

Figure 10.1: The Illustrations show a fractured central incisor (above left) restored quite realistically
with composite resin.

USES

1. Restoration of anterior (Fig. 10.1) and posterior teeth (directly or indirectly).

2. To veneer metal crowns and fixed partial dentures (prosthodontic resins).

4. Bonding of orthodontic brackets, etched cast restorations, ceramic crowns,

posts, inlays, onlays and laminates.

5. Pit and fissure sealant.

6. Esthetic laminates.

7. Repair of chipped porcelain restorations.

(Different composites are available for the above purposes. Each of them have their properties adjusted
to suit the

specific application for which it was intended. They are usually not interchangeable).

TYPES

122

Composites are classified by initiation techniques (curing mechanism), filler

size and viscosity.

Based on Curing Mechanism

ISO 4049/ ANSI/ADA Sp. No. 27

Type 1: Polymer based materials suitable for restorations involving occlusal

surfaces

Type 2: Other polymer based materials

Class 1 — Self cured materials

Class 2 — Light cured materials

Group 1 — Energy applied intraorally

Group 2 — Energy applied extraorally

Class 3 — Dual cured materials

Willems developed an extensive classification based on a number of parameters

such as Young’s modulus, the percentage (by volume) of inorganic filler, the

size of the main particles, surface roughness and compressive stress. Though

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Composite Resins and Bonding Agents

the classification is not presented, terminology from Willems classification is

still used today to describe some commercially available composites. With the

inclusion of nano sized particles the particle sizes can be described as

Particle size > 3 μm

μm

Nano range (5-100 nm or 0.005-0.01 μm)

Based on Filler Particle Size

Fillers play an important role in the composite performance. However, a

universal system of classifying fillers has not been agreed upon. Differences

exist on the nomenclature and the size range of the filler particles.

-100 μm)

-10 μm)

-1 μm)

-0.1 μm)

a. homogenous — contains only microfillers

b. heterogenous — microfillers combined with prepolymerized fillers

— spherical prepolymerized particles

c. agglomerated — microfiller sintered to form larger filler complexes

-0.01 μm)

rid

(range of sizes which usually includes micro or nano fillers

with macro, midi or mini fillers

Based on Viscosity

Viscosity determines the flow characteristics during placement. A flowable

composite flows like liquid or a loose gel. A packable composite is firm and

offers some resistance to condensation.

Based on Applications and Commercial Availability

—direct intraoral restorations

—Hybrids (Fig. 10.2)

—Microfilled (Fig. 10.3)

—Flowable (Fig. 10.4)

—Packable

—Nanocomposites (Fig. 10.6)

-up composites (Fig. 10.27)

RESTORATIVE COMPOSITE RESINS

early 1960s by Bowen (also known as Bowen’s resin). The early composite resins

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Basic DENTAL MATERIALS

Figure 10.2: Representative microhybrid composite.

Figure 10.3: A microfilled composite.

were generally macrofilled resins and were referred to as conventional composites.

These were chemically activated. This was followed by U-V light activated and

later visible light activated systems. The early composites had poor wear resistance

and stained easily. This was attributed to the large sized (macrofillers) filler

particles used. The introduction of the microfilled composites improved wear

resistance and better esthetics. However, they had poor mechanical properties.

The hybrid composites attempted to combine the esthetics and wear resistance of

the microfilled with the mechanical properties of the macrofilled composites. The

latest entry into the field—the nanocomposites (Fig. 10.6) holds the promise of

high polishability with further improvement in mechanical properties.

SUPPLIED AS

Composites used for restoring teeth are usually supplied as a kit (Fig. 10.2)

containing the following:

site resin—either chemical or light cured

Chemically Activated Composite Resins are Available as

Two paste (base and catalyst) system Supplied in small jars or syringes (Fig. 10.5).
Figure 10.4: Flowable composites are often identified by

the suffix ‘flow’.

124

Figure 10.5: Chemically cured composite.

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Composite Resins and Bonding Agents

10 10 10 10 10

Powder-liquid systems Powder (inorganic phase plus the initiator) is supplied

in jars. Liquid (BIG-GMA diluted with monomers) in bottles.

Light Activated Resins are Available as

Single paste form in dark or light proof syringes (Fig. 10.4).

Trade names: Various commercial products available are presented in Table

10.2.

INDICATIONS FOR VARIOUS COMPOSITE RESINS

The indications for different products are presented in Table 10.1.

Table 10.1

Various

restorative

composites

currently

marketed and

their uses

Type Indications

Hybrid or universal Anterior and posterior restorations in high stress areas

(microhybrids) requiring improved polishing (e.g., Classes I, II, III, IV)

improved contact with adjacent teeth.

Flowable Hybrids– Class V lesions subjected to flexing stresses.– Mini cavities– Repair of composite– In
layered composite restorations as first layer (for

better adaptation)

Microfilled (homogenous– Low stress areas

and hetrogenous)– Areas requiring high polish (to reduce plaque accumu

lation, e.g., subgingival areas, Class V lesions, etc.)

Hybrid or universal Anterior and posterior restorations in high stress areas

(Nanohybrids) requiring greater polishability, e.g., Classes I-IV and

including Class V cervical lesions.

Table 10.2

Representative

commercial

products

Chemically Activated—Isopast, Alfa comp (voco), Brilliant (coltene), Medicept

Light Activated

Hybrid (Universal) Filtek Z250 (3M), Herculite (Kerr), TPH spectrum, Venus and

Charisma (Heraeus), Tetric Ceram (Ivoclar), Point-4 (Kerr)

etc.

Microfilled Helio Progress, Durafil VS (Heraeus), A110 (3M-ESPE),

Sculpt-it (Jeneric/Pentron), Amelogen Microfill (Ultra-dent),

Renamel Microfill (Cosmedent).

Flowable C- Fill Flow, Synergy D6 Flow (Coltene), Tetric flow, Venus

Flow (Heraeus), Flow Plus (Medicept), etc.

Packable Surefil (Dentsply), Heliomolar HB (Ivoclar), Solitaire 2

Nanocomposite Grandio (Voco), Filtek Supreme (3 M), Venus Diamond

(Heraeus),Composite-nanohybrid (Medicept)

COMPOSITION AND STRUCTURE

The Essentials Components of a Composite Resin (Fig. 10.7)

Resin matrix/ binder — BisGMA or urethane dimethacrylate

Filler — Quartz, colloidal silica or heavy metal glasses

Coupling agent — Organo silanes

Basic DENTAL MATERIALS

Figure 10.6: Universal nano-hybrid

composite.

In Addition They Contain

A curing system

Inhibitors (0.01%)

UV absorbers

Opacifiers (0.001 to 0.007%)

Color pigments

RESIN MATRIX

— Chemical or light curing chemicals

— Prevents premature polymerization,

e.g., butylated hydroxytoluene (BHT)

— to improve color stability

— e.g., titanium dioxide and aluminum oxide

— to match tooth color

Dental composites use a blend of monomers that are aromatic or aliphatic

dimethacrylate (UDMA) and Bis-EMA (Bisphenol-A-polyethylene glycol diether

dimethacrylate) are most commonly used. Triethylene glycol dimethacrylate

(TEGDMA) is added to control the viscosity.

Bis-GMA was developed by RL Bowen (Bowens resin) in the early 1960s. Its

properties were superior to those of acrylic resins. However, it had a few

limitations like:

inkage and thermal dimensional changes still existed.

Figure 10.7: Essentials of a

composite.

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Composite Resins and Bonding Agents

To make it clinically acceptable, diluent monomers are added to the resin matrix

to reduce the viscosity of the resin. It also allows more fillers to be incorporated.

Diluents allow extensive cross-linking between chains, thereby increasing the

resistance of the matrix to solvents. The commonly used diluent monomer is

TEGDMA (triethylene glycol dimethacrylate). Thus composite resins have to be

blended with different monomers to optimize their properties.

Drawbacks of TEGDMA include

-life by migration in to the plastic walls.

thickening or softening of the paste in certain climatic conditions.

(Because of these drawbacks some manufacturers have replaced the majority of

the TEGDMA with a blend of UDMA and Bis-EMA).

The refractive index is an important property for anterior restorative materials.

To have acceptable esthetics composite resins must match the translucency of

enamel. Bis-GMA and TEGDMA have a refractive index of 1.55 and 1.46

respectively which average to around 1.5 when combined together.

FILLER PARTICLES

Fillers play a crucial role in the composite resin. Most of the important properties

of the resin is determined by its filler content. Composite fillers are classified

by material, shape and size. Many different classifications of fillers have been

proposed. They are broadly classified into 3 groups - macrofillers, microfillers

and nanofillers. A mixture of different particle sizes is referred to as a hybrid.

For details of filler size and nomenclature see ‘classification of composite resins.’

Advantages of Fillers

Addition of filler particles in to the resin significantly improves its properties:

1. As less resin is present, the curing shrinkage is reduced thereby reducing

marginal leakage.

2. Fillers play a crucial role in the wearing of composite resins. The smaller

the size and higher the concentration of fillers the better the wear resistance.

3. Fillers play a crucial role in the surface smoothness and subsequent esthetics

of the composite.
4. Reduces water sorption.

5. Improves mechanical properties like strength, stiffness, hardness, etc.

6. Reduces thermal expansion and contraction.

7. Improves clinical handling (increased viscosity makes them easier to handle

clinically).

8. Radiopaque fillers help improve diagnostics (caries detection through

roentgenograms, etc.).

Important attributes of fillers, that determine the properties and clinical

application of composites are:

— Amount of filler added (filler loading)

— Size of particles and its distribution

— Shape of fillers

127

Basic DENTAL MATERIALS

— Index of refraction

— Radiopacity

— Hardness

Filler size The size of the fillers affect the surface smoothness and the wear

resistance. The smaller the fillers the greater the surface smoothness. Microfilled

composites have the best surface smoothness and lowest wear. This is because

the particles are removed at the same rate as the resin matrix if they are smaller.

Larger particles result in a rougher surface. The introduction of the nano

particles hold great promise of improved smoothness, good wear resistance as

well as improved mechanical properties.

Filler loading Filler loading refers to the amount of fillers that can be practically
incorporated into the resin. The amount of filler that can be added depends on

the type of filler and the purpose for which it is intended. Most hybrid composites

have a filler loading ranging from 60 to 70% volume. The introduction of the

newer nanofillers allow a greater filler loading of up to 79.5% vol. Microfillers

thicken the resin quickly. Thus microfilled resins usually do not have the same

filler loading as resins with larger particle sizes such as the hybrids.

Particle size distribution Most modern hybrid composites have particles range

in size from 0.01 to 10 μm. Microfillers are usually in the range of 0.01 - 0.07

(average 0.04 μm). In order to increase the filler amount in the resin, it is

necessary to add the fillers in a range of particle sizes. If a single particle size is

used, a space will exist between the particles. Smaller particles can then fill-up

these spaces, thus increasing the filler content (Fig. 10.8).

Shape of fillers Based on shape 3 types of fillers are used—irregular, spherical

and fibrous. The shape affects the filler loading and the handling characteristics

of the composite.

Refractive index For esthetics, the filler should have a translucency similar to

tooth structure. To achieve this, the refractive index of the filler should closely

match that of the resin. Most glass and quartz fillers have a refractive index of

1.5, which match that of Bis-GMA and TEGDMA.

Measurement of Filler Content—Volume versus Weight Percentage

Filler content is designated in percent volume (vol.%) or percent weight (wt.%).

Weight percent is usually higher in value than percent volume. The volume

Figure 10.8: Effect on particle size on surface smoothness: A - Traditional composite; B - Hybrid
composite; C - Microfilled

heterogenous type (showing prepolymerized fillers); D - Microfilled homogenous type; E -

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Composite Resins and Bonding Agents

percentage may be a more reliable indicator of filler content than the weight

percentage. This is because of differences in density between different fillers.

For example, composites can have a similar volume percentage of fillers yet

different weight percentages. This is because the composite containing a larger

fraction of heavy metal glass fillers will have a higher weight percentage.

Fillers Types

Composite resins use many types of fillers:

Quartz fillers They are obtained by grinding or milling quartz. They are

mainly used in conventional composites. They are chemically inert and very

hard. This makes the restoration more difficult to polish and can cause abrasion

of the opposing teeth and restorations.

Glasses/ceramics containing heavy metals These fillers provide radiopacity

to the resin restoration. Increased radiopacity make composites detectable on

radiographs which aid diagnostics. Examples are barium, zirconium and

strontium glasses. The most commonly used is barium glass. It is not as inert
as quartz. Some barium may leach out with time.

Fluoride releasing fillers Some current composites have fluoride releasing

capability. This includes fillers like Ytterbium trifluoride and Ba-Al-fluorosilicate

glass. In one commercial product (Tetric ceram) the YbF3 content is as high as

17 wt.%. The Ba-Al-fluorosilicate glass content was 5 wt.%.

Colloidal silica Referred to as ‘microfillers’. They are obtained by a pyrolytic

or a precipitation process. Colloidal silica particles (Fig. 10.9) have a large surface

area (50 to 400 m2/g), thus, even small amounts of microfillers thicken the resin.

They are added in small amounts in hybrid composites (5 wt %) to adjust the paste

viscosity. The hybrid varieties have a microfiller loading of 10 to 15% weight. In

microfilled composites it is the main filler used (20 to 59% volume). Since they

cannot be added in large amounts the overall filler loading of microfilled composites

is lower than conventional or hybrid varieties.

Figure 10.9: Electron microscopic picture

of colloidal silica 0.06 μm.

129

Basic DENTAL MATERIALS

Methods to increase microfiller loading

Manufacturers are constantly on the look out for methods to increase the filler

content of the microfilled composites.

1. One method is to sinter (fuse) the colloidal silica particles, thereby reducing

surface area. These are known as agglomerated silica.

2. Addition of prepolymerized fillers: This is the more common method. Also

known as ‘organic fillers’. They are prepared by adding 60 to 70 wt.% of

silane coated colloidal silica to the monomer, which is held at a slightly

The composite is obtained by adding these prepolymerized fillers along with

more silane coated microfillers into unpolymerized resin matrix (Fig. 10.13).

Silica nanoparticles These are currently the smallest filler particles used in

dental composites. Adoption of nanoparticle technology have ushered in the

next generation of composite resins. Incorporation of silica nanoparticles into

the composite resins have improved many of the properties of composite resins,

particularly wear resistance and polishability. Nanoparticles in composites can

be used in 2 forms.

- a single nanoparticle (size ranges from 5-25 nm)

- a group of nanoparticles (forms larger sized particles)

Manufacture of Fillers

Filler particles can be generated: (1) by crushing, grinding, and sieving large

blocks of ceramic, (2) by condensation of SiO2 from the vapor phase as small

droplets of microfiller, or (3) by precipitation of filler particles from solution

(sol-gel). The smallest fillers can only be manufactured in a practical way from

the vapor phase or by sol-gel processes.

COUPLING AGENTS

Coupling agents bond the filler particles to the resin matrix. The earliest

composites did not use coupling agents. This resulted in microscopic defects

between the filler and surrounding resin. Microleakage of fluids into these defects

led to surface staining and failure. Typically the manufacturer treats the surface

of the filler with the coupling agent.

Function of Coupling Agents

1. They improve the properties of the resin through the transfer of stresses
from the more plastic resin matrix to transfer stresses to the stiffer filler

particles.

2. They prevent water from penetrating the filler-resin interface.

3. They bond the fillers to the resin matrix thereby reducing the wear.

The most commonly used coupling agents are organosilanes (i.e., 3-methacryl

oxypropyl-trimethoxysilane).

II

OCH3

CH2

=C—C—O—CH2

CH2

CH2

—Si—OCH3

II

CH3

OCH3

The agent is a molecule with a methacrylate groups on one end and methoxy

groups (OCH3) on the other end. In the presense of adsorbed water the methoxy

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Composite Resins and Bonding Agents

groups hydrolyze to form silanol groups (-Si-OH) which then form ionic bonds

with the silanol groups of the filler forming a siloxane bond (-Si-O-Si-). The
other end has a methacrylate group which forms a covalent bond with the resin

when it is polymerized. This completes the coupling process. Zirconates and

titanates can also be used as coupling agents.