Resin-based restorative

materials

Dr Piyaphong Panpisut
Faculty of Dentistry
Thammasat University
Outline

• Introduction
• Composition of resin
composites
• Classification of resin
composites
• Polymerisation of resin
composite
What is resin composite

• A material made up of at least two distinct

components, insoluble in each other which produce
better characteristics than the single component
• Three main component are
1) organic resin matrix (monomer, liquid phase)
2) inorganic filler particles (powder phase)
3) silane coupling agent that coat particle
Composition of resin
composite

Silane coupling agent

Glass fillers

Polymer matrix
Compositions
1. Monomer phase (Matrix phase)
- Monomers polymerised changing from paste/low viscous material to
a rigid and strong materials upon light curing
- Base monomer, diluent monomer (crosslinking monomers) à contain
polymerisable groups, mostly methacrylate group (ex. Bis-GMA,
TEGDMA)
- Functional monomerà contain functional group to promote actions
such as adhesion (HEMA, MDP-10)

MW = 512, Viscosity = 1,200 Pa.s MW = 286, Viscosity = 0.05 Pa.s

1.1 Base monomer

• Base monomer: highly viscous due to its high molecular

weight
• Provide strength and rigidity of the polymer matrix of resin
composite
• Example: Bis-GMA, UDMA
• Rapid hardening with low polymerisation shrinkage à high
strength
• Bis-GMA à Two aromatic rings --> limit flexibility of the
monomer
• Mix with other low MW monomer (diluent) --> reduce viscosity
• The core of Bis-GMA is identical to Bisphenol-A (BPA)

Bis-GMA UDMA
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1.2 Diluent monomer

• Low molecular weight monomer

• Reduce the viscosity
• Improve the handling properties, and increase monomer
conversion
• Using high level of diluent monomer may increase
volumetric shrinkage and heat generation
• Ex. TEGDMA (triethylene glycol dimethacrylate)

TEGDMA
9
1.3 Light initiators

CQ TPO

Ivocerin

- CQ (Camphorquinone) usually combine with tertiary amine activator (eg DMPT)

yield one active radicals
- TPO (2,4,6 trimethylbenzoyl phosphine oxide (TPO) yields two active free radicals

- Ivocerin : high absorbance and hightly effective initiator !!

Compositions
2. Filler phase

• Mineral or glass or transparent fillers

• Borosilicate, quartz, aluminum silicate,
lithium aluminum silicate, ytterbium
fluoride, and barium (Ba), strontium (Sr),
zirconium (Zr), and zinc glasses
• Refractive index of fillers should match
with polymer (~ 1.5)
 Compositions

Glass fillers

- Improve mechanical/physical
properties
- Optical properties
- Relieve polymerisation
shrinkage stress and heat
generation
- Control of handling properties
- Radiopacity
- Reduce water sorption
 Compositions

Fibres

- improve fracture
toughness via crack
bridging
- Limited use in direct
composite due to the
increase in roughness
and packing
 Compositions

“Pre-polymerise” filler (PPF)

- Made by grinding cured

composites that may
originally filled with nano
and/or micron-sized particle
- Increase filler loading
Compositions

3. Coupling agent (silane)

• Fillers are usually inert but can

chemically bond with glass via silane
coupling agent (γ-
methacryloxypropyltrimethoxy silane,
MPS) or called “silane treated”

• Silane is difunctional monomer

- One end can be hydrolysed and

attached to OH group of silica particles by
forming siloxane/oxane bond (Si-O-Si)

- The other end is methacrylate group

can polymerise with resin monomers
- Alkoxy groups on silicon hydrolysed to form silanols (Si-OH)
- The silanols coordinate with metal hydroxyl groups on the inorganic
surface to form oxane bond (Si-O-metal/glass) with an elimination of
water
Classification of composites

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Type of Average Filler size and Commercia Indications limitations
composite filler size distribution l examples

1. Microfill 40-50 nm Durafill VS, Small cavity Low filler

composite Renamel in aesthetic load, low
Microfill, areas mechanical
Heliomolar properties
etc.

2. Hybrid 10-50 um Herculite Moderate Loss of

composite + 40 nm XRV, load bearing surface
Spectrum areas gloss, wear
TPH,
Charisma
etc.
3. Midifil 1-10 um Z100, Moderate Loss of
+ 40 nm Clearfil load bearing surface
photo areas gloss,
posterior
Type of Average Filler size and Commercia Indications limitations
composite filler size distribution l examples

4. 0.6-1 um Filtek 250, Universal composites

Mycrohybrid + 40 nm Synergy D6,
or Minifil Gradia
direct, Tetric
Ceram,
Venus etc.
5. 0.6-1 um Premise, Universal composites
Nanohybrid + 5-100 Clearfil
composite nm majesty
(very similar esthetic,
to Z250XT,
myccrohybri CeramX
d)
6. Nanofill 5-100 nm Filtek Z350, Universal composites,
Estelite excellent aesthetics
Nanofill composite

Nanofill composite:
1) Nanomer : single particle (5 -
100 nm) à poor flowability
2) Nanocluster (cluster of grapes,
0.6 um): form cluster to control
particle size distribution
Classification: Physical (observation)

Classifications Viscosity Filler load Indication

1. Packable High viscosity > 60 vol% Univeral

composite composite

2. Flowable Low viscosity 40 – 50 vol% Small lesions,

composite low-load bearing
areas

3. Laboratory High viscosity ~ 50 vol% Indirect

composite restorations
Classification: Handling
characteristic
1) Packable resin composites
- Increased stiffness the composite paste
(mimic amalgam)
- Low polymerization shrinkage and heat
generation
- Good mechanical properties and
aesthetic
- Dentine/enamel replacement (high
strength) in most areas
Classification: Handling
characteristic
2) Flowable resin composites
- Low viscosity through a reduced
filler loading
- Flow readily, spread uniformly,
intimate adaptation to a cavity form
- Strength lower than conventional
composite
- high polymerization shrinkage
and heat generation !!!
- Indications: low load bearing areas,
liner in deep class II proximal cavity
Flowable composites are non-Newtonian, shear-thinning materials
which showed a decrease in viscosity as the shear rate increased
Classification: Handling
characteristic
3) Laboratory composites
- High filler load
- Cured by heat, vacuum, pressure, and
oxygen-free polymerisation techniques (in
laboratory) enable greater degree of
polymerisation
- High mechanical properties, lower
polymerization stress at tooth-dentine
interface, better control of occlusal
morphologies
- Eg., Gradia (GC), Sinfony (3M)
Bulk-fill composites

- Can be placed in bulk (>4 mm) in deep cavity

high viscosity, flowable composite (require
capping layer), and sonicated delivered (reduce
viscosity)

- Should limit to 4-5 mm per layer

- Shrinkage ~ 2 vol% (high viscosity), ~3 vol% (for

low viscosity)

- Comparably low mechanical properties and

aesthetics compared with conventional
composites
Bulk-fill composites

Improved depth of cure (DOC)

1) Reducing filler content, increasing filler

particle size

- Reduce light scattering, increase light

transmission

- Increase amount of absorbed light

2) The use of additional photoinitiator

- Ivocerin à highly reactive photoinitiator à

alow materials to polymerise in large
increment

3) Modification of monomer systems (AFT)

In the short term, the use of bulk-fill composites provide clinical results
that are comparable with conventional composite placement.

28
Low viscosity with the use of sonic vibration
(allowing the material to flow into the cavity).
32
Polymerisation of resin composites

Principle: Polymers are formed by a large number of monomers linked to

build up macromolecules
Polymer chain configurations: composites consisted of crosslinked polymer
Free-radical polymerisation

34
Polymerisation of resin
composites
Oxygen interference
- Diatomic molecules (O2.) à
diradicals that will react with free
radicals
- Net outcome is oxygen inhibition
layer à ~ 10 – 50 um
Akhundov, 2015
- Allow for polymerisation of
additional layer Non-polymerisation allow
for additional composite
Air placement
Polymerisation of resin
composites

Degree of monomer conversion

- monomer conversions (50 - 75 %)
- High level of monomer conversion
is required to improve
mechanical/physical properties
and may reduce the risk of toxic
unreacted monomer monomers
Light curing unit (LCU)

1. QTH (Quartz-Tungsten-
Halogen Light)
2. Plasma Arc curing unit
(PAC)
3. Light-emitting-diode
(LED)
(all LCU units emit blue light,
the spectral ranges the
radiant powers are not the
same)
Light curing unit (LCU)
Absorption of initiator
(320 – 510 nm)
1) CQ (468 – 470 nm;
blue region)
2) Lucirin TPO (375-410
nm)
3) Ivocerin (~400-430nm)
4) PPD (~400)

Lucirin TPO and Ivocerin are more reactive and have a higher
quantum efficiency
40
41
Light curing unit (LCU)

1. QTH (Quartz-Tungsten-Halogen
Light)
- Deliver a broad emission spectrum
- Low radiant power (Watt) and low
irradiance (mW/cm2)
- Require 30-60 s to adequately ligh-
cure a 2-mm-thick increment of resin
composites
- Short service life and main power and
cooling fan was noisy
Light curing unit (LCU)

2. Plasma Arc curing unit (PAC)

- Attempt to reduce light exposure time
- High irradiance and only required a
short 3–5-s exposure time to light cure
a 2-mm-thick increment of resin
composite
- Expensive, noisy fan, they are large,
and they cannot be battery operated à
not very popular
Light curing unit (LCU)

2. Argon-ion laser
- Developed about the same time as the PAC lights
- generates several very intense emission peaks in the blue spectral
region and is a viable light source for a high-power curing light
- Expensive, not portable, they have a narrow emission spectrum
Light curing unit (LCU)

3. Light-emitting-diode (LED) (2nd

Generation)
- Emission spectrum from LEDs
closely matched the absorption of
the CQ (468 nm) in most resin
composite
- 40 s for a 2 mm composite
thickness is recommended
- Lightweight, battery driven, long
working life
- Example: Elipar Freelight 2 (3M)
 Light curing unit (LCU)

3. Light-emitting-diode (LED)
- 3rd generation (violet and blue
light) provide emit light below 400
nm to enable photoactivation of
other initiators (eg TPO 375-410
nm, Ivocerin ~ 400 -430 nm)
• Irredance: 1000 - 3000 mW/cm2
- Example: Bluphase G2(ivoclar
vivadent ), Demi Ultra (Kerr)
How long should we cure composites?

• 40 s at a minimum irradiance of 250–400 mW/cm2 per

2 mm increment (10 to 16 J/cm2 radiant exposure)
was required for adequate polymerisation
• Please extend curing time beyond manufacturer
recommendation
• Using longer time the resin will be more fully cured

47
How long should we cure composites?

• Reaction rate is at best related to the square root of

the irradiance
• Ex. Reducing curing time from 20 to 5 s (4 times) will
require 16x of irradiance to achieve the same level of
polymerisation
• Using 3000-4000 mW/cm2 (some 3rd gen LED) for 5 s
will not give the same level of polymerisation as 500
mW/cm2 for 40 s à need 500x16 = 8000 mW/cm2)
• Doubling the radiant exposure received will not double
the depth of cure
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Different locations
in the restoration
can receive very
different amounts
of light
Beam profiles:
- Irridance distribution and their own maximum irradiance value
- Inhomogeneous irradiance distribution across the light tip
the irradiance and radiant
exposure received at the
gingival margins of the
proximal boxes from some
curing lights may be inadequate
53
 The blue light hazard

• The greatest blue light hazard is at 440

nm
• Blue light is transmitted through the
ocular media and absorbed by the retina
• High levels of blue light can cause
immediate and irreversible retinal
burning
• Low level and chronic exposure can lead
to accelerated retinal ageing and age-
related macular degeneration (ARMD)
• Use eye protection !!!!

54
Tips for light curing

• Always extend curing time !!

• The more you light cure, the
best mechanical and optical
properties you will be obtain
• Visually check curing position
with proper eye protection

55
Federlin et. al, 2002 56
Polymerisation shrinkage
- A polymer occupies less volume than the monomers, the effect of which is
well known as polymerisation shrinkage

- Stress developed due to the restriction of material’s flow

- C=C converted to C-C (distance between monomer reduced from 4 to 1.5

Angstrom)
Polymerisation shrinkage

- The shrinkage of commercial

dental composites was reported to
be 1–6 vol%

- generate contraction stress

impairing bonded surface which
may lead to gap formation
postoperative sensitivity, and
bacterial microleakage
Polymerisation shrinkage

Before filling After light cured

Ferracane and Hilton, 2015 SOARES et. al , 2017

Polymerisation shrinkage

Pre-gel phase Post-gel phase

Gel point

Viscosity increase

Monomer Shrinkage
increase stress
conversion

Distance
between Decrease
monomers
Polymerisation reaction
Factor affecting polymerisation shrinkage
1) Material factors à monomer conversion, type of monomer

Low MW monomer High MW monomer

high crosslinking density Low crosslinking density
 Polymerisation shrinkage
2) Tooth factor; configuration factor (C-factor)

S2 ΔL
Post-cure

L2

Precure S1

L1

Composites do not contract toward light source but it is contracted to the most
adapted wall
C-factor = Bonded/Unbonded surfaces

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 Polymerisation shrinkage
2) Tooth factor; configuration factor (C-factor)

ΔL Shrinkage is not
Post-cure S2
unidirectional,
L2
and stress
Precure S1 distortions are
complicated
L1
Proposed methods to reduce
polymerisation shrinkage
1. Placement technique

- Incremental layering technique à used to believe that shrinkage may be

reduced with less cavity walls

- The beneficial effect on shrinkage stress is not yet concluded

- Recommended to ensure sufficient polymerisation in deep cavity

Anusavice et. al,, 2013

 Proposed method to
reduce polymerisation
shrinkage
2. Light curing protocols
- Soft start polymerisation; prolong pre-gel
phase to allow stress relief
- Examples: ramp cure, staged cure, pulse
delay curing techniques
- For high crosslinking polymer, stress mostly
develop during or after vitrification stage
(post-gel phase)
- The technique not provide significant
clinical benefit compared with traditionally
curing method polymerisation and could lead
to poor monomer conversion
Price, 2017
Aljosa et. al, 2014
Proposed methods to reduce
polymerisation shrinkage
3. Stress absorbing layer

- Use of flowable composites as “stress-

absorbing layer” à create elastic cavity wall

- Shrinkage from high modulus materials

(packable composite) can be absorbed by
lower modulus materials (flowable
composite)

- Studies did not support clinical benefit of

such method
 Proposed methods to reduce
polymerisation shrinkage
4. Pre-warming composites

- Warm and low viscosity promote free

radical mobility enhancing
polymerisation

- help composite to reach maximum

polymerisation before the vitrification
point

- No clinical evidence to support this

technique and it might increase
technique sensitivity
Proposed method to reduce polymerisation
shrinkage

Low shrinkage composite

- Silorane monomers

- Polymerisation by oxirane ring

opening polymerisation

- Volumetric shrinkage (<1%) but

failed to provide clinical benefits
compared with conventional
materials

- Not very popular

 Proposed method to reduce polymerisation
shrinkage

Addition-Fragmentation Transfer
(AFT) monomer system

- AFM monomer and break their

covalent bond upon light
polymerisation à reduction of
shrinkage stress

- AFM allow bond exchange and re-

arrangement of net work

Bowman, et. al, 2017

Toxicity of resin composites

- What is eluted à monomers, additive,

reactive products, fillers
- Bis-GMA, UDMA, TEGDMA,
HEMAà most investigated and
detected monomers
à Cause mild to severe inflammatory
pulp reactions
à released monomers may shift
bacterial communities toward
more cariogenicity
Toxicity of resin composites
Bisphenol A (BPA)
- Considered weakly
estrogenic -> Mimic action of
oestrogen
- Some animal studies showed
potential effect on obesity,
fetal and infant brain
development, Dopaminergic
system, Reproductive systems
and sexual behaviour
- No direct evidence on human
Toxicity of resin composites
Toxicity of resin composites
Bisphenol A (BPA)
- BPA derivetives à Bis-GMA, Bis-EMA, Bis-
DMA
- Derivatives with ester linkage (-O-CO-) such
as Bis-DMA can be hydrolysed to BPA
- Bis-GMA and Bis-EMA (-O- linkage) cannot
covert to BPA by hydrolysis
- Primary sources: diet, air, dust, water/drink
- Estimated daily intake (USA) à 0.5 ug/kg-
body weight/day
- Maximum safe dose à 50 ug/kg-body
weight/day
- National Toxicology Program (NTP) à
negligible concern for reproductive effects
and pregnancy for dental composites
Toxicity of resin composites
- The amount of BPA released from BPA-derivatives is verly low and usually
not detectable (< 2 ppm)
- Typical unpolymerised composite (eg 2 gram) may contain ~ 500 ng of BPA
à if all leach out in one year à still much lower than the 0.1% of daily intake
and far below 100,000 – 1,000,000 times of maximum safe dose
- Animal study confirmed BPA did not cumulate in pregnancy mice and all was
discharged within 5 days
- No adverse effect has been reported

“The ADA fully supports continued research into the safety of BPA; but, based
on current evidence, the ADA does not believe there is a basis for health
concerns relative to BPA exposure from any dental material.” ADA (2013)
Composite (nano) dust
- Human bronchial cells
exposed to respirable fraction
of composite dust
- Composite dust was taken up
by a bronchial epithelial cell
(endocytosis)
- All tested composites
provoked a mild genotoxic
effect

Cokic et. al, 2020

79
Future Development

Low shrinkage composites Mereis et. al, 2018

Future Development

Remineralising antibacterial composites

Balhaddad et. al, 2015
Future Development
Self healing composites

Wu et. al, 2019

Syrett et. al, 2018