AB STRACT

1382 JADA, Vol. 134, October 2003

A D VA NC E S I N DE NTAL P R ODUCT S
Background. This article reports the
authors development of nanofillers and a
resulting nanocomposite. They measured
the nanocomposites properties in vitro in
comparison with those of several existing
composites (hybrids, microhybrids and
microfill).
Methods. The authors developed two
types of nanofillers: nanomeric particles
and nanoclusters. They used optimal combi-
nations of these nanofillers in a proprietary
resin matrix to prepare the nanocomposite
system with a wide range of shades and
opacities. The properties they studied were
compressive, diametral tensile and flexural
strengths; in vitro three-body wear; fracture
resistance; polish retention; and surface
morphology after toothbrush abrasion.
They performed statistical analysis using
analysis of variance/Tukey-Kramer paired
analysis at a 95 percent confidence interval.
Results. The compressive and diametral
strengths and the fracture resistance of the
nanocomposite were equivalent to or higher
than those of the other commercial compos-
ites tested. The three-body wear results of
the nanocomposite system were statistically
better than those of all other composites
tested. The nanocomposite showed better
polish retention than the hybrids and
microhybrids tested at the extended
brushing periods. After extended tooth-
brush abrasion, the dentin, body and
enamel shades showed polish retention
equivalent to that of the microfill tested,
while translucent shades showed better
polish retention than the microfill.
Conclusions. The dental nanocomposite
system studied showed high translucency,
high polish and polish retention similar
to those of microfills while maintaining
physical properties and wear resistance
equivalent to those of several hybrid
composites.
Clinical Implications. The strength
and esthetic properties of the resin-based
nanocomposite tested should allow the clini-
cian to use it for both anterior and posterior
restorations.
An application of
nanotechnology in
advanced dental
materials
SUMITA B. MITRA, Ph.D., M.Sc.; DONG WU, Ph.D.;
BRIAN N. HOLMES, Ph.D.
N
anotechnology, also known as molecular
nanotechnology or molecular engineering, is
the production of functional materials and
structures in the range of 0.1 to 100
nanometersthe nanoscaleby various
physical or chemical methods.
1
Today, the revolutionary
development of nanotechnology has become the most
highly energized discipline in science
and technology.
2
The intense interest in using nanoma-
terials stems from the idea that they
may be used to manipulate the structure
of materials to provide dramatic
improvements in electrical, chemical,
mechanical and optical properties.
3
At a
billionth of a meter, a nanometer is the
essence of small. For perspective, the
size of one hydrogen atom is 0.1 to 0.2
nm and of a small bacterium about 1,000
nm or 1 micrometer. A large amount of
research is being devoted to the develop-
ment of nanocomposites of different
types for various applications, including
structural materials, high performance coatings, cata-
lysts, electronics, photonics and biomedical systems.
4
Every property has a critical length scale, and by using
building blocks smaller than the critical length scale
such as nanoparticlesone can capitalize on the manifes-
tations of physics at small sizes. An example of this is in
light scattering. When a particle shrinks to a fraction of
the wavelength of visible light (0.4-0.8 m), then it would
not scatter that particular light, resulting in the human
eyes inability to detect the particles. This has tremendous
The strength
and esthetic
properties of
the resin-based
nanocomposite
tested should
allow the
clinician to use
it for both
anterior and
posterior
restorations.
Copyright 2003 American Dental Association. All rights reserved.
implications for the optical properties of materials,
as this article will demonstrate.
One of the most significant contributions to
dentistry has been the development of resin-based
composite technology. Adhesively bonded compos-
ites have the advantage of conserving sound tooth
structure with the potential for tooth reinforce-
ment, while at the same time providing a cosmeti-
cally acceptable restoration.
5
However, no one
composite material has been able to meet both the
functional needs of a posterior Class I or II
restoration and the superior esthetics required for
anterior restorations.
6
Our objective was to
develop a composite dental filling material that
could be used in all areas of the mouth with high
initial polish and superior polish
retention (typical of microfills), as
well as excellent mechanical proper-
ties suitable for high stressbearing
restorations (typical of hybrid com-
posites).
7
To this end, we developed
novel nanofillers and then nanocom-
posites using advanced methacry-
late resins and curing technologies.
Nanofillers are very different from
traditional fillers and require a shift
from a top-down to a bottom-up man-
ufacturing approach. To make filler
particles of the mechanically strong
composites of today (such as macrofills, hybrids and
microhybrids) one starts from dense, large particles
(mined quartz, melt glasses, ceramics) and commin-
utes them to small particle size. However, these
milling procedures usually cannot reduce the filler
particle size below 100 nm (1 nm =
1
/1,000 m). To cir-
cumvent this roadblock, our team used synthetic
chemical processes to produce building blocks on a
molecular scale. We then assembled these materials
into progressively larger structures and transformed
them into nanosized fillers suitable for a dental com-
posite. This article describes our research toward
the development of a new dental nanocomposite,
Filtek Supreme Universal Restorative (3M ESPE
Dental Products, St. Paul, Minn.), that has the
esthetic properties required for cosmetic restora-
tions and the mechanical properties necessary for
posterior restorations. In our research, we compared
the properties of these materials with those of sev-
eral commercial composites.
MATERIALS
Nanofiller particles. We synthesized two new
types of nanofiller particles for this investigation:
JADA, Vol. 134, October 2003 1383
A D V A NC E S I N DE NT AL P R ODUCT S
nanomeric, or NM, particles and nanoclusters, or
NCs. The NM particles are monodisperse nonag-
gregated and nonagglomerated silica nanoparti-
cles. In this investigation, we used aqueous col-
loidal silica sols to synthesize dry powders of
nanosized silica particles 20 and 75 nm in diam-
eter. We treated the silica particles with
3-methacryloxypropyltrimethoxysilane, or MPTS,
using a proprietary method. MPTS, a bifunctional
material also known as a coupling agent, contains
a silica ester function on one end for bonding to
the inorganic surface and a methacrylate group
on the other end to make the filler compatible
with the resin before curing to prevent any
agglomeration or aggregation. MPTS also allows
chemical bonding of the NM filler to
the resin matrix during curing.
We synthesized two types of NC
fillers using proprietary processes.
The first type consists of zirconia-
silica particles synthesized from a
colloidal solution of silica and a zir-
conyl salt. The primary particle size
of this NC filler ranges from 2 to 20
nm, while the spheroidal agglomer-
ated particles have a broad size dis-
tribution, with an average particle
size of 0.6 m. The second type of
NC filler, which we synthesized
from 75-nm primary particles of silica, has a
broad secondary particle size distribution with a
0.6-m average. We treated the surfaces of both
types of nanocluster filler particles with an MPTS
coupling agent to provide compatibility and chem-
ical bonding with the organic resin.
Resin system. The resin system used in the
nanocomposites in this investigation is the same
proprietary mixture used in Filtek Z250 Uni-
versal Restorative composite (3M ESPE Dental
Products): bisphenol A glycidyl dimethacrylate,
ethoxylated bisphenol A dimethacrylate,
triethylene glycol dimethacrylate,
1,6-bis(2-methacryloyl-oxyethoxycarbonylamino)
-2,4,4-trimethylhexane, photoinitiators and
stabilizers.
Nanocomposite preparation. Using statisti-
cally designed experimentation methodology, we
studied many combinations of NC and NM fillers
to determine an optimal formulation for the
Filtek Supreme Universal Restorative dental
nanocomposite system. The formulations for the
dentin, body and enamel shades of Filtek
Supreme Standard, or FSS, pastes contain
Nanofillers are very
different from
traditional fillers and
require a shift from
a top-down to a
bottom-up
manufacturing
approach.
Copyright 2003 American Dental Association. All rights reserved.
another wheel acting as an
antagonistic cusp (the
second body). The two
wheels counter-rotated
against each other, drag-
ging an abrasive slurry
(the third body) between
them. We determined
dimensional loss during
156,000 cycles by profilom-
etry at regular intervals
(that is, after every 39,000
cycles). As the wear in this
method typically followed a
linear pattern, we plotted
the data using linear
regression and determined
the wear rates from the
slope.
12
We tested three
samples of each material.
Fracture toughness. We determined the frac-
ture resistance of materials using a short rod
fracture toughness method.
12
We cut a chevron-
shaped notch into the end of a cured rod of mate-
rial (8 millimeters in length 4 mm in diameter)
that had been stored in water at 37 C for seven
days, and we propagated a crack through the
chevron by pulling the two halves of the specimen
apart at a controlled rate. The values reported for
fracture resistance are related to the energy
required to propagate a crack.
12,13
We tested five
samples of each material studied.
Flexural strength. Flexural strength was
measured (n = 3) using the three-point bending
test method of the International Organization for
Standardization.
14
Polish retention. Samples of composite paste
were cured in a rectangular 20 9 3mm mold
between two pieces of polyester film. We cured
each specimen with a curing unit (Visilux 2, 3M
ESPE Dental Products) for 80 seconds followed by
curing for 90 seconds in a light box (UniXS, Her-
aeus Kulzer, Armonk, N.Y.). Specimens were
mounted with double-sided adhesive tape (Scotch
Brand Tape, Core series 2-1300, 3M, St. Paul,
Minn.) to a sample holder (Ecomet 4 Grinder/Pol-
isher, Buehler, Lake Bluff, Ill.). The mounted
samples were polished using a polisher (Buehler
Ecomet 4 Grinder/Polisher) with a special pol-
ishing head (Automet 2 Polishing Head, Buehler).
The following sequence of abrasives was used for
each sample: 320-grit and 600-grit silicon carbide
abrasive, 9-mm diamond polishing paste, 3-mm
zirconia-silica NCs and silica NPs. The effective
primary particle size is 20 nm. The formulations
of Filtek Supreme Translucent, or FST, shades
contain a filler predominantly composed of indi-
vidual NM particles 75 nm in diameter and a
minor amount of silica NCs.
Commercial materials. We also tested sev-
eral commercial composites currently on the
market for comparative purposes. Table 1 lists
the name of the product, the type of product, the
name of the manufacturer and the lot number of
each of the composites we tested.
METHODS
Compressive strength and diametral tensile
strength. We prepared cured cylindrical rods of
composite materials and tested and measured
them for compressive strength according to the
method described in Mitra and Kedrowski,
8
with
the exception that there was no mixing necessary.
We tested and measured diametral tensile
strength according to a modification of ADA speci-
fication no. 27.
9
We stored the cured specimens
(N = 5) in distilled water at 37 C for 24 hours
before measurement using an Instron testing
instrument (Instron 4505, Instron, Canton,
Mass.).
Wear. We determined the wear rate by an in
vitro three-body wear test according to a modified
Academisch Centrum Trandheelkunde Am-
sterdam, or ACTA, method.
10,11
In this test, we
loaded composite (the first body) onto a wheel and
cured it, then brought the wheel into contact with
1384 JADA, Vol. 134, October 2003
A D V A NC E S I N DE NT AL P R ODUCT S
TABLE 1
COMMERCIAL COMPOSITES TESTED.
PRODUCT COMPOSITE TYPE MANUFACTURER LOT NO.
Microfill
Hybrid
Hybrid
Microhybrid
Microhybrid
Nanocomposite
Nanocomposite
1BC
1LC
001025
0110036
111432
EXM 612
EXM 612
3M ESPE Dental
Products, St. Paul,
Minn.
3M ESPE
Dentsply Caulk, York,
Pa.
Dentsply Caulk
Kerr, Orange, Calif.
3M ESPE
3M ESPE
Filtek A110
Filtek Z250
TPH Spectrum
EsthetX
Point4
Filtek Supreme
Standard
Filtek Supreme
Translucent
Copyright 2003 American Dental Association. All rights reserved.
JADA, Vol. 134, October 2003 1385
A D V A NC E S I N DE NT AL P R ODUCT S
diamond polishing paste and finally a polishing
suspension (Masterpolish Polishing Suspension,
Buehler). A microtri-gloss instrument (BYK-
Gardner, Columbia, Md.) was used to collect pho-
toelectric measurements of specularly reflected
light from the sample surface after polishing and
after tooth brushing. We conducted the procedure
according to American Society for Testing and
Materials standard for measuring specular
gloss
15
for measurements made at 60 degrees
geometry with the following analysis. Initial gloss
after polishing (G
I
) was measured for sample
immediately after preparation. Final gloss was
measured after 500 toothbrushing cycles (G
F
). The
G value was calculated with the following for-
mula: G = (G
F
) (G
I
). gloss retention (GR) = 100
G/G
I
. Each sample was brushed for a total of
500 cycles with a straight toothbrush (Oral B 40
medium, Oral B Laboratories, Belmont, Calif.)
using (Crest Regular Flavor, Procter & Gamble,
Cincinnati). We ran three replicates for each for-
mulation tested.
Surface morphology after toothbrush
abrasion. We mounted samples for scanning
electron microscopy, or SEM, analysis on an alu-
minum stub using double-sided tape with the
toothbrush-abraded surface facing upward. We
ground the samples on the edges with colloidal
graphite and gold-palladium sputter-coated for 30
seconds in a sputter coater (Desk II Cold Sputter-
coater/Etch Unit, Denton Vacuum, Moorestown,
N.J.). We performed SEM analysis using two
models of scanning electron microscopes (models
820 and 840, JEOL USA, Peabody, Mass.). We
performed SEM analysis on all dental composite
samples at magnifications of 100, 500, 2,500
and 10,000 and at a stage tilt of 45 degrees.
Transmission electron microscopy. We
prepared samples for transmission electron
microscopy, or TEM, analysis by microtomy on a
microtome (Leica UCT, Reichert Analytical
Instruments, Depew, N.Y.) at room temperature
conditions, using a diamond knife (at a 45-degree
angle) (UCT, Diatome U.S., Fort Washington,
Pa.). We did the sectioning at 0.2 mm/second to
provide a section thickness of 80 nm. Sections
were floated on water and collected on 200 mesh
copper grids with carbon stabilized embedding
material substrates. We performed TEM on a
JEOL 200CX (JEOL USA) at 200 kilovolts.
Statistical analysis. We performed an
analysis of variance, or ANOVA /Tukey-Kramer
paired analysis using a software program (JMP
4.0 Statistical Discovery Software, SAS Institute,
Cary, N.C.) at the 95 percent confidence interval,
or CI.
RESULTS
Figure 1 shows three transmission electron
micrographs:
done of a nanocomposite filled with 75-nm
diameter NM particles only;
done of an experimental nanocomposite filled
with NCs alone;
done of a commercial composite made with
large-particle-size dense hybrid filler (particle
size, approximately 1 m).
Table 2 lists the mechanical properties of FSS
and FST along with those of the materials with
which we compared them. Figure 2 shows a com-
parative summary of the results of diametral ten-
sile strength, compressive strength, flexural
strength and fracture resistance. Statistical
Figure 1. Schematics and transmission electron micro-
scopic images of composites studied. A. Composite with
nanometric particles ( 60,000 magnification). B. Com-
posite with nanocluster particles (300,000 magnifica-
tion). C. Composite with hybrid fillers (300,000 magnifi-
cation). nm: Nanometers. APS: Average particle size. m:
Micrometer.
Copyright 2003 American Dental Association. All rights reserved.
analysis by the ANOVA/ Tukey-Kramer paired
test showed that the compressive and diametral
tensile strengths of the FSS and FST were equiv-
alent to or higher than
those of the other com-
mercial composites
tested. The flexural
strength of FSS and
FST was higher than
that of three of the
other composites and
equivalent to that of
the other commercial
composites tested at
the 95 percent CI
(Table 2). Statistical
analysis showed that
the fracture resistance
of FSS and FST was
higher than that of one
of the composites tested
and equivalent to that
of the other commercial
composites tested at
the 95 percent CI.
Figure 3 shows the
three-body wear rates
of the nanocomposites
and the other commer-
cial composites examined in this
study. The wear rate of the FSS for-
mulation was statistically equivalent
to that of the Filtek Z250 and lower
than that of the other commercial
materials, as determined by ANOVA
at the 95 percent CI. The wear rate
of the Filtek Supreme translucent
formulation was statistically equiva-
lent to or lower than that of commer-
cial composites TPH Spectrum
(Dentsply Caulk, York, Pa.), EsthetX
(Dentsply Caulk), Point 4 (Kerr,
Orange, Calif.) and Filtek A110
Anterior Restorative (3M ESPE
Dental Products) at the 95 percent
CI.
Gloss retention data for up to 500
brushstrokes are shown in Figure 4.
After short-term toothbrush cycles
(that is, 100 brushstrokes), both the
standard and translucent formula-
tions of Filtek Supreme nanocom-
posite showed very high gloss reten-
tion, at 91 to 95 percent, respectively, of the
original value. The commercial materials also
retained gloss at around 80 to 90 percent of orig-
1386 JADA, Vol. 134, October 2003
A D V A NC E S I N DE NT AL P R ODUCT S
TABLE 2
MECHANICAL PROPERTIES OF THE NANOCOMPOSITE
AND FIVE COMMERCIAL COMPOSITES STUDIED.
SAMPLE* PROPERTY ( SD

)
Diametral
Tensile
Strength
(MPa

)
Comprehensive
Strength
(MPa)
Flexural Strength
(MPa)
Fracture
Resistance
(MPa/m
1
/2
)
96.6 (5.6)
a
80.7 (5.3)
b
76.6 (6.8)
b
66.7 (4.1)
c
52.3 (2.9)
d
87.6 (9.0)
a
80.7 (3.2)
b
454.5 (10.2)
a
378.6 (26.7)
b
433.8 (15.7)
a
422.1 (36.8)
a,b
376.6 (32.6)
b
458.6 (20.8)
a
426.2 (27.5)
a
161.2 (17.2)
a,b
136.1 (10.6)
d
136.0 (15.0)
d
140.6 (6.9)
c
94.0 (5.7)
e
177.1 (19.0)
a
153.1 (14.1)
b,c
1.4 (0.1)
a
1.4 (0.0)
a
1.2 (0.1)
b
1.2 (0.1)
b
0.9 (0.1)
c
1.2 (0.1)
b
1.3 (0.1)
a,b
Filtek Z250
TPH Spectrum
Point4
EsthetX
Filtek A110
Filtek Supreme
Translucent
Filtek Supreme
Standard
* Manufacturers and lot numbers of the composites tested are identified in Table 1.
SD: Standard deviation.
MPa: Megapascals.
MPa/m
1
/
2
: Megapascals per meter
1
/
2
.
Statistical comparisons are presented as superscripts after numerical values. Values within any column
identified by the same superscipt lowercase letters are not significantly different (P < .05).
1.2
1
0.8
0.6
0.4
0.2
0
Z250 TPH Point 4 EsthetX A110 FSS FST
COMPOSITES STUDIED
R
E
L
A
T
I
V
E

V
A
L
U
E
Diametral Tensile Strength Flextural Strength
Compressive Strength Fracture Resistance
Figure 2. Comparison of mechanical properties of composites normalized
to Filtek Z250 Universal Restorative composite (hybrid) (3M ESPE Dental
Products, St. Paul, Minn.). Z250: Filtek Z250. TPH: TPH Spectrum
(Dentsply Caulk, York, Pa.). Point 4: Point 4 (Kerr, Orange, Calif.).
EsthetX: EsthetX (Dentsply Caulk). A110: Filtek A110 (3M ESPE Dental
Products). FSS: Filtek Supreme Standard formulation of dentin, body and
enamel shades (3M ESPE Dental Products). FST: Filtek Supreme Translu-
cent formulation (3M ESPE Dental Products).
Copyright 2003 American Dental Association. All rights reserved.
inal value at the early stages (100
brushstrokes) of the brushing experi-
ment.
Much more differentiation in gloss
retention between various composites
was apparent after extended tooth-
brush abrasion cyclesfor example,
at 500 brushstrokes. For hybrid and
microhybrid materials, gloss reten-
tion dropped to around 20 to 40 per-
cent of original value. From the trend
shown in the figures, the gloss reten-
tion is expected to continue to
decrease with increasing brush
cycles. As expected, gloss retention
was very good for the microfill ma-
terial and appeared to reach a
plateau at 80 percent of the original
value. For the Filtek Supreme stan-
dard material, which is a 20-nm NM
particle filler in combination with
NCs, the gloss retention also reached
a plateau at about 80 percent of the
original value, which statistically
was not different from that of the
microfill material tested. For Filtek
Supreme Translucent, in which a
majority of the filler is NM particle
and a minor portion is NCs, gloss
retention plateaued at around the 90
percent level. Thus, both the stan-
dard and translucent formulations of
Filtek Supreme Universal Restora-
tive showed gloss retention compa-
rable or superior to the microfill
after 500 toothbrush abrasion cycles.
SEM images of composite specimens
after 500 cycles of toothbrush abra-
sion are displayed in Figure 5.
DISCUSSION
Our objective was to develop a dental
composite material that had the
mechanical strength and wear resis-
tance of hybrid composites yet had
the superior polish and gloss reten-
tion associated with microfill mate-
rials. Our investigative approach
achieved this by using nanotechnology. The
greatest challenge in preparing nanocomposites
lies in preventing the association of small parti-
cles to form more thermodynamically favorable
aggregates and agglomerates. By using a propri-
etary process for application of MPTS to the dis-
crete particles, we isolated the NM particles for
these experiments as a dry, nonaggregated
powder. The TEM of the experimental nanocom-
posite made by dispersing 75-nm NM-particle
JADA, Vol. 134, October 2003 1387
A D V A NC E S I N DE NT AL P R ODUCT S
4
3.5
3
2.5
2
1.5
1
0.5
0
Z250 TPH Point 4 EsthetX A110 FSS FST
COMPOSITES STUDIED
M
I
C
R
O
M
E
T
E
R
S

P
E
R

3
9
,
0
0
0

C
Y
C
L
E
S
Figure 3. Wear resistance of Filtek Supreme Universal Restorative (3M
ESPE Dental Products, St. Paul, Minn.) nanocomposites as compared with
that of the other composite materials in the study. Z250: Filtek Z250 Uni-
versal Restorative composite (3M ESPE Dental Products). TPH: TPH Spec-
trum (Dentsply Caulk, York, Pa.) Point 4: Point 4 (Kerr, Orange, Calif.).
EsthetX: EsthetX (Dentsply Caulk). A110: Filtek A110 (3M ESPE Dental
Products). FSS: Filtek Supreme Standard formulation of dentin, body and
enamel shades (3M ESPE Dental Products). FST: Filtek Supreme Translu-
cent formulation (3M ESPE Dental Products).
N
N
N
N
N
N

G
I
I I
I
I
I
I
G
G
G
G
G
G

L
L
L
L
L
L

NN 100.00
80.00
60.00
40.00
20.00
0.00
0 100 200 300 400 500
G
L
O
S
S

R
E
T
E
N
T
I
O
N

%
NUMBER OF TOOTHBRUSH CYCLES
Z250
TPH
Point 4
EsthetX
A110
FSS
FST
Figure 4. Gloss retention of Filtek Supreme Universal Restorative (3M
ESPE Dental Products, St. Paul, Minn.) nanocomposites as compared with
that of other composites in the study. Z250: Filtek Z250 Universal
Restorative composite (3M ESPE Dental Products). TPH: TPH Spectrum
(Dentsply Caulk, York, Pa.). Point 4: Point 4 (Kerr, Orange, Calif.).
EsthetX: EsthetX (Dentsply Caulk). A110: Filtek A110 (3M ESPE Dental
Products). FSS: Filtek Supreme Standard formulation of dentin, body and
enamel shades (3M ESPE Dental Products). FST: Filtek Supreme Translu-
cent formulation (3M ESPE Dental Products).
Copyright 2003 American Dental Association. All rights reserved.
1388 JADA, Vol. 134, October 2003
A D V A NC E S I N DE NT AL P R ODUCT S
filler in resin (Figure 1A, page 1385) shows the
NM-particle filler as discrete nonaggregated
particles.
Although the average cluster size of the NCs
developed for our work is similar to that in con-
ventional hybrid fillers, NC particles are funda-
mentally different from hybrid filler particles.
Hybrid fillers, typically, are large, dense particles
of an average size of about 1 m, as shown by
schematic drawing and TEM in Figure 1C (page
1385). These particles cannot be further subdi-
vided under normal abrasive forces in the mouth.
Similar remarks apply to microhybrids, which are
only slightly smaller than hybrids in average par-
ticle size. By contrast, we propose that the nano-
sized primary particles in the NCs, clearly seen in
the cluster domain of Figure 1B (page 1385), wear
by breaking off individual primary particles
(rather than plucking out the larger secondary
particle from the resin). Thus, the resulting wear
surfaces have smaller defects and better gloss
retention. The SEMs of wear facets of toothbrush-
abraded surface of the NC composite (Figure 5B)
contrasts with those of a hybrid material (Figure
5A), which clearly show large particles protruding
from the surface, as well as pits where particles
have been plucked from the surface. Microhybrid
composites contain particles somewhat smaller in
size than do hybrids. However, the two microhy-
brid materials we tested showed significant sur-
face roughness after 500 cycles of toothbrush abra-
sion. This is because the mechanism of abrasion in
a microhybrid is similar to that of a hybrid. Indi-
vidual filler particles were plucked out, leaving
voids that are only slightly smaller than those in
traditional hybrids. The resultant surface is not as
Figure 5. Scanning electron microscopic images of toothbrush-abraded surfaces of restorative dental composites. A.
Hybrid. B. Microfill. C. FSS: Filtek Supreme Standard formulation of dentin, body and enamel shades (3M ESPE Dental
Products, St. Paul, Minn.). D. FST: Filtek Supreme Translucent formulation (3M ESPE Dental Products).
Copyright 2003 American Dental Association. All rights reserved.
rough as that of a hybrid
material but certainly not as
glossy as that of a microfill.
NM particles and NCs also
are fundamentally different
from particles in microfill
fillers. Typical microfill fillers
are made using pyrogenic
processes, which produce
materials with an average pri-
mary particle size of about 40
nm, but in which the primary
particles typically aggregate
in fibrous, low-density, chain-
like secondary structures. The
fibrous structures of microfill
fillers limits paste filler load-
ings and results in poor han-
dling and lower mechanical
properties than are demon-
strated by hybrids and microhybrids. Commercial
microfills generally contain prepolymerized resin
particles previously filled with fumed silica (com-
monly known as organic filler) to improve the
handling characteristics. Because of the small pri-
mary particle size, microfills display high gloss
retention but poor bonding between the organic
filler particles, and the resin matrix lowers the
mechanical properties. Thus, indications for
microfills usually are limited to low
stressbearing anterior restorations.
The use of spheroidal NC fillers with their
broad particle distribution enabled us to obtain
high filler loading, desirable handling character-
istics and physical properties comparable with
those of commercial hybrid composites. The
diametral tensile strength, compressive strength,
flexural strength and fracture resistance of the
FSS and FST formulations of Filtek Supreme
Universal Restorative are statistically equivalent
to or higher than those of the hybrid or microhy-
brid composites tested and significantly higher
than those of the microfill material tested. These
results, combined with the wear results (and
other data not reported here), support the use of
these materials for the same indications as those
for other universal restoratives.
Although microhybrid composites contain par-
ticles somewhat smaller in size than hybrids, the
two microhybrid materials we tested showed sig-
nificant surface roughness after 500 cycles of
toothbrush abrasion. This is because the microhy-
brids mechanism of abrasion is similar to that of
JADA, Vol. 134, October 2003 1389
A D V A NC E S I N DE NT AL P R ODUCT S
a hybrid. Individual filler particles are plucked
out, leaving voids that are only slightly smaller
than those in traditional hybrids. The resultant
surface is not as rough as that of a hybrid but cer-
tainly not as glossy as that of a microfill.
The FST and FSS nanocomposites use combi-
nations of NM-particle and NC fillers in opti-
mized ratios for desirable performance. The NM
particles in these formulations fill the interstitial
spaces between the clusters. The resultant sur-
face, thus, is densely packed with fillers. The FST
and FSS materials consequently display high
polish retention after toothbrush abrasion. When
these materials undergo toothbrush abrasion,
only nanosized particles are plucked away,
leaving the surfaces with defects smaller than the
wavelength of light. The visual appearance
retains a high gloss and is consistent with the
smooth surfaces displayed in the SEM of Figure
5D. In this study, the maintenance of surface
smoothness of the abraded Filtek Supreme
translucent material, which consists of predomi-
nantly NM particles and is qualitatively equiva-
lent to the microfill we tested. The major portion
of the FSS filler consists of NCs (that is, the NM
particle concentration here is lower than that of
the FST). Not surprisingly, the FSS showed a
slightly rougher surface than did the FST. How-
ever, the abraded surface of FSS still was found
to be very smooth compared with those of the
hybrids and microhybrids in this study. It is evi-
dent from the SEMs that individual nanoparticles
of the zirconia-silica NC sheared off. This is in
Figure 6. Optical effect of nanocomposite material versus that of the other types
of composite materials studied. FST: Filtek Supreme Translucent formulation
(3M ESPE Dental Products, St. Paul, Minn.).
Copyright 2003 American Dental Association. All rights reserved.
contrast to the situation in
hybrids of microhybrids, where
large particles sheared off in
totality, leaving much larger craters on abrasion.
Nanofillers also offer advantages in optical
properties. In general, it is desirable to provide
low visual opacity in unpigmented dental compos-
ites. This allows the clinician to construct a wide
range of shades and opacities and, thus, provide
highly esthetic restorations. In hybrid materials,
fillers consist of particles averaging 1 mm in size.
When particles and resin are mismatched in the
refractive index, which measures the ability of
the material to transmit light, the particles will
scatter light and produce opaque materials. In
NM-particle materials, the size of the particles is
far below the wavelength of light, making them
unmeasurable by the refractive index. When light
comes in, long-wavelength light passes directly
through and materials show high translucency.
As shown in Figure 6, the disks made with hybrid
and microfill fillers are rather opaque. The FST
sample made predominantly with the NM particle
filler is very clear, as the background can be seen
through the composite. In addition, when placed
on a black background, the nanoparticles prefer-
entially scatter blue light, giving the composite an
opalescent effect. The ability to create a nanocom-
posite with a very low opacity provides the ability
to formulate a vast range of shade and opacity
options from the very translucent shades needed
for the incisal edge and for the final layer in mul-
tilayered restorations to the more opaque shades
desired in the enamel, body and dentin shades.
The commercial material is available in three
translucent shades, seven enamel shades, 13 body
shades and seven dentin shades. This allows the
clinician the flexibility to make a choice of using a
single shade or a multishade layering technique,
1390 JADA, Vol. 134, October 2003
A D V A NC E S I N DE NT AL P R ODUCT S
depending on the clinical case in question.
Clinical studies are under way to determine
the long-term in vivo efficacy of the Filtek
Supreme material.
CONCLUSIONS
This article describes the use of nanotechnology
to make a dental restorative composite system
that offers high translucency, high polish and
polish retention similar to those of microfills
while maintaining physical properties and wear
resistance equivalent to several commercial
hybrid composites. Combinations of two types of
nanofillers result in the best combination of phys-
ical properties. With the combination of superior
esthetics, long-term polish retention and other
optimized physical properties, it is expected that
this novel nanocomposite system would be useful
for all posterior and anterior restorative applica-
tions. Clinical studies are needed to confirm the
laboratory findings. I
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Dr. Mitra is a corporate
scientist, 3M ESPE
Dental Products, 3M,
Building 260-2B-13,
3M Center, St. Paul,
Minn. 55144, e-mail
sbmitra@mmm.
com. Address reprint
requests to Dr. Mitra.
Dr. Holmes is a senior
research specialist, 3M
ESPE Dental Products,
3M, St. Paul, Minn.
Dr. Wu is a research
specialist, 3M ESPE
Dental Products, 3M,
St. Paul, Minn.
Copyright 2003 American Dental Association. All rights reserved.