A D V A N C E S I N D E N TA L P R O D U C T S

ABSTRACT
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 combinations 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 composites 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 toothbrush 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 clinician 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.

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 2 The strength and technology. The intense interest in using nanomaand esthetic terials stems from the idea that they properties of may be used to manipulate the structure the resin-based of materials to provide dramatic nanocomposite improvements in electrical, chemical, tested should mechanical and optical properties.3 At a allow the billionth of a meter, a nanometer is the clinician to use essence of small. For perspective, the size of one hydrogen atom is 0.1 to 0.2 it for both nm and of a small bacterium about 1,000 anterior and nm or 1 micrometer. A large amount of posterior research is being devoted to the developrestorations. ment of nanocomposites of different types for various applications, including structural materials, high performance coatings, catalysts, 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 manifestations 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

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implications for the optical properties of materials, nanomeric, or NM, particles and nanoclusters, or as this article will demonstrate. NCs. The NM particles are monodisperse nonagOne of the most significant contributions to gregated and nonagglomerated silica nanopartidentistry has been the development of resin-based cles. In this investigation, we used aqueous colcomposite technology. Adhesively bonded composloidal silica sols to synthesize dry powders of ites have the advantage of conserving sound tooth nanosized silica particles 20 and 75 nm in diamstructure with the potential for tooth reinforceeter. We treated the silica particles with ment, while at the same time providing a cosmeti3-methacryloxypropyltrimethoxysilane, or MPTS, cally acceptable restoration.5 However, no one using a proprietary method. MPTS, a bifunctional composite material has been able to meet both the material also known as a coupling agent, contains functional needs of a posterior Class I or II a silica ester function on one end for bonding to restoration and the superior esthetics required for the inorganic surface and a methacrylate group anterior restorations.6 Our objective was to on the other end to make the filler compatible develop a composite dental filling material that with the resin before curing to prevent any could be used in all areas of the mouth with high agglomeration or aggregation. MPTS also allows initial polish and superior polish chemical bonding of the NM filler to the resin matrix during curing. retention (typical of microfills), as We synthesized two types of NC well as excellent mechanical properNanofillers are very fillers using proprietary processes. ties suitable for high stressbearing different from The first type consists of zirconiarestorations (typical of hybrid com7 traditional fillers and silica particles synthesized from a posites). To this end, we developed require a shift from colloidal solution of silica and a zirnovel nanofillers and then nanocomconyl salt. The primary particle size posites using advanced methacrya top-down to a of this NC filler ranges from 2 to 20 late resins and curing technologies. bottom-up nm, while the spheroidal agglomerNanofillers are very different from manufacturing ated particles have a broad size distraditional fillers and require a shift approach. tribution, with an average particle from a top-down to a bottom-up mansize of 0.6 m. The second type of ufacturing approach. To make filler NC filler, which we synthesized particles of the mechanically strong composites of today (such as macrofills, hybrids and from 75-nm primary particles of silica, has a microhybrids) one starts from dense, large particles broad secondary particle size distribution with a (mined quartz, melt glasses, ceramics) and commin0.6-m average. We treated the surfaces of both utes them to small particle size. However, these types of nanocluster filler particles with an MPTS milling procedures usually cannot reduce the filler coupling agent to provide compatibility and chemparticle size below 100 nm (1 nm = 1/1,000 m). To cirical bonding with the organic resin. cumvent this roadblock, our team used synthetic Resin system. The resin system used in the chemical processes to produce building blocks on a nanocomposites in this investigation is the same molecular scale. We then assembled these materials proprietary mixture used in Filtek Z250 Uniinto progressively larger structures and transformed versal Restorative composite (3M ESPE Dental them into nanosized fillers suitable for a dental comProducts): bisphenol A glycidyl dimethacrylate, posite. This article describes our research toward ethoxylated bisphenol A dimethacrylate, the development of a new dental nanocomposite, triethylene glycol dimethacrylate, Filtek Supreme Universal Restorative (3M ESPE 1,6-bis(2-methacryloyl-oxyethoxycarbonylamino) Dental Products, St. Paul, Minn.), that has the -2,4,4-trimethylhexane, photoinitiators and esthetic properties required for cosmetic restorastabilizers. tions and the mechanical properties necessary for Nanocomposite preparation. Using statistiposterior restorations. In our research, we compared cally designed experimentation methodology, we the properties of these materials with those of sevstudied many combinations of NC and NM fillers eral commercial composites. to determine an optimal formulation for the Filtek Supreme Universal Restorative dental MATERIALS nanocomposite system. The formulations for the Nanofiller particles. We synthesized two new dentin, body and enamel shades of Filtek types of nanofiller particles for this investigation: Supreme Standard, or FSS, pastes contain
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TABLE 1

another wheel acting as an antagonistic cusp (the COMMERCIAL COMPOSITES TESTED. second body). The two PRODUCT COMPOSITE TYPE MANUFACTURER LOT NO. wheels counter-rotated against each other, dragMicrofill 1BC 3M ESPE Dental Filtek A110 ging an abrasive slurry Products, St. Paul, Minn. (the third body) between them. We determined Hybrid 1LC 3M ESPE Filtek Z250 dimensional loss during Hybrid 001025 Dentsply Caulk, York, TPH Spectrum 156,000 cycles by profilomPa. etry at regular intervals Microhybrid 0110036 Dentsply Caulk EsthetX (that is, after every 39,000 Microhybrid 111432 Kerr, Orange, Calif. cycles). As the wear in this Point4 method typically followed a Nanocomposite EXM 612 3M ESPE Filtek Supreme linear pattern, we plotted Standard the data using linear Nanocomposite EXM 612 3M ESPE Filtek Supreme regression and determined Translucent the wear rates from the slope.12 We tested three samples of each material. zirconia-silica NCs and silica NPs. The effective Fracture toughness. We determined the fracprimary particle size is 20 nm. The formulations ture resistance of materials using a short rod of Filtek Supreme Translucent, or FST, shades fracture toughness method.12 We cut a chevroncontain a filler predominantly composed of indishaped notch into the end of a cured rod of matevidual NM particles 75 nm in diameter and a rial (8 millimeters in length 4 mm in diameter) minor amount of silica NCs. that had been stored in water at 37 C for seven Commercial materials. We also tested sevdays, and we propagated a crack through the eral commercial composites currently on the chevron by pulling the two halves of the specimen market for comparative purposes. Table 1 lists apart at a controlled rate. The values reported for the name of the product, the type of product, the fracture resistance are related to the energy name of the manufacturer and the lot number of required to propagate a crack.12,13 We tested five each of the composites we tested. samples of each material studied. Flexural strength. Flexural strength was METHODS measured (n = 3) using the three-point bending Compressive strength and diametral tensile test method of the International Organization for strength. We prepared cured cylindrical rods of Standardization.14 composite materials and tested and measured Polish retention. Samples of composite paste them for compressive strength according to the were cured in a rectangular 20 9 3mm mold method described in Mitra and Kedrowski,8 with between two pieces of polyester film. We cured the exception that there was no mixing necessary. each specimen with a curing unit (Visilux 2, 3M We tested and measured diametral tensile ESPE Dental Products) for 80 seconds followed by strength according to a modification of ADA specicuring for 90 seconds in a light box (UniXS, Herfication no. 27.9 We stored the cured specimens aeus Kulzer, Armonk, N.Y.). Specimens were (N = 5) in distilled water at 37 C for 24 hours mounted with double-sided adhesive tape (Scotch before measurement using an Instron testing Brand Tape, Core series 2-1300, 3M, St. Paul, instrument (Instron 4505, Instron, Canton, Minn.) to a sample holder (Ecomet 4 Grinder/PolMass.). isher, Buehler, Lake Bluff, Ill.). The mounted Wear. We determined the wear rate by an in samples were polished using a polisher (Buehler vitro three-body wear test according to a modified Ecomet 4 Grinder/Polisher) with a special polAcademisch Centrum Trandheelkunde Amishing head (Automet 2 Polishing Head, Buehler). sterdam, or ACTA, method.10,11 In this test, we The following sequence of abrasives was used for loaded composite (the first body) onto a wheel and each sample: 320-grit and 600-grit silicon carbide cured it, then brought the wheel into contact with abrasive, 9-mm diamond polishing paste, 3-mm
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diamond polishing paste and finally a polishing suspension (Masterpolish Polishing Suspension, Buehler). A microtri-gloss instrument (BYKGardner, Columbia, Md.) was used to collect photoelectric 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 gloss15 for measurements made at 60 degrees geometry with the following analysis. Initial gloss after polishing (GI) was measured for sample immediately after preparation. Final gloss was measured after 500 toothbrushing cycles (GF). The G value was calculated with the following formula: G = (GF) (GI). gloss retention (GR) = 100 G/GI. 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 formulation tested. Surface morphology after toothbrush abrasion. We mounted samples for scanning electron microscopy, or SEM, analysis on an aluminum 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 Sputtercoater/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

Figure 1. Schematics and transmission electron microscopic images of composites studied. A. Composite with nanometric particles ( 60,000 magnification). B. Composite with nanocluster particles ( 300,000 magnification). C. Composite with hybrid fillers ( 300,000 magnification). nm: Nanometers. APS: Average particle size. m: Micrometer.

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 comparative summary of the results of diametral tensile strength, compressive strength, flexural strength and fracture resistance. Statistical
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TABLE 2

alent to or higher than those of the other comMECHANICAL PROPERTIES OF THE NANOCOMPOSITE mercial composites AND FIVE COMMERCIAL COMPOSITES STUDIED. tested. The flexural strength of FSS and SAMPLE* PROPERTY ( SD ) FST was higher than Comprehensive Flexural Strength Fracture Diametral that of three of the Strength (MPa) Resistance Tensile (MPa) (MPa/m / ) other composites and Strength (MPa ) equivalent to that of 96.6 (5.6)a 454.5 (10.2)a 161.2 (17.2)a,b 1.4 (0.1)a the other commercial Filtek Z250 composites tested at 80.7 (5.3)b 378.6 (26.7)b 136.1 (10.6)d 1.4 (0.0)a TPH Spectrum the 95 percent CI 76.6 (6.8)b 433.8 (15.7)a 136.0 (15.0)d 1.2 (0.1)b Point4 (Table 2). Statistical 66.7 (4.1)c 422.1 (36.8)a,b 140.6 (6.9)c 1.2 (0.1)b analysis showed that EsthetX the fracture resistance 52.3 (2.9)d 376.6 (32.6)b 94.0 (5.7)e 0.9 (0.1)c Filtek A110 of FSS and FST was 87.6 (9.0)a 458.6 (20.8)a 177.1 (19.0)a 1.2 (0.1)b Filtek Supreme higher than that of one Translucent of the composites tested 80.7 (3.2)b 426.2 (27.5)a 153.1 (14.1)b,c 1.3 (0.1)a,b Filtek Supreme and equivalent to that Standard of the other commercial * Manufacturers and lot numbers of the composites tested are identified in Table 1. composites tested at SD: Standard deviation. MPa: Megapascals. the 95 percent CI. MPa/m : Megapascals per meter . Figure 3 shows the 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). three-body wear rates of the nanocomposites and the other commercial composites examined in this 1.2 study. The wear rate of the FSS formulation was statistically equivalent 1 to that of the Filtek Z250 and lower than that of the other commercial 0.8 materials, as determined by ANOVA at the 95 percent CI. The wear rate 0.6 of the Filtek Supreme translucent 0.4 formulation was statistically equivalent to or lower than that of commer0.2 cial composites TPH Spectrum (Dentsply Caulk, York, Pa.), EsthetX 0 Z250 TPH Point 4 EsthetX A110 FSS FST (Dentsply Caulk), Point 4 (Kerr, COMPOSITES STUDIED Orange, Calif.) and Filtek A110 Diametral Tensile Strength Flextural Strength Anterior Restorative (3M ESPE Dental Products) at the 95 percent Compressive Strength Fracture Resistance CI. Gloss retention data for up to 500 Figure 2. Comparison of mechanical properties of composites normalized brushstrokes are shown in Figure 4. to Filtek Z250 Universal Restorative composite (hybrid) (3M ESPE Dental After short-term toothbrush cycles Products, St. Paul, Minn.). Z250: Filtek Z250. TPH: TPH Spectrum (Dentsply Caulk, York, Pa.). Point 4: Point 4 (Kerr, Orange, Calif.). (that is, 100 brushstrokes), both the EsthetX: EsthetX (Dentsply Caulk). A110: Filtek A110 (3M ESPE Dental standard and translucent formulaProducts). FSS: Filtek Supreme Standard formulation of dentin, body and enamel shades (3M ESPE Dental Products). FST: Filtek Supreme Translutions of Filtek Supreme nanocomcent formulation (3M ESPE Dental Products). posite showed very high gloss retenanalysis by the ANOVA / Tukey-Kramer paired tion, at 91 to 95 percent, respectively, of the test showed that the compressive and diametral original value. The commercial materials also tensile strengths of the FSS and FST were equivretained gloss at around 80 to 90 percent of orig
1
2
1

/2

/2

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inal value at the early stages (100 brushstrokes) of the brushing experiment. Much more differentiation in gloss retention between various composites was apparent after extended toothbrush abrasion cyclesfor example, at 500 brushstrokes. For hybrid and microhybrid materials, gloss retention dropped to around 20 to 40 percent of original value. From the trend shown in the figures, the gloss retention is expected to continue to decrease with increasing brush cycles. As expected, gloss retention was very good for the microfill material and appeared to reach a plateau at 80 percent of the original value. For the Filtek Supreme standard 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 standard and translucent formulations of Filtek Supreme Universal Restorative showed gloss retention comparable or superior to the microfill after 500 toothbrush abrasion cycles. SEM images of composite specimens after 500 cycles of toothbrush abrasion are displayed in Figure 5.
DISCUSSION

MICROMETERS PER 39,000 CYCLES

4 3.5 3 2.5 2 1.5 1 0.5 0

Z250 TPH Point 4 EsthetX A110 FSS FST

COMPOSITES STUDIED

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 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 Translucent formulation (3M ESPE Dental Products).

GLOSS RETENTION %

v x s 100.00 q

80.00 60.00 40.00 20.00 0.00 0

q s v x

q s v x

s q v

s q

s q x

Z250 TPH Point 4 EsthetX A110 FSS FST

v v x q

x x

100

200

300

400

500

NUMBER OF TOOTHBRUSH CYCLES

Figure 4. Gloss retention of Filtek Supreme Universal Restorative (3M

Our objective was to develop a dental ESPE Dental Products, St. Paul, Minn.) nanocomposites as compared with that of other composites in the study. Z250: Filtek Z250 Universal composite material that had the Restorative composite (3M ESPE Dental Products). TPH: TPH Spectrum mechanical strength and wear resis- (Dentsply Caulk, York, Pa.). Point 4: Point 4 (Kerr, Orange, Calif.). EsthetX: EsthetX (Dentsply Caulk). A110: Filtek A110 (3M ESPE Dental tance of hybrid composites yet had Products). FSS: Filtek Supreme Standard formulation of dentin, body and the superior polish and gloss retenenamel shades (3M ESPE Dental Products). FST: Filtek Supreme Translucent formulation (3M ESPE Dental Products). tion associated with microfill materials. Our investigative approach achieved this by using nanotechnology. The etary process for application of MPTS to the disgreatest challenge in preparing nanocomposites crete particles, we isolated the NM particles for lies in preventing the association of small partithese experiments as a dry, nonaggregated cles to form more thermodynamically favorable powder. The TEM of the experimental nanocomaggregates and agglomerates. By using a propriposite made by dispersing 75-nm NM-particle
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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).

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 conventional hybrid fillers, NC particles are fundamentally 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 subdivided under normal abrasive forces in the mouth. Similar remarks apply to microhybrids, which are only slightly smaller than hybrids in average particle size. By contrast, we propose that the nanosized primary particles in the NCs, clearly seen in the cluster domain of Figure 1B (page 1385), wear by breaking off individual primary particles
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(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 toothbrushabraded 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 microhybrid materials we tested showed significant surface roughness after 500 cycles of toothbrush abrasion. This is because the mechanism of abrasion in a microhybrid is similar to that of a hybrid. Individual filler particles were plucked out, leaving voids that are only slightly smaller than those in traditional hybrids. The resultant surface is not as

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A D V A N C E S IN DENTAL PRODUCTS

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 primary particle size of about 40 nm, but in which the primary particles typically aggregate in fibrous, low-density, chainlike secondary structures. The fibrous structures of microfill fillers limits paste filler loadFigure 6. Optical effect of nanocomposite material versus that of the other types ings and results in poor hanof composite materials studied. FST: Filtek Supreme Translucent formulation dling and lower mechanical (3M ESPE Dental Products, St. Paul, Minn.). properties than are demonstrated by hybrids and microhybrids. Commercial a hybrid. Individual filler particles are plucked microfills generally contain prepolymerized resin out, leaving voids that are only slightly smaller particles previously filled with fumed silica (comthan those in traditional hybrids. The resultant monly known as organic filler) to improve the surface is not as rough as that of a hybrid but cerhandling characteristics. Because of the small pritainly not as glossy as that of a microfill. mary particle size, microfills display high gloss The FST and FSS nanocomposites use combiretention but poor bonding between the organic nations of NM-particle and NC fillers in optifiller particles, and the resin matrix lowers the mized ratios for desirable performance. The NM mechanical properties. Thus, indications for particles in these formulations fill the interstitial microfills usually are limited to low spaces between the clusters. The resultant surstressbearing anterior restorations. face, thus, is densely packed with fillers. The FST The use of spheroidal NC fillers with their and FSS materials consequently display high polish retention after toothbrush abrasion. When broad particle distribution enabled us to obtain these materials undergo toothbrush abrasion, high filler loading, desirable handling characteronly nanosized particles are plucked away, istics and physical properties comparable with leaving the surfaces with defects smaller than the those of commercial hybrid composites. The wavelength of light. The visual appearance diametral tensile strength, compressive strength, retains a high gloss and is consistent with the flexural strength and fracture resistance of the smooth surfaces displayed in the SEM of Figure FSS and FST formulations of Filtek Supreme 5D. In this study, the maintenance of surface Universal Restorative are statistically equivalent smoothness of the abraded Filtek Supreme to or higher than those of the hybrid or microhytranslucent material, which consists of predomibrid composites tested and significantly higher nantly NM particles and is qualitatively equivathan those of the microfill material tested. These lent to the microfill we tested. The major portion results, combined with the wear results (and of the FSS filler consists of NCs (that is, the NM other data not reported here), support the use of particle concentration here is lower than that of these materials for the same indications as those the FST). Not surprisingly, the FSS showed a for other universal restoratives. slightly rougher surface than did the FST. HowAlthough microhybrid composites contain parever, the abraded surface of FSS still was found ticles somewhat smaller in size than hybrids, the to be very smooth compared with those of the two microhybrid materials we tested showed sighybrids and microhybrids in this study. It is evinificant surface roughness after 500 cycles of dent from the SEMs that individual nanoparticles toothbrush abrasion. This is because the microhyof the zirconia-silica NC sheared off. This is in brids mechanism of abrasion is similar to that of
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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
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. Wu is a research specialist, 3M ESPE Dental Products, 3M, St. Paul, Minn. Dr. Holmes is a senior research specialist, 3M ESPE Dental Products, 3M, St. Paul, Minn.

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 composites. 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 preferentially scatter blue light, giving the composite an opalescent effect. The ability to create a nanocomposite 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 multilayered 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,

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 physical 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 applications. Clinical studies are needed to confirm the laboratory findings. s
1. Kirk RE, Othmer DF, Kroschwitz J, Howe-Grant M. Encyclopedia of chemical technology. 4th ed. New York: Wiley; 1991:397. 2. Schulz W. Crafting a national nanotechnology effort. Chem Eng News 2000;78(42):39-42. 3. Whitesides GM, Christopher Love J. The art of building small. Sci Am 2001;285(3):38-47. 4. Dagani R. Building from the bottom up. Chem Eng News 2000; 78(42):27-32. 5. Fortin D, Vargas MA. The spectrum of composites: new techniques and materials. JADA 2000;131(6)(supplement):26S-30S. 6. Denehy GE. A direct approach to restore anterior teeth. Am J Dent 2000;13(special issue):55-9. 7. Craig RG, Ward ML. Restorative dental materials. 10th ed. St. Louis: Mosby; 1997:245. 8. Mitra SB, Kedrowski BL. Long-term mechanical properties of glass ionomers. Dent Mater 1994;10:78-82. 9. American National Standards Institute and American Dental Association. Specification no. 27: Resin-based filling materials. Chicago: American Dental Association; 1993. 10. Wu D, Holmes BN, Mitra SB, Kolb BU, Thompson W, Johnson NJ. Wear resistance and mechanical properties of novel dental nanocomposites (abstract 64). J Dent Res 2002;81(special issue A): A-37. 11. deGee AJ, Pallav P, Davidson CL. Effect of abrasion medium on wear of stress-bearing composites and amalgam in vitro. J Dent Res 1986;65:654-8. 12. Mitchell CA, Douglas WH, Cheng V-S. Fracture toughness of conventional, resin-modified glass-ionomer and composite luting cement. Dent Mater 1999;15:7-13. 13. Lin CP, Douglas WH, Mitra SB, Fields RP. Fracture toughness of dental cements using the short rod method (abstract 74). J Dent Res 1992;72(special issue):524. 14. International Organization for Standardization. Standard 4049, Section 7.11: DentistryPolymer-based filling, restorative and luting materials. Geneva: International Organization for Standardization; 2000. 15. American Society for Testing and Materials. D523-89(1999) standard test method for specular gloss. West Conshohocken, Pa.: American Society for Testing and Materials; 1999.

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