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Polymer Nanocomposites with Nanowhiskers Isolated from Microcrystalline Cellulose
Jeffrey R. Capadona,,,,| Kadhiravan Shanmuganathan,, Stephanie Trittschuh, Scott Seidel, Stuart J. Rowan,, and Christoph Weder*,,
Departments of Macromolecular Science and Engineering, Biomedical Engineering, and Chemistry, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106, and Rehabilitation Research and Development, Louis Stokes Cleveland DVA Medical Center, 10701 East Blvd. Cleveland, Ohio 44106 Received September 25, 2008; Revised Manuscript Received February 5, 2009

The ability to produce polymer nanocomposites, which comprise a percolating, three-dimensional network of well-individualized nanobers, is important to maximize the reinforcing effect of the nanobers. While microcrystalline cellulose (MCC) has been previously shown to improve the mechanical properties of polymer composites, the formation of brous percolating networks within the nanocomposites has been stied. Through the utilization of a template approach, nanocomposites based on an ethylene oxide/epichlorohydrin copolymer and nanowhiskers isolated from MCC were produced that display the maximum mechanical reinforcement predicted by the percolation model.

Introduction
The incorporation of small amounts of high-stiffness, highaspect-ratio nanometer-sized llers into polymers is a design approach that has rapidly emerged to a broadly exploited framework for the creation of new materials with tailored mechanical properties.1-3 Crystalline cellulose nanobers are attracting signicant interest in this context, mainly due to their intriguing mechanical properties and the abundance of cellulose in the biomass.4 These ber-like crystals, often referred to as nanowhiskers, display an elastic modulus of 120-150 GPa5 and are readily obtained from renewable biosources such as bacteria, wood, cotton, and sessile sea creatures called tunicates.4 Owing to their strongly interacting surface hydroxyl groups,6 cellulose nanowhiskers have a signicant tendency for self-association, which is advantageous for the formation of load-bearing percolating architectures within the host polymer matrix: the spectacular reinforcement of polymers observed for this class of materials is attributed to the formation of rigid nanowhisker networks in which stress transfer is facilitated by hydrogen-bonding between the nanowhiskers;7 van der Waals interactions also have been shown to play a signicant role.8 However, these same nanowhisker-nanowhisker interactions can also lead to aggregation during the nanocomposite fabrication,9 which signicantly reduces the mechanical properties of the resulting materials compared to predicted values.7 The traditional approach to solve this problem is surface functionalization,
* To whom correspondence should be addressed. Tel.: (216) 368 6374. E-mail: christoph.weder@case.edu. These authors contributed equally. Department of Macromolecular Science and Engineering, Case Western Reserve University. Department of Biomedical Engineering, Case Western Reserve University. | Louis Stokes Cleveland DVA Medical Center. Department of Chemistry, Case Western Reserve University.

which mediates particle-particle and particle-polymer interactions and signicantly inuences nanoparticle dispersion.10-13 However, the advantages of surface groups are often negated because they suppress desirable nanoparticle interactions and limit their reinforcing impact. To solve this dilemma, we recently explored a template approach to nanocomposite fabrication.14 The process is based on the formation of a three-dimensional scaffold of well-individualized nanowhisker, which is subsequently lled with a polymer of choice. We demonstrated that this technique, which is somewhat different from other recently developed impregnation schemes,15 is applicable to cellulose nanowhiskers isolated from tunicates16 and cotton4 (both exhibit average diameters of 20-26 nm, and lengths of 2.2 m or 210 nm, respectively). Both nanowhisker types were incorporated into a range of polymers, and the resulting nanocomposites display signicantly improved mechanical properties. We here report that the template approach is also suitable for the fabrication of polymer nanocomposites with commercially available microcrystalline cellulose (MCC). MCC is produced by partially hydrolyzing cellulose pulp, for example, from wood, with mineral acids. The properties of the resulting particles are inuenced by the conditions of the hydrolysis process.17 Typical MCC features particles with dimensions on the order of 10-100 m.18 However, the material can be dispersed by ultrasonication so that mainly nanowhiskers with dimensions on the order of 20 200 nm are obtained.18,19 The nanowhiskers produced here from MCC were of similar dimensions (23 260 nm, Figure 1a). The main applications of MCC are as an excipient in the formulation of tablets, emulsier, stabilizer, and anticaking agent. The commercial availability of MCC has also triggered signicant interest in its use as reinforcing ller in polymer composites.20-22 Unfortunately, the dramatic reinforcement effects displayed by cellulose nanowhiskers from other sources have hitherto

10.1021/bm8010903 CCC: $40.75 2009 American Chemical Society Published on Web 03/03/2009

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Figure 1. Transmission electron microscopy (TEM) images of cellulose nanowhiskers prepared by (a) dispersion of microcrystalline cellulose (MCC) in water and subsequent fractionation; (b) dispersion of microcrystalline cellulose (MCC) in DMF; (c) hydrolysis of cotton and dispersion in water; scale bars (a,c) ) 500 nm; (b) ) 2 m.

not been observed in the case of MCC-based composites. Wu et al. attributed this shortcoming to the inability of MCC to form percolating brous networks within the nanocomposites.21 The present study supports this nding for materials that comprise small volume fractions of ultrasonicated, but not fractionated MCC dispersions. We further demonstrate that MCC nanocomposites with properties that appear to reach the theoretical limit can be fabricated by fractionation of the MCC and using the template approach.

Experimental Section
Materials. All reagents, except acetone, were used as received. Dimethyl formamide (DMF, water <50 ppm), acetone (dried with potassium carbonate), sulfuric acid, and potassium hydroxide were purchased from Sigma Aldrich (Milwaukee, WI). The ethylene oxide/ epichlorohydrin copolymer (EO-EPI copolymer, Epichlomer, comonomer ratio ) 1:1, ) 1.39 g/mL) was received from Daiso Co. Ltd. (Osaka, Japan). Cotton nanowhiskers were isolated from Whatman lter paper and lyophilized as previously described.14a,23 Microcrystalline cellulose (MCC) was received from FMC Biopolymer under the brand name Avicel (Lattice NT-100). A value of 1.46 g/mL was assumed for the density of crystalline cellulose nanowhiskers.24 Instrumentation. Transmission electron micrographs (TEMs) were acquired using a JEOL 1200EX Transmission Electron Microscope. Briey, TEM samples were prepared by deposition of 5 L (0.01 mg/mL) of the appropriate nanowhisker dispersions on Formvar/carboncoated copper grids (aqueous dispersions) or a 400 mesh carbon-coated copper grid (DMF dispersions). After 2 min, the excess dispersion was removed from the grids with a small piece of lter paper. Next, samples were stained using a standard uranyl acetate negative staining method (three 5 min treatments with 1% uranyl acetate)25 and were then allowed to dry for 15 min. For ultrasonication of nanowhisker dispersions, a

Fischer Scientic FS60H ultrasonic bath (100 W, 9.5 L bath) was used. Mechanical measurements were performed on rectangular nanocomposite lms (ca. 15 3 x 0.30 mm) using a TA Instruments DMA 2980. Cotton Cellulose Nanowhiskers. Cellulose nanowhiskers from cotton were prepared using the procedure by Dong et al.23 with minor modications. Briey, 5.2 g of Whatman No. 1 lter paper was combined with 250 mL of deionized water and blended in a Waring blender at high speed until a lumpy pulp was formed. In a beaker, sulfuric acid (98%, 140 mL) was slowly added under vigorous mechanical stirring to the cooled lter paper pulp (250 mL, 20 C). After this addition, the suspension was heated to 50 C for 3.5 h while stirring. The mixture was then cooled to room temperature, ltered over a small-pore fritted glass lter, and washed with deionized water until the pH was neutral. The resulting dispersion was then dialyzed in four successive 24 h treatments with deionized water to remove any remaining salts and sonicated for approximately 7 h. After the dispersion was left to settle at ambient temperature for at least 16 h, the supernatant dispersion was decanted off. The concentration of the nanowhiskers in that dispersion was determined gravimetrically to be 20 mg/mL. Dispersions of this concentration were used for the fabrication of gels. Further, aliquots of this solution were lyophilized and the aerogel thus produced was dispersed in DMF at a concentration 5 mg/mL via sonication for approximately 7 h. These DMF solutions were employed for the production of solution cast nanocomposites. Dispersion of MCC in Solvents. The MCC powder received from FMC Biopolymer had a particle size of the order of 100 m, with a pH of 6.6. The MCC was added to deionized water at a concentration of 20-21 mg/mL, or to DMF at a concentration of 15 mg/mL, and was dispersed via ultrasonication for 4-6 h. The temperature of the water bath increased during sonication and was not monitored nor controlled. The suspensions were allowed to settle overnight (typically 12 h) before the well-dispersed top layer was collected by decanting,

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frequency of 1 Hz, a static force of 10 mN, an oscillation amplitude of 15.0 m, and an automatic tension setting of 125%. Measurements were carried out at a heating rate of 3/min (range of 15-45 C). Shear storage moduli G were calculated from the experimentally determined tensile storage moduli E, utilizing the relationship E ) 2G( + 1), where ) 0.3 is the Poissons ratio.26 Conductometric Titration of Cotton and MCC Nanowhiskers. Surface charge densities of both cellulose nanowhiskers derived from cotton and MCC were quantied by conductometric titration to better understand their ability to disperse in aqueous and organic solvents. Between 6.6 and 8.8 mL of aqueous dispersions of either cellulose source (15 mg/mL) was placed into a 250 mL beaker with 200 mL of deionized water (in the case of the MCC, 0.3 mL of 0.01 M HCl was added to the beaker to ensure a counterion for titration). Suspensions were placed on a magnetic stir plate, and stirred during the entire titration to increase homogeneity. Ionic equilibrium was determined from measurements of pH and conductivity made against 50 L additions of 0.01 M KOH using an Accumet AR50 (Fisher Scientic; accuTupH pH probe #13-620-183; accumet conductivity probe #13-620-163).

leaving behind any sediments at the bottom (especially in the case of aqueous dispersions). The nal concentrations of the nanowhisker dispersions created from MCC dispersions were determined gravimetrically to be 5.0 g/mL (stder ) 1.3, N ) 12) and 15 mg/mL (stder ) 0.5, N ) 12) in water and DMF, respectively. The dimensions of the isolated nanowhiskers were evaluated with TEM. Formation of Cotton Nanowhisker Organogels. Cotton whisker organogels were prepared from aqueous dispersions using a solventexchange sol-gel process, previously described.14a Formation of MCC Nanowhisker Organogels. MCC nanowhisker/ acetone gels were prepared in a similar fashion as the cotton nanowhisker gels with slight modications, that is, by using a solventexchange sol-gel process in which gelation was induced through the addition of a water-miscible nonsolvent to the whisker dispersion.14a In a typical example, the aqueous MCC nanowhisker dispersion (5.0 mg/mL) was heated to evaporate water and increase the MCC concentration to 7.4 mg/mL. A total of 150 mL of this dispersion was added to a large beaker (1000 mL), followed by brief sonication to remove air bubbles. After cooling to room temperature (RT; 23-25 C), acetone (850 mL) was gently added on top of the aqueous MCC nanowhisker dispersion to form an organic layer on top of the aqueous dispersion. The organic layer was exchanged 1-2 times daily until the bottom portion had assembled into a mechanically coherent nanowhisker-acetone gel (typically 4-5 days). During that process, the acetone layer was gently agitated (1-2 times daily) to facilitate the solvent exchange. The absence of refractive index gradients at the sol/gel interface was taken as an indication that the solvent exchange was complete. At this point, the MCC nanowhisker gel was released from the beaker, and the solvent was exchanged two more times with dry acetone (overnight, in same beaker). The resulting MCC nanowhisker gel was cut into pieces of about 1 0.75 1.5 cm for polymer infusion. Determination of Cellulose Content in Organogels. The cotton nanowhisker or MCC nanowhisker content of the organogels was determined gravimetrically. The gels were weighted in their swollen and dried state and the whisker to total weight ratio was determined as an average of at least three independently prepared samples. Fabrication of Polymer/Cellulose Nanocomposites by Solution Casting. Lyophilized cotton nanowhiskers or MCC (vide supra) were dispersed in DMF at a concentration of 5 or 15 mg/mL for cotton and MCC, respectively. EO-EPI was dissolved in DMF (5% w/w) by stirring for two days. Nanocomposites were prepared by combining the desired amounts (to yield materials containing 0.9-33.3% v/v whiskers) of the colloidal nanowhisker dispersion and polymer solution and solutioncasting the resulting mixture into Teon Petri dishes. The dishes were placed into a vacuum oven (60 C, 15 mbar, 48 h) to evaporate the solvent and dry the resulting lms before the material was compressionmolded between spacers in a Carver laboratory press (at 80 C and 6000 psi for 2 min) to yield 300-400 m thin nanocomposite lms which were stored in a vacuum oven (40 C, 15 mbar) until they were tested. Fabrication of Polymer/Cellulose Nanocomposites by Template Approach. Cotton or MCC nanowhisker acetone gels, prepared as described above, were placed at room temperature into solutions of between 1.0 and 30.0 mg/mL of EO-EPI in tetrahydrofuran for 16-36 h. The gels were subsequently removed from the polymer solutions and dried at room temperature in air for up to 2 h to remove (most of) the solvent before the material was compression-molded at 60 C between spacers (above the Tg of the neat polymer at 9000 psi) for 2 min to yield 300-400 m thin nanocomposite lms which were stored in a vacuum oven (40 C, 15 mbar) until they were tested. The nanowhisker content of the nanocomposites was determined gravimetrically from the weights of the wet acetone gel and the nal dried material. Dynamic Mechanical Thermal Analyses (DMTA). DMTA measurements were performed on rectangular lms (ca. 15 3 0.3 mm) using a TA Instruments DMA 2980 in tensile mode with an oscillation

Results and Discussion

The analysis of transmission electron micrographs (TEMs) reveals that the nanowhiskers produced through sonication of commercially available MCC in water and subsequent fractionation (cf. Experimental Section, yield 25%) exhibit a width (d) of 23 ( 1 nm and a length (L) of 260 ( 12 nanometers (Figure 1a, L/d ) 11; N ) 32). Unfractionated dispersions of MCC in DMF appear homogeneous to the eye and do not show any settlements upon standing for several days. TEM images display well separated nanowhiskers of similar dimensions and also occasional larger aggregates (Figure 1b). Attempts to separate these aggregates by ltration showed only a minor (of the order of 10%) weight loss, suggesting that a substantial fraction of the MCC has indeed been dispersed into nanoscale whiskers. The MCC nanowhiskers display similar dimensions as cellulose nanowhiskers derived from cotton (Figure 1c, d ) 20 ( 1 nm, L ) 210 ( 19 nm, and L/d ) 10.5; N ) 106). The TEMs of both cellulose sources reveal that MCC nanowhiskers more readily forms small bundles or bers, compared to the well-individualized nanowhiskers obtained from cotton. The latter were isolated by hydrolysis with sulfuric acid, which introduces negatively charged sulfate groups to the whisker surface (67 mmol SO4-/Kg cellulose). The electrostatic repulsion among these groups greatly enhances the whisker dispersibility in aqueous and organic solvents,4,27 which is instrumental for the formation of nanocomposites with well dispersed whisker networks.4,7,9,14,16 Conductometric titration revealed no net surface charge for the MCC nanowhiskers used here. This major difference in surface charge density is the result of different hydrolysis protocols and likely to be a key factor for differences in their dispersibility and the morphology of polymer nanocomposites produced from such dispersions (vide infra). To investigate to what extent the successful processing protocols for nanocomposites comprising cellulose nanowhiskers isolated from tunicates and cotton (solution-casting from dimethyl formamide, DMF, and the template approach) could be applied to MCC, we prepared a series of nanocomposites based on a rubbery 1:1 ethylene oxide-epichlorohydrin copolymer (EO-EPI). Given the similar dimensions of cotton-based and MCC derived nanowhiskers, these two llers were studied in a comparative mode. Between 0 and 35% v/v of either cellulose type were incorporated into the matrix polymer via solution

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Figure 3. Pictures of cellulose gels created from nanowhiskers isolated from cotton (left) or microcrystalline cellulose (MCC, right).

Figure 2. Shear storage moduli, Gc, of EO-EPI nanocomposites comprising either cellulose nanowhiskers isolated from cotton (triangles) or microcrystalline cellulose (MCC, circles) at 25 C. The nanocomposites were created via either solution-casting (open shapes) or the template approach (lled shapes). The experimental data were t to the percolation model for mechanical reinforcement (solid line). Error bars represent standard error, and are only shown for samples with at least three repeated measurements.

casting from DMF. The mechanical properties of these materials were established by dynamic mechanical thermal analysis (DMTA). Figure 2 shows the shear storage moduli (Gc) of dry EO-EPI nanocomposites extracted from the DMTA traces for a temperature of 25 C, that is, in the rubbery regime of the matrix. In case of the cotton nanowhisker nanocomposites, Gc increased with the nanowhisker content from 1.6 (neat polymer) to 43 MPa (24% v/v whiskers). By contrast, Gc of the MCC nanowhisker nanocomposites increased from 1.6 MPa (neat polymer) to just 17 MPa at a similar whisker content (25% v/v MCC). Thus, while in both cases a signicant increase in stiffness is observed, the reinforcing effect of the cotton nanowhiskers is more than twice as large as that observed for the MCC. The reinforcement observed in the cotton nanowhisker nanocomposites is, as we demonstrated before,14 related to the formation of a percolating nanober network in which stress transfer is facilitated by hydrogen-bonding between the nanowhiskers. Under these circumstances, the mechanical properties can be predicted by calculations obtained using a percolation model.16 Within the framework of the model, Gc can be expressed as28,29

(1 - 2 + Xr)GsGr + (1 - Xr)Gr2 Gc ) (1 - Xr)Gr + (Xr - )Gs

with

(1)

) Xr

Xr - Xc 1 - Xc

0.4

(2)

where is the volume fraction of nanowhiskers that participate in the load transfer, Xr is the volume fraction of the randomly orientated ller, Gs is the experimentally determined shear storage modulus of the neat EO-EPI (1.6 MPa), and Xc is the critical whisker percolation volume fraction calculated by 0.7/ A. A is the aspect ratio of the ller (10.5 for cotton nanowhiskers and 11 for MCC nanowhiskers). The shear storage modulus of the network formed by the rigid phase, Gr, for the EO-EPI/

cotton whisker nanocomposites was determined to be 250 MPa from a least-squares t of eq 1.14a The t utilized experimental values for A, Xc, Xr, and Gs and experimental results for Gc. The determined value for Gr was slightly higher than the value reported by Yamanaka et al. for cotton whiskers (85 MPa).30 While the experimental results for the solution-cast EO-EPI/ cotton nanowhisker nanocomposites match with the percolation model (above the onset of percolation),14a the solution-cast EOEPI/MCC nanocomposites do not exhibit the predicted reinforcement (Figure 2). The limited reinforcing effect of the MCC nanowhiskers can, in principle, be related to a lower stiffness of the individual nanobers, lower interactions among them (and/or with the matrix) when incorporated into the polymer matrix, or as discussed above and suggested by others,21 stied formation of a percolating network due to particle aggregation. Note that below the percolation threshold, the nanocomposites surpass the predictions of the percolation model, which neglects the reinforcing effect achieved by the incorporation of noninteracting reinforcing agents.31 As pointed out above, TEM images of the neat MCC nanowhiskers (Figure 1), and the absence of surface charges indeed suggest that aggregation may be at play. Moreover, the data points of the solution-cast MCC nanowhisker nanocomposites (Figure 2, open circles) would be difcult to t to the percolation model, even if a lower intraparticle interaction strength or lower nanober stiffness was assumed. The data are consistent with the hypothesis that at low MCC concentrations, the fraction of not dispersed MCC particles plays a more pronounced role than at higher concentrations, in that it lowers the actual contribution of nanowhiskers that participate in the percolating network. Finally, the solution-cast EO-EPI nanocomposite comprising 35% v/v MCC reached a Gc of 73 MPa, matching that of a cellulose nanowhisker nanocomposite of similar concentration; because at high loading levels increased ller content only marginally increases Gc, this data point seems to suggest that at higher loading levels percolation is in fact achieved in the MCC-based nanocomposites. To demonstrate this point, we sought to compare the properties of nanocomposites fabricated from preformed percolating networks of cotton and MCC nanowhiskers, respectively, utilizing the template approach.14a Despite their rather low aspect ratio, cellulose nanowhiskers isolated from cotton are able to form robust macroscopic gels (Figure 3) if the dispersing solvent (water) is carefully exchanged with a miscible nonsolvent (acetone). We previously exploited the fact that such gels form porous scaffolds and can be imbibed with any polymer if placed in a solvent that does not redisperse the nanowhiskers (see Experimental Section for nanocomposite fabrication).14a Unfortunately, only nanowhisker-rich compositions could be created on account of the high molecular weight of the host polymer used (resulting in high viscosity solutions).14a Indeed here, EO-EPI/cotton whisker nanocomposites created with the template approach exhibit the predicted reinforcement of the percolation model and match the mechanical properties of solution-cast materials

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(Figure 2).14a For template-made EO-EPI/cotton whisker nanocomposites, Gc increases from 1.6 MPa (neat polymer) to 56 MPa for a 32.4% v/v cotton whisker nanocomposite, and up to 74 MPa for material comprising 48.1% v/v whiskers. We produced MCC gels in the same manner (Figure 3) and were able to fabricate EO-EPI/MCC nanocomposites by the template approach. These materials display signicantly higher moduli than the solution-cast materials. For example, the Gc of EOEPI/MCC nanocomposites with 25% v/v MCC increased from 18 MPa for solution-cast materials to 39 MPa for templatemade materials. Figure 2 shows that Gc of EO-EPI/MCC nanocomposites created with the template approach follows the predicted reinforcement of the percolation model. EO-EPI/MCC nanocomposites with 42.3% v/v MCC reach a Gc of 73 MPa, which is similar to the 74 MPa for the nanocomposite comprising 48.1% v/v cotton whiskers. The data shown in Figure 2 clearly demonstrate that if appropriately processed, for example, by fractionating the nanowhiskers and employing the template approach, MCC-based nanocomposites can display virtually identical mechanical properties as nanocomposites comprising cellulose nanowhiskers isolated from cotton. The excellent agreement of the experimental Gc with predictions of the percolation model suggests that the percolating network of the MCC nanoparticles formed in a sol/gel process is maintained through the steps of imbibing with polymer, drying, and compression molding into lm samples. The results imply that the percolating network formed by the MCC brils is comparable to that of cellulose isolated from cotton.

SOURCE fellowship (to S.S.), and from the Department of Veterans Affairs Career Development Program (to J.C.).

References and Notes

(1) Ajayan, P. M.; Schadler, L. S.; Braun, P. B. Nanocomposite Science and Technology Wiley VCH: Weinheim, 2003. (2) Whitesides, G. M. Small 2005, 1, 172. (3) Hussain, F.; Hojjati, M.; Okamoto, M.; Gorga, R. E. J. J. Compos. Mater. 2006, 40, 1511. (4) For recent reviews see:(a) Azizi Samir, M. A.; Alloin, F.; Dufresne, A. Biomacromolecules 2005, 6, 612. (b) Dufresne, A. J. Nanosci. Nanotechnol. 2006, 6, 322. (c) Hubbe, M. A.; Rojas, O. J.; Lucia, L. A.; Sain, M. BioResources 2008, 3, 929. (5) Sturcova, A.; Davies, J. R.; Eichhorn, S. J. Biomacromolecules 2005, 6, 1055. (6) van den Berg, O.; Schroeter, M.; Capadona, J. R.; Weder, C. J. Mater. Chem. 2007, 17, 2746. (7) Capadona, J. R.; Shanmuganathan, K.; Tyler, D. J.; Rowan, S. J.; Weder, C. Science 2008, 319, 1370. (8) Wgberg, L.; Decher, G.; Norgren, M.; Lindstrom, T.; Ankerfors, M.; Axnas, K. J. Mater. Chem. 2007, 17, 2746. (9) Schroers, M.; Kokil, A.; Weder, C. J. Appl. Polym. Sci. 2004, 93, 2883. (10) Bonini, C.; Heux, L.; Cavaille, J. Y.; Lindner, P.; Dewhurst, C.; Terech, P. Langmuir 2002, 18, 3311. (11) Gousse, C.; Chanzy, H.; Excofer, G.; Soubeyrand, L.; Fleury, E. Polymer 2002, 42, 2645. (12) Araki, J. M.; Wada, M.; Kuga, S. Langmuir 2001, 17, 21. (13) Yuan, H.; Nishiyama, Y.; Wada, M.; Kuga, S. Biomacromolecules 2006, 7, 696. (14) (a) Capadona, J. R.; van den Berg, O.; Capadona, L. A.; Schroeter, M.; Rowan, S. J.; Tyler, D. J.; Weder, C. Nature Nanotech. 2007, 2, 765. (b) van den Berg, O.; Capadona, J. R.; Weder, C. Self-Assembled Nanober Templates: A Versatile Approach for Polymer Nanocomposites, U.S. Provisional Patent Application led, 2007. (15) (a) Nakagaito, A. N.; Yano, H. Appl. Phys. A: Mater. Sci. Process. 2005, 80, 155. (b) Henriksson, M; Berglund, L. J. Appl. Polym. Sci. 2007, 106, 2817. (16) Favier, V.; Chanzy, H.; Cavaille, J. Y. Macromolecules 1995, 28, 6365. (17) Battista, O. A. Ind. Eng. Chem. 1950, 42, 502. (18) Petersson, L.; Kvien, I.; Oksman, K. Compos. Sci. Technol. 2007, 67, 2535. (19) Battista, O. A. Microcrystal Polymer Science, 1st ed.; McGraw Hill: New York, 1975, Chapter 2. (20) Petersson, L.; Oksman, K. Compos. Sci. Technol. 2006, 66, 2187. (21) Wu, Q.; Henriksson, M.; Liu, X.; Berglund, L. A. Biomacromolecules 2007, 8, 3687. (22) Braun, B.; Dorgan, J.; Knauss, D. J. Polym. EnViron. 2006, 14, 49. (23) Dong, X. M.; Kimura, T.; Revol, J-F.; Gray, D. G. Langmuir 1996, 12, 2076. (24) Sun, C. J. Pharm. Sci. 2005, 94, 2132. (25) Le Cam, E.; Frechon, D.; Barray, M.; Fourcade, A.; Delain, E. Proc. Natl. Acad. Sci. U.S.A. 1994, 91, 11816. (26) Gere, J. M.; Timoshenko, S. P. Mechanics of Materials, 3rd ed; Pearson Higher Education: New Jersey, 1990. (27) van den Berg, O.; Capadona, J. R.; Weder, C. Biomacromolecules 2007, 8, 1353. (28) Takayanagi, M.; Uemura, S.; Minami, S. J. Polym. Sci., Part C: Polym. Lett. 1964, 5, 113. (29) Ouali, N.; Cavaille, J. Y.; Perez, J. Plast., Rubber Compos. 1991, 16, 55. (30) Yamanaka, S.; Watanabe, K.; Kitamura, N.; Iguhci, M.; Mitsuhashi, S.; Nishi, Y.; Uryu, M. J. Mater. Sci. 1989, 24, 3141. (31) Morin, A.; Dufresne, A. Macromolecules 2002, 35, 2190.

Conclusions
The ability to produce polymer nanocomposites, which comprise a percolating, three-dimensional network of wellindividualized nanobers, is important to diverse areas of polymer science. While MCC has been previously shown to improve the mechanical properties of polymer composites, it has thus far not been reported to form brous percolating networks within the nanocomposites. This limitation has resulted in polymer composites that did not exploit the full reinforcing potential of MCC. Through the utilization of optimized processing conditions, nanowhisker fractionation and the template approach, we here describe for the rst time the formation of EO-EPI/MCC nanocomposites, which achieve the maximum mechanical reinforcement predicted by the percolation model. The materials reported display signicantly improved mechanical properties, which are of interest in their own right. However, more importantly, the application of the template approach to MCC nanocomposite fabrication promises to expand upon the abundant uses of MCC in composite applications, while further supporting the signicance of the newly developed technique. Acknowledgment. We thank Dr. Midori Hitomi for the TEM characterization and acknowledge generous nancial support through an Ohio Innovation Incentive Fellowship (to K.S.), a

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