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1 Supporting Inoration or Surace ngineering o Ultraine ellulose Nanoibrils towars Polyer Nanocoposite Materials By Shuji Fujisawa, Tsuguyuki Saito, Satoshi Kiura, Taahisa Iwata, an Akira Isogai* *orresponing author. -ail: aisogai@ail.ecc.u-tokyo.ac.jp This ile inclues: Supporting igures, Figs. S to S Supporting Tables S

2 Deterination o Average Distance between Two Ajacent Grating Points on TMPO-Oxiize ellulose Nanoibril Suraces The average ensity o carboxyl groups on the TMPO-oxiize cellulose nanoibril suraces was eterine by ollowing equation : H OH H OH where H OH is the average ensity o 6 priary hyroxyl groups expose on the original cellulose icroibril surace, an H OH an are the contents o 6 priary hyroxyl group expose on the original cellulose crystalline surace an 6 carboxyl groups o the TMPO-oxiize cellulose, respectively, expresse as ol per ol o onoer unit ol ol o onoer unit. The paraeters, OH, an were expresse as ollows. OH H Because the length o the repeating cellobiose unit in cellulose chains is.04 n, escribe as: S H OH H H OH was where is a -spacing o 0.60 n, which correspons to the 0 plane o cellulose I β, an is 0.4 n, which correspons to the 0 plane o cellulose I β. S In this stuy, cellulose icroibrils were assue to have square cross sections with sies o the sae length. S3 Fro equation, H OH was calculate to be.7 n. Following a previous paper, H OH was expresse by the ollowing equation 3: H OH 3

3 where an are crystal sizes o 3. an 4. n, which correspon to an, respectively, S an H OH was eterine to be 0.3 ol ol o the onoer unit. Because the olecular weights o glucuronosyl aci Na salt an glucosyl units are 9 an 6, respectively, H OH is expresse as: S B B 6 4 where B is the carboxylate content o TMPO-oxiize cellulose ol g, which was eterine by the conuctivity titration etho to be.3 ol g. Fro equation 4, was calculate to be 0. ol ol o the onoer unit. Fro equation 4, was eterine to be.6 n The average istance between two ajacent carboxyl groups on the TMPO-oxiize cellulose nanoibril suraces D was presente as: A D H OH H OH A is the conversion ratio ro ree carboxyl groups to aine salt oration calculate by eleental analysis to be. Fro equation, D was eterine to be 0.7 n. The Thickness o the Polyer Brush Layer on ellulose Nanoibril Suraces For polyer chains in a goo solvent, the chain size is eine by the Flory raius R F : S4 S6 R F an 3 6 where a an N are the size o the onoer units an the egree o polyerization o the grate chains, respectively. For PG chains, a is 0.3 n, an in this stuy, N was 4. The R F calculate by equation 6 is 3.6 n while average istance between two ajacent grating points D is 0.7 n; the grating points are so close to each other that grate PG chains are orce 3

4 to stretch away ro the grat surace to avoi overlapping. When D < R F, the thickness o grate chain layer L in a goo solvent was estiate as: S4,S L anad 3 D < R F 7 Fro equation 7, the thickness o PG layer was estiate to be ~ n. The Light Transittances o PG-Grate ellulose NanoibrilOrganic Solvent Dispersions 00 Transittance % Light transittance at 600 n in toluene 99.6% in chloroor 96.7% in THF 94.4% Wavelength n Figure S. U-vis transittance spectra o 0.4 % wv PG-grate cellulose nanoibril ispersions in toluene, chloroor, an THF. The ierence in light transittance is ue to that in reractive inex between TMPO-oxiize cellulose nanoibril an the solvent. The reractive inices o TMPO-oxiize cellulose nanoibril, toluene, chloroor, an THF are.4,.49,.44, an.40, respectively, at ; a larger ierence in reractive inex causes higher light scattering. 4

5 Theral Properties o PG-Grate ellulose NanoibrilsPLLA Nanocoposite The egree o crystallinity X c o the PLLA atrix was estiate ro DS therogras o the coposites using the ollowing equation : S7 where H is the elting enthalpy an H c is the crystallization enthalpy o the PLLA coponent o the coposites. H c is the theoretical elting enthalpy o 00% crystalline PLLA 93.0 Jg. S7 Theoretical Approach or Preicting Young s Moulus o the oposites The ollowing our ierent oels were use to preict the Young s oulus o each PGgrate cellulose nanoibrilplla nanocoposite, assuing that the nanoibrils were ranoly lainate in the atrix, an the results were copare with experiental values.. Halpin-Tsai oel S, S9 where an are the ouli o a single cellulose nanoibril an the PLLA atrix, respectively, an l,, an are the length, with, an volue raction o cellulose nanoibrils in the coposite, respectively. was calculate assuing that the ensities o cellulose nanoibril an PLLA were.6 an.6 g c 3, respectively. S0. oigt-reuss oel S T T L L HT 3 l L l T R 3 00% c c c H H H X

6 3. Moiie ixture law S,S MML 4. ox oel S S3 ox 0 L 0 tanh βs L βs l s r β π ν ln Tensile properties o the PG-grate cellulose nanoibrilplla coposite ils an paraeters use or the above oel calculations are shown in Tables S. Table S. Paraeters use or oels. GPa a GPa l n b n c ν a Reerence S4. b Average value estiate ro TM iages. c Reerence S Stress MPa Strain % Figure S. Stress strain curves o neat PLLA il soli black curve, PG-grate cellulose nanoibrilplla nanocoposite il containing.0 wt % cellulose an 3.0 wt % grate PG soli green curve, an PGPLLA coposite il containing 3 wt % PG otte green curve. 6

7 Supporting Inoration Reerences S Okita, Y.; Saito, T.; Isogai, A. Bioacroolecules 00,, S Waa, M.; Okano, T.; Sugiyaa, J. ellulose 997, 4, 3. S3 Revol, J.-F. arbohyr. Poly. 9,, S4 Israelachvili, J. N. Interolecular an Surace Forces, n e.; Acaeic Press: Lonon, 99; pp S De Gennes, P. G. Macroolecules 90, 3, S6 Zhao, B.; Brittain, W. J. Prog. Poly. Sci. 000,, S7 Na, J. Y.; Ray, S. S.; Okaoto, M. Macroolecules 003, 36, S Zhang, X.; Liu, T.; Sreekuar, T..; Kuar, S.; Moore,..; Hauge, R. H.; Salley, R..; Nano Lett. 003, 3,. S9 Halpin, J..; Karos, J. L.; Poly. ng. Sci. 976, 6, S0 Nishiyaa, Y.; Langan, P.; hanzy, H. J. A. he. Soc. 00, 4, S Guzán e illoria, R.; Miravete, A. Acta Matter. 007,, S Labore-Lahoz, P.; Maser, W.; Martinez, T.; Bonito, A.; Seeger, T.; ano, P.; Guzán e illoria, R.; Miravete, A. Mech. Av. Mater. Struct. 003, 9, S3 ox, H. L. Br. J. Appl. Phys. 9, 3, S4 Iwaoto, S.; Kai, W.; Isogai, A.; Iwata, T. Bioacroolecules 009, 0, S Saito, T.; Kuraae, R.; Wohlert, J.; Berglun, L. A.; Isogai, A. Bioacroolecules 03, 4,