Supporting Information for

Transcription

1 Supporting Information for Phosphorylated cellulose nanofibrils: A renewable nanomaterial for the preparation of intrinsically flameretardant materials Maryam Ghanadpour,*, Federico Carosio, Per Tomas Larsson, ξ and Lars Wågberg,,* Department of Fiber and Polymer Technology, KTH Royal Institute of Technology, SE Stockholm, Sweden Dipartimento di Scienza Applicata e Technologia, Politecnico di Torino, sede di Alessandria, Viale Teresa Michel 5, Alessandria, Italy Wallenberg Wood Science Center at the Department of Fiber and Polymer Technology, KTH Royal Institute of Technology, SE Stockholm, Sweden ξ Innventia AB, Drottning Kristinas Väg 61, SE , Stockholm, Sweden 1-S

2 Supplementary information Concentration of different elements on unmodified and phosphorylated fibers from XPS study, values of bulk and surface DS phosphate/carboxylate and total charge of unmodified and phosphorylated fibers and the gravimetric yield, mechanical properties and cone calorimeter data of phosphorylated CNF. Table S1. Relative surface concentrations of C, O and P elements on unmodified and phosphorylated fibers determined by XPS Relative Surface concentration % C O P Unmodified L10 H L30 H L60 H L90 H S

3 Table S2. Values of bulk DS phosphate and bulk DS carboxylate from XPS and total charge determined by conductometric titration for unmodified and phosphorylated fibers Bulk Charges (µeq/g) from phosphate Bulk Charges (µeq/g) from carboxylate Total charge (µeq/g) (conductometric DS phosphate groups a DS carboxylate groups b titration) Unmodified ± ± ± 7 L ± ± ± ± ± 7 L ± ± ± ± ± 8 L ± ± ± ± ± 45 L ± ± ± ± ± 48 H ± ± ± ± ± 12 H ± ± ± ± ± 18 H ± ± ± ± ± 37 H ± ± ± ± ± 6 a Calculated for dibasic acids based on DS values obtained from XPS b Calculated for monobasic acids based on DS values obtained from XPS 3-S

4 Table S3. Values of total charge, gravimetric yield and width of enzymatic and phosphorylated CNF (the work of Fall et al. 1 and the present work) Total Charge Gravimetric Width Width (µeq/g) yield (%) (nm)/afm (nm)/cryo-tem Enzymatic CNF P-CNF ± ± ± 1.2 P-CNF ± ± ± 1.2 P-CNF ± ± ± 0.8 Table S4. Mechanical properties of the nanopaper sheets prepared in the present work and from the work of Henriksson et al. 2 Nanopaper Viscosity Density Strain at Specific strength Specific modulus sample DP (kg/m 3 ) break (%) (Nm/kg) *10-5 (Nm/kg) *10-6 P-nanosheet ± ± ± ± 0.21 DP ± ± ± ± 0.62 DP ± ± ± ± 1.15 DP ± ± ± ± S

5 Table S5. Values of bulk and surface DS phosphate (per anhydroglucose unit) for unmodified and phosphorylated fibers, as determined by XPS and NMR. The surface-to-volume ratio (q) determined from NMR spectra used for calculating the surface DS phosphate was ± Total charge (µeq/g) Bulk DS phosphate (XPS) Surface DS phosphate on fibril aggregate(nmr) Unmodified 65 ± L ± ± ± 0.02 L ± ± ± 0.02 H ± ± ± 0.03 H ± ± ± 0.03 Table S6. Cone Calorimeter data for the filter paper and the P-nanosheet TTI (s) PHRR (kw/m 2 ) THR (MJ/m 2 ) Residue (%) Filter paper 44 ± ± ± ± 1 P-nanosheet Not recorded a Not recorded a Not recorded a 28 ± 6 a TTI, PHRR and THR were not recorded since all P-nanosheet showed no ignition 5-S

6 Figure S1. Images of the filter paper and the P-nanosheet before and after cone calorimetry test References (1) Fall, A. B.; Lindström, S. B.; Sundman, O.; Ödberg, L.; Wågberg, L. Langmuir 2011, 27, (2) Henriksson, M.; Berglund, L. A.; Isaksson, P.; Lindström, T.; Nishino, T. Biomacromolecules 2008, 9, S