Negative Diamagnetic Anisotropy and Birefringence of Cellulose Nanocrystals

We report magnetic birefringence measurements up to high fields (17.5 T) of dilute aqueous suspensions of rod-like cellulose nanocrystals with well characterized distributions of lengths, widths and thicknesses. We compare these data with three models, one with colinear (1), one with perpendicular cylindrically symmetric tensors for diamagnetic susceptibility and refractive index (2) and one with biaxial diamagnetic anisotropy (3). We find that taking into account polydispersities of length, width, and thickness is essential for accurate fitting and that model 1 is the most appropriate, presumably because of the twisting of the suspended nanocrystal along their long axis. The best-fitted susceptibility anisotropy was Δχ z ( xy ) = χ zz –(χ xx +χ yy )/2 = −2.44 × 10 –6 when considering only the crystalline core of nanocrystals and, more appropriately, Δχ z ( xy ) = −0.95 × 10 –6 when including crystalline core and skin. The latter value is slightly higher than Δχ z ( xy ) = −0.68(5) × 10 –6 deduced from estimations using Pascal’s additivity law. The specific birefringence of the nanocrystals in water was found to be δn 0 = +0.120(2), which is well accounted for by the intrinsic birefringence of crystalline cellulose ( δn 0 intr = n ∥ – n ⊥ = +0.0744) and the birefringence arising from the slender shape of nanocrystals.