Interfacial Mechanisms of Water Vapor Sorption into Cellulose Nanofibril Films as Revealed by Quantitative Models.

Humidity is an efficient instrument for facilitating changes in local architectures of two-dimensional surfaces assembled from nanoscaled biomaterials. Here, complementary surface-sensitive methods are used to collect explicit and precise experimental evidence on the water vapor sorption into (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) oxidized cellulose nanofibril (CNF) thin film over the relative humidity (RH) range from 0 to 97%. Changes in thickness and mass of the film due to water vapor uptake are tracked using spectroscopic ellipsometry and quartz crystal microbalance with dissipation monitoring, respectively. Experimental data is evaluated by the quantitative Langmuir/Flory-Huggins/clustering model and the Brunauer-Emmett-Teller model. The isotherms coupled with the quantitative models unveil distinct regions of predominant sorption modes: specific sorption of water molecules below 10% RH, multilayer build-up between 10 to 75% RH, and clustering of water molecules above 75% RH. The study reveals the sorption mechanisms underlying the well-known water uptake behavior of TEMPO oxidized CNF directly at the gas-solid interface.

Viscoelastic Properties of Core-Shell-Structured, Hemicellulose-Rich Nanofibrillated Cellulose in Dispersion and Wet-Film States.

We report the viscoelastic properties of core-shell-structured, hemicellulose-rich nanofibrillated cellulose (NFC) in dispersion and wet-film states. The hemicellulose-rich NFC (hemicellulose neutral sugars 23%, carboxylate 0.2 mmol g(-1)), prepared from Japanese persimmons, had a core crystallite thickness of 2.3 nm and unit fibril thickness of 4.2 nm. A carboxylate-rich NFC (hemicellulose neutral sugars 7%, carboxylate 0.9 mmol g(-1)) with crystallite and fibril widths of 2.5 and 3.3 nm, respectively, was used as a reference. The solid-concentration dependencies of the storage moduli of gel-like water dispersions of the hemicellulose-rich NFC were weaker than those of carboxylate-rich NFC, and the dispersions were loosely flocculated even at high salt concentrations and low pH values. The viscoelastic properties of wet NFC films were similar to those of their dispersions; the hemicellulose-rich NFC films were significantly less sensitive to salt concentration and pH and were soft and swollen at high salt concentrations and low pH values.

Direct Interfacial Modification of Nanocellulose Films for Thermoresponsive Membrane Templates.

This letter proposes a strategy to construct tunable films combining the physical characteristics of cellulose nanofibrils and smart polymers for membrane applications. A functional membrane template was obtained by first fabricating a water stable film from cellulose nanofibrils and subsequently surface grafting it with a thermoresponsive polymer, poly(N-isopropylacrylamide). The behavior of the membrane template was dependent on temperature. The increment in slope of relative water permeance around the lower critical solution temperature of poly(N-isopropylacrylamide) increased from 18 to 100% upon polymer attachment. Although the membrane template essentially consisted of wood-based materials, the benefits of smart synthetic polymers were achieved.

Effect of interfibrillar PVA bridging on water stability and mechanical properties of TEMPO/NaClO2 oxidized cellulosic nanofibril films.

TEMPO/NaClO2 oxidized cellulosic nanofibrils (TCNF) were covalently bonded with poly(vinyl alcohol) (PVA) to render water stable films. Pure TCNF films and TCNF-PVA films in dry state showed similar humidity dependent behavior in the elastic region. However, in wet films PVA had a significant effect on stability and mechanical characteristics of the films. When soaked in water, pure TCNF films exhibited strong swelling behavior and poor wet strength, whereas covalently bridged TCNF-PVA composite films remained intact and could easily be handled even after 24h of soaking. Wet tensile strength of the films was considerably enhanced with only 10 wt% PVA addition. At 25% PVA concentration wet tensile strengths were decreased and films were more yielding. This behavior is attributed to the ability of PVA to reinforce and plasticize TCNF-based films. The developed approach is a simple and straightforward method to produce TCNF films that are stable in wet conditions.