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In this study, changes in the vibro-mechanical properties of fungi-treated wood, during sorption and desorption at different humidity levels, were investigated. Norway spruce resonance wood (with uniform narrow annual rings and high tonal quality for musical instrument craftsmanship) was incubated with Physisporinus vitreus for 36weeks. Stiffness, internal friction, and tonal performance indices of control (untreated) and fungi-treated wood were compared after exposure to a stepwise variation of relative humidity. It was demonstrated that fungal treatment increased the internal friction and decreased the specific modulus of elasticity, during reduction of wood density. Internal friction of both control and fungi-treated wood significantly increased during dynamic sorption, especially during early stages (hours) of each humidity change step. Both specific modulus of elasticity and internal friction showed a hysteretic behavior during humidity variation cycles. Hysteresis was smaller in fungi-treated wood. Also, tonal performance indices were improved after fungal treatment and showed a reduced variation at different relative humidity conditions. Dynamic vapor sorption tests and FT-IR microscopy studies revealed changes in hygroscopicity and the supramolecular structure of wood, which may explain the observed vibrational behavior. Less dependency of wood vibrational properties to the variation of the ambient humidity is important for the acoustic performance of string instruments.

Biobased nanofibers are increasingly considered in purification technologies due to their high mechanical properties, high specific surface area, versatile surface chemistry and natural abundance. In this work, cellulose and chitin nanofibers functionalized with carboxylate entities have been prepared from pulp residue (i.e., a waste product from the pulp and paper production) and crab shells, respectively, by chemically modifying the initial raw materials with the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) mediated oxidation reaction followed by mechanical disintegration. A thorough investigation has first been carried out in order to evaluate the copper(II) adsorption capacity of the oxidized nanofibers. UV spectrophotometry, X-ray photoelectron spectroscopy and wavelength dispersive X-rays analysis have been employed as characterization tools for this purpose. Pristine nanofibers presented a relatively low content of negative charges on their surface thus adsorbing a low amount of copper(II). The copper adsorption capacity of the nanofibers was enhanced due to the oxidation treatment since the carboxylate groups introduced on the nanofibers surface constituted negative sites for electrostatic attraction of copper ions (Cu2+). The increase in copper adsorption on the nanofibers correlated both with the pH and carboxylate content and reached maximum values of 135 and 55mgg−1 for highly oxidized cellulose and chitin nanofibers, respectively. Furthermore, the metal ions could be easily removed from the contaminated nanofibers through a washing procedure in acidic water. Finally, the adsorption capacity of oxidized cellulose nanofibers for other metal ions, such as nickel(II), chromium(III) and zinc(II), was also demonstrated. We conclude that TEMPO oxidized biobased nanofibers from waste resources represent an inexpensive and efficient alternative to classical sorbents for heavy metal ions removal from contaminated water.

Films of cellulose nanofibrils (CNF) (referred to as nanopaper) present a great potential in many applications due to the abundance, low environmental impact, excellent oxygen barrier properties and good mechanical performance of CNF. However, the strong hygroscopic character of the natural nanofibers limits their use in environments with high relative humidity. In this paper, we introduce a simple route for the esterification and processing of CNF with the aim of reducing their hydrophilicity, and producing hydrophobic cellulose nanopaper with reduced moisture sensitivity. The preparation steps of hydrophobic nanopapers involve vacuum filtration, solvent exchange from water to acetone, and reaction with anhydride molecules bearing different hydrophobic alkyl chains by hot pressing. Porous films having a surface area between 38 and 47g/m2 and pore sizes in the 3-200nm rangeare obtained. This method preserves the crystalline structure of native cellulose, and successfully introduces hydrophobic moieties on CNF surface as confirmed by FTIR, XPS and elemental analysis. As a result, modified nanopapers have a reduced moisture uptake, both higher surface water contact angle and wet tensile properties as compared with reference non-modified nanopaper, thus illustrating the benefit of the modification for the use of cellulose nanopaper in humid environments.

Native cellulose nanofibers (CNF) constitute an abundant resource for pyrolysis leading to char materials offering a wide range of properties and application possibilities. With the aim to produce chars having large surface area and pore volume for dyes adsorption and oil absorption, respectively, we herein explore the slow pyrolysis process of cellulose nanofibers from wood, Cladophora algae and bacteria that were subjected to various drying routes. Whereas algae CNF with their large crystallites lead to high surface area (S-BET) substrates using conventional drying from aqueous suspension, CNF from wood having smaller crystallites requires drying from solvents to reach high S-BET substrates, which results in chars with a good adsorption capacity for both anionic and cationic dyes. Moreover, the porosity of the CNF substrate can be tuned via an ice-templating freeze-drying procedure reaching values as high as 99.7% and corresponding chars capable of absorbing 64-120 g g(-1) of various oils and organic solvents. Besides the absorption/adsorption properties of the chars, we report effects of CNF source and structure on the thermal properties assessed by thermogravimetric and thermomechanical analyses, differential scanning calorimetry, and mass spectrometry, and we identified over 20 decomposition products and 3 expansion events occurring during CNF pyrolysis., QC 20170510

Cellulose nanocrystals (CNCs) with different charge densities were utilized to examine the role of electrostatic interactions on surface-initiated atom transfer radical polymerization (SI-ATRP) in aqueous media. To this end, growth of hydrophilic uncharged poly(N,N-dimethylacrylamide) (PDMAM) brushes was monitored by electrophoresis, 1H NMR spectroscopy, and dynamic light scattering (DLS). Molecular weight and polydispersity of PDMAM brushes was determined by GPC analysis of hydrolytically cleaved polymers. Initiator and polymer brush grafting densities, and thus, initiator efficiencies were derived from elemental analysis. Higher initiator efficiency of polymer brush growth was observed for CNCs with higher anionic surface sulfate half-ester group density, but at the expense of high polydispersity caused by inefficient deactivation. PDMAM grafts with number-average molecular weights up to 530 kDa and polydispersity indices <1.5 were obtained under highly diluted monomer concentrations. The role of surface chemistry on the growth of neutral polymer brushes from CNCs in water is emphasized and a model of the interfacial region at the onset of polymerization is proposed. The results presented here could have implications for other substrates that present surface charges and for the assumption that the kinetics of Cu-mediated SI-CRP are analogous to those conducted in solution., Peer Reviewed, Postprint (updated version)