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Hybrid sol–gel coatings are widely used as protective layers for aluminum alloys because of their barrier abilities. This study aims at explaining the barrier properties of a sol–gel coating based on alkyltrimethoxysilane and methacrylate resin by its film structure. This approach was examined by modifying one photopolymerization parameter, e.g., by varying the content of radical photoinitiator. By neutral salt spray test and electrochemical impedance spectroscopy, the barrier properties are highlighted. The film structure is related to thermomechanical properties of films whose glass transition temperature and elastic modulus are measured by dynamic mechanical analysis and nanoindentation, respectively. On a finer scale, conversion of methacrylate functions calculated from Fourier transform infrared spectroscopy has given information on the chemical structure of films. The morphology of these coatings is studied by scanning electron microscopy, transmission electron microscopy, atomic force microscopy operating in tapping mode, and X-ray diffraction. Results revealed that formulations containing between 3 and 9 wt% of radical photoinitiator exhibit the maximal conversion of methacrylate functions and, at a microscopic scale, a homogeneous coating where the two organic and inorganic networks are well interpenetrated. This hybrid sol–gel microstructure corresponds to the highest glass transition temperature and the highest mechanical characteristics (elastic modulus, E and hardness, H) and the highest protection performance. This results in the best barrier properties, and thus the highest corrosion resistance. [ABSTRACT FROM AUTHOR]

Nanofibrillated cellulose (NFC) was used as bio-based stabilizing agent in the heterophase polymerization of methyl methacrylate (MMA) to nanoscale poly(methyl methacrylate) (PMMA) spheres. NFC/MMA suspensions at different NFC/MMA ratios were prepared in water, and the suspension stability was evaluated before the subsequent polymerization. The resulting polymerization products as well as products from several control experiments were analyzed via optical microscopy, SEM, and isolation experiments associated with thermogravimetric analysis. PMMA spheres had diameters in the range of 150-250 nm and were regularly distributed within the NFC network, whereas NFC acted as a stabilizer during the polymerization. The appearance of the resulting PMMA spheres within the NFC network was influenced by different factors, such as the reaction conditions, the initiator, and the solubility of the monomer. [ABSTRACT FROM AUTHOR]

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 36 weeks. 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. [ABSTRACT FROM AUTHOR]

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 (Cu). The increase in copper adsorption on the nanofibers correlated both with the pH and carboxylate content and reached maximum values of 135 and 55 mg g 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. [ABSTRACT FROM AUTHOR]

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 47 g/m and pore sizes in the 3-200 nm range are 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. [ABSTRACT FROM AUTHOR]

The study explores the potential of cellulose nanocrystals (CNC), cellulose nanofibers (CNF) and chitin nanocrystals (ChNC) isolated from bioresidues to remove silver ions from contaminated water. Zeta sizer studies showed negatively charged surfaces for CNC and CNF isolated from cellulose sludge in the acidic and alkaline pHs, whereas ChNC isolated from crab shell residue showed either positive or negative charges depending on pH conditions. Model water containing silver ions showed a decrease in Ag ion concentration (measured by inductively coupled plasma-optical emission spectrometer; inductively coupled plasma mass spectrometry), after treatment with CNC, CNF and ChNC suspensions. The highest Ag ion removal was measured near neutral pH for CNC, being 34.4 mg/g, corresponding to 64 % removal. ChNC showed 37 % and CNF showed 27 % removal of silver ions. The WDX (wavelength dispersive X-ray analysis) and XPS (X-ray photoelectron spectroscopy) analysis confirmed the presence of silver ions on the surface of the nanocellulose and nanochitin after adsorption. Surface adsorption on the nanoparticles via electrostatic interactions is considered to be the prominent mechanism of heavy metal ion capture from aqueous medium, with CNC with negative surface charge and negatively charged functional groups being most favourable for the adsorption of positively charged Ag ions compared to other native bionanomaterials. [ABSTRACT FROM AUTHOR]