Amphiphilic cellulose nanocrystals from acid-free oxidative treatment: physicochemical characteristics and use as an oil-water stabilizer.

A chemical pretreatment for producing cellulose nanocrystals (CNCs) with periodate oxidation and reductive amination is reported. This new functionalization of cellulose fibers dispenses an alternative method for fabricating individual CNCs without the widely used acid hydrolysis process. CNCs can be directly modified during the pretreatment step, and no additional post-treatments are required to tune the surface properties. Three butylamine isomers were tested to fabricate CNCs with amphiphilic features. After mechanical homogenization, CNCs occurred as individual crystallinities without aggregation where high uniformity in terms of shape and size was obtained. The elemental analysis and (1)H NMR measurement show that iso- and n-butylamine attach the highest number of butylamino groups to the cellulose fibers. Linking the alkyl groups increases the hydrophobic nature of the CNCs, where water contact angles from self-standing films up to 110.5° are reported. Since these butylamino-functionalized CNCs have hydrophobic characteristics in addition to the hydrophilic backbone of cellulose, the stabilization impact on oil/water emulsions is demonstrated as a potential application.

Enhancement of the nanofibrillation of wood cellulose through sequential periodate-chlorite oxidation.

Sequential regioselective periodate-chlorite oxidation was employed as a new and efficient pretreatment to enhance the nanofibrillation of hardwood cellulose pulp through homogenization. The oxidized celluloses with carboxyl contents ranging from 0.38 to 1.75 mmol/g could nanofibrillate to highly viscous and transparent gels with yields of 100-85% without clogging the homogenizer (one to four passes). On the basis of field-emission scanning electron microscopy images, the nanofibrils obtained were of typical widths of approximately 25 ± 6 nm. All of the nanofibrillar samples maintained their cellulose I crystalline structure according to wide-angle X-ray diffraction results, and the crystallinity index was approximately 40% for all samples.

Phosphonated nanocelluloses from sequential oxidative-reductive treatment-Physicochemical characteristics and thermal properties.

Nanocellulosic materials with good thermal stability are highly desirable for applications, such as reinforcement and filler agents in composites. In the present work, phosphonated cellulose was utilized to obtain nanocelluloses with good thermal stability and potential intumescent properties. Phosphonated cellulose was synthetized from birch pulp via sequential periodate oxidation and reductive amination using a bisphosphonate group-containing amine, sodium alendronate, as a phosphonating reagent. After high-pressure homogenization, bisphosphonate cellulose nanofibres or nanocrystals were obtained, depending on the initial oxidation degree. Nanofibres had a typical diameter of 3.8nm and length of several micrometers, whereas nanocrystals exhibited a width of about 6nm and an average length of 103-129nm. All nanocelluloses exhibited cellulose I crystalline structures and high transparency in water solutions. Phosphonated nanocelluloses exhibited good thermal stability and a greater amount of residual char was formed at 700°C compared to birch pulp and mechanically produced, non-chemically modified NFC.

Distinctive green recovery of silver species from modified cellulose: mechanism and spectroscopic studies.

The present study aimed to recover precious silver in order to identify the adsorption coupled reduction pathways that determine this process. A combination technique of adsorption and nanocrystallization was used to investigate the recovery of silver species from taurine-cellulose (T-DAC) samples. The non-synthetic route of nanocrystallization yielded spherical zero-valent silver sized ∼ 18 nm. Rate-controlling steps were modeled by adsorption parameters by the best fit of Langmuir capacity (55 mg/g), pseudo-second order curves, and exothermic chemical reactions. The T-DAC was an excellent sorbing phase for the treatment of silver-polluted waters over a broad range of pH (2.1-10.1) and varying ionic strengths (8.5-850 mM, as NaCl), which are the conditions often encountered in industrial and mining effluents. A good recovery of silver (40-65%) was also obtained in the presence of Cd(II), Co(II), Cr(VI), Ni(II), and As(V) at lower or equivalent concentrations with Ag(I), either from individually added metals or from all metal ions mixed together. Desorption was compared with a series of five eluents including complexing agents. In these experiments acidified thiourea yielded 86% desorption of Ag(I). Aqueous silver reduced to metallic silver on the surface of the T-DAC samples, which was confirmed by X-ray photo electron spectroscopy.

Fabrication of cationic cellulosic nanofibrils through aqueous quaternization pretreatment and their use in colloid aggregation.

The aqueous pre-treatment of cellulose with periodate and Girard' reagent T was employed as a novel and promising method to promote nanofibrillation of wood pulp and to obtain cellulosic nanofibrils with cationic functionality (CNFC). To demonstrate the feasibility of CNFCs in particle aggregation, a kaolin clay model suspension was aggregated by the CNFCs. Direct high-pressure homogenization of cationized cellulose resulted in nanofibrils exhibiting typical widths of 10-50 nm and cationic charge densities ranging from 1.10 to 2.13 mequiv.g(-1). The nanofibril suspensions existed in the form of highly transparent gels and possessed cellulose I crystalline structures. All of the CNFCs promoted strong aggregation of kaolin and produced voluminous kaolin-CNFC aggregates with lateral dimensions of several millimeters. Moreover, the CNFCs maintained good aggregation performance through wide pH (3-9) and temperature (25-60 °C) ranges. Thus, CNFCs were shown to be highly potential candidates for replacement of present synthetic soluble flocculation and coagulation aids.

Optimization of dicarboxylic acid cellulose synthesis: reaction stoichiometry and role of hypochlorite scavengers.

The reaction conditions in terms of reaction time, sodium chlorite stoichiometry, and the effect of hypochlorite scavengers on the chlorite oxidation of dialdehyde cellulose (DAC) was studied. The impact of storage on the reactivity of DAC fibers was also investigated. It was found that chlorite oxidation of DAC is a rapid reaction, resulting in oxidation of 71% of the aldehyde after only 8 min when 2.5 times excess of sodium chlorite compared to aldehyde groups was used. Reactivity of DAC was observed to decrease quickly during the storage and only 68% of the aldehyde groups reacted after two weeks storage compared to the reaction performed with freshly prepared DAC. Hydrogen peroxide and sulfamic acid were observed to increase the reaction efficiency of chlorite oxidation by reducing the amount of side-reactions between chlorite and hypochlorite. A minor amount of sulfamic acid can be used to replace acetic acid as a catalyst.

Biocomposite cellulose-alginate films: promising packaging materials.

Biocomposite films based on cellulose and alginate were produced using unmodified birch pulp, microfibrillated cellulose (MFC), nanofibrillated cellulose (NFC) and birch pulp derivate, nanofibrillated anionic dicarboxylic acid cellulose (DCC), having widths of fibres ranging from 19.0 µm to 25 nm as cellulose fibre materials. Ionically cross-linked biocomposites were produced using Ca(2+) cross-linking. Addition of micro- and nanocelluloses as a reinforcement increased the mechanical properties of the alginate films remarkably, e.g. addition of 15% of NFC increased a tensile strength of the film from 70.02 to 97.97 MPa. After ionic cross-linking, the tensile strength of the film containing 10% of DCC was increased from 69.63 to 125.31 MPa. The biocomposite films showed excellent grease barrier properties and reduced water vapour permeability (WVP) after the addition of cellulose fibres, except when unmodified birch pulp was used.

Porous thin film barrier layers from 2,3-dicarboxylic acid cellulose nanofibrils for membrane structures.

To fabricate a strong hydrophilic barrier layer for ultrafiltration (UF) membranes, 2,3-dicarboxylic acid cellulose nanofibrils with high anionic surface charge density (1.2 mekv/g at pH 7) and a width of 22 ± 4 nm were used. A simple vacuum filtration method combined with a solvent exchange procedure resulted in a porous layer with a thickness of ∼ 0.85 µm. The fabricated membranes reached high rejection efficiencies (74-80%) when aqueous dextrans up to 35-45 kDa were filtrated to evaluate the molecular weight cut-offs (MWCO). A linear correlation between the barrier layer thickness and the flux rate was observed in all tested cases. Further optimization of the barrier layer thickness can lead to an even more effective structure.

Strong, self-standing oxygen barrier films from nanocelluloses modified with regioselective oxidative treatments.

In this work, three self-standing nanocellulose films were produced from birch pulp using regioselective oxidation and further derivatization treatments. The modified celluloses were synthesized using periodate oxidation, followed by chlorite oxidation, bisulfite addition, or reductive amination with amino acid taurine, which resulted in dicarboxylic acid cellulose (DCC), α-hydroxy sulfonic acid cellulose (HSAC), and taurine-modified cellulose (TC), respectively. The nanocelluloses were fabricated by mechanical disintegration using high-pressure homogenization. Mechanical and barrier properties of the nanocellulose films were characterized. Two (2,2,6,6-tetramethyl-piperidin-1-yl)oxyl (TEMPO) oxidation-based nanocellulose films were also produced, and their properties were compared to the periodate-based nanocellulose films. All of the periodate-based nanocellulose films showed high tensile strength (130-163 MPa) and modulus (19-22 GPa). Oxygen barrier properties of the films were superior to many synthetic and composite materials; in particular, the nanofibrillated DCC films had oxygen permeability as low as 0.12 cm(3) µm/(m(2) d kPa) at 50% relative humidity. Compared to films of TEMPO-oxidized nanocelluloses, all of the periodate-based nanocellulose films had similar or even better mechanical and barrier properties, demonstrating versatility of periodate oxidation to obtain nanocellulose films with adjustable properties. Also, for the first time, amino-acid-based cellulose modification was used in the production of nanocellulose.

High-strength nanocellulose-talc hybrid barrier films.

Hybrid organic-inorganic films mimicking natural nacre-like composite structures were fabricated from cellulose nanofibers obtained from sequential periodate-chlorite oxidation treatment and talc platelets, using a simple vacuum-filtration method. As a pretreatment, commercial talc aggregates were individualized into well-dispersed talc platelets using a wet stirred media mill with high-shear conditions to promote the homogeneity and mechanical characteristics of hybrids. The nanofiber-talc hybrids, which had talc contents from 1 to 50 wt %, were all flexible in bending, and possessed tensile strength and Young's modulus values up to 211 ± 3 MPa and 12 ± 1 GPa, respectively, the values being remarkably higher than those reported previously for nanofibrillated cellulose-talc films. Because of the lamellar and well-organized structure of hybrids in which the talc platelets were evenly embedded, they possessed a small pore size and good oxygen barrier properties, as indicated by the preliminary results. The talc platelets decreased the moisture adsorption of highly talc-loaded hybrids, although they still exhibited hydrophilic surface characteristics in terms of contact angles.

Use of nanoparticular and soluble anionic celluloses in coagulation-flocculation treatment of kaolin suspension.

In this work, the effectiveness of a novel, combined coagulation-flocculation treatment based on alum and soluble or nanoparticular anionic derivatives of dialdehyde cellulose, ADAC, was evaluated by studying the removal of colloidal material in a model suspension containing kaolin. Four different ADACs with varying degrees of substitution, size and water solubility were synthesized by periodate oxidation and sulfonation of cellulose. The effects of ADAC dosage, solution pH and temperature on flocculation were studied by measuring residual turbidity of the settled suspension. Moreover, the charge densities, sizes, ζ-potentials and stability of the ADACs in aqueous solutions were studied. The combined treatment was effective in the removal of colloidal particles, as demonstrated by reduced residual turbidity with remarkably lower total chemical consumption compared with coagulation with alum alone. Of the ADACs, samples with lower solubility that contained cellulose nanoparticles performed better than the fully water-soluble sample. Due to the restricted pH tolerance of alum, the combined treatment was effective only at acidic conditions (pH < 5), although the ADACs were found to be stable in a much broader pH range (pH of 3 to about 9). ADACs also retained strong activity at higher temperatures (30-60 °C) and after several days of storage in aqueous solution.

Flocculation performance of a cationic biopolymer derived from a cellulosic source in mild aqueous solution.

The flocculation behavior of cationic, quaternary ammonium groups containing cellulosic biopolymers, CDACs, synthesized by cationizing dialdehyde cellulose in mild aqueous solution was studied in a kaolin suspension. In particular, the role of CDAC dosage and solution pH, NaCl concentration, and temperature were clarified. In addition, the initial apparent charge densities (CDs), particle sizes, ζ-potential, and stability of CDs were determined. CDACs possessed a high flocculation activity in neutral and acidic solutions, but a significant decrease was observed in alkaline solutions (pH >9). This was also seen as a decline in the apparent CD and particle size of the CDACs in alkaline conditions. The measurements also indicated that the apparent CD decreased to a constant level of 3 mmol/g in aqueous solutions. However, no notable decrease in flocculation performance was obtained after several days of storage. Moreover, the variation of NaCl concentration and temperature did not affect the flocculation activity.

Chemical methods in the development of eco-efficient wood-based pellet production and technology.

Up to 20 million tons of waste wood biomass per year is left unused in Finland, mainly in the forests during forestry operations, because supply and demand does not meet. As a consequence of high heat energy prices, the looming threat of climate change, the greenhouse effect, and due to global as well as national demands to considerably increase the proportion of renewable energy, there is currently tremendous enthusiasm in Finland to substantially increase pellet production. As part of this European objective to increase the eco- and cost-efficient utilization of bio-energy from the European forest belt, the aim of our research group is - by means of multidisciplinary research, especially through chemical methods - to promote the development of Nordic wood-based pellet production in both the qualitative and the quantitative sense. Wood-based pellets are classified as an emission-neutral fuel, which means that they are free from emission trading in the European Union. The main fields of pellet research and the chemical toolbox that has been developed for these studies, which includes a new specific staining and optical microscope method designed to determine the cross-linking of pellets in the presence of various binding compounds, are described in this paper. As model examples illustrating the benefits of this toolbox, experimental data is presented concerning Finnish wood pellets and corresponding wood-based pellets that include the use of starch-containing waste potato peel residue and commercial lignosulfonate as binding materials. The initial results concerning the use of the developed and optimized specific staining and microscopic method using starch-containing potato peel residue as binding material are presented.