Thermal, biodegradation and theoretical perspectives on nanoscale confinement in starch/cellulose nanocomposite modified via green crosslinker.

In this research work, we propose a synergistic effect of a green crosslinker and cellulose nanomaterial on the crystallinity, viscoelastic, and thermal properties of starch nanocomposites. A disaccharide derivative was used as a bio crosslinker and nanofiber from pineapple leaf as a reinforcing phase for starch. Sucrose was oxidised using periodate, that can selectively oxidise the vicinal hydroxyl group of sucrose and form tetra aldehyde derivative. Crystallinity of films after crosslinking decreased with successive addition of crosslinker. The melting temperature of films increased because of formation of more dense structure after crosslinking. Morphological investigations were analysed by atomic force microscopy. Polymer chain confinement and mechanics were quantified. The crosslink densities of the films were calculated using two models, phantom model and affine model, using storage modulus data. By using very low amount of crosslinker and nanoreinforcement, the properties of thermoplastic starch were significantly improved.

Nanocomposites of LLDPE and Surface-Modified Cellulose Nanocrystals Prepared by Melt Processing.

Cellulose nanocrystals (CNCs) were surface modified by esterification in tetrahydrofuran (THF) at 25 °C using different catalysts and anhydrides bearing different alkyl side chain lengths. Unmodified and acetic anhydride (AcAnh)-modified CNCs were studied as potential nanofillers for linear low-density poly(ethylene) (LLDPE). Nanocomposites were prepared by melt processing. Determination of the size and size distribution of CNCs in the nanocomposites by SEM revealed an enhanced compatibility of the AcAnh-modified CNCs with the LLDPE matrix, since the average size of the aggregates of the modified CNCs (0.5⁻5 µm) was smaller compared to that of the unmodified CNCs (2⁻20 µm). Tensile test experiments revealed an increase in the nanocomposites' stiffness and strain at break-by 20% and up to 90%, respectively-at the CNC concentration of 5 wt %, which is close to the critical percolation concentration. Since the CNC nanofiller simultaneously reduced LLDPE crystallinity, the reinforcement effect of CNCs was hampered. Therefore, the molding temperature was increased to 120 °C, and, in this way, the greatest increase of the Young's modulus was achieved (by ~45%). Despite the enhanced compatibility of the AcAnh-modified CNCs with the LLDPE matrix, no additional effect on the mechanical properties of the nanocomposites was observed in comparison to the unmodified CNC.

Morphology, transport characteristics and viscoelastic polymer chain confinement in nanocomposites based on thermoplastic potato starch and cellulose nanofibers from pineapple leaf.

Eco-friendly "green" nano composites were fabricated from potato starch and cellulose nanofibers from pineapple leaf. Nanocomposites of starch/cellulose nanofibers were prepared by solution mixing followed by casting. The investigation of the viscoelastic properties confirms starch macromolecular chain confinement around the nano scale cellulose surface, superior dispersion and very good interaction between thermoplastic starch and cellulose nanofibers. The degree of chain confinement was quantified. The chain confinement was associated with the immobilization of the starch macromolecular chains in the network formed by the nano-scale cellulose fibers as a result of hydrogen boding interactions. From the results, it was assumed that the starch glycerol system exhibits a heterogenous nature and cellulose nanofibers tend to move towards glycerol rich starch phase. Barrier properties also improved with the addition of nanofiller up to 3wt.% but further addition depreciated properties due to possible fiber agglomeration. The kinetics of diffusion was investigated and typical kinetic parameters were determined and found that the nanocomposites follow pseudo fickian behaviour. The outcome of the work confirms that the prepared nanocomposites films can be used as a swap for packaging applications.

The fast and effective isolation of nanocellulose from selected cellulosic feedstocks.

A new process for the production of nanocellulose from selected cellulose-containing natural materials has been developed. The liquefaction reaction, using glycols and mild acid catalysis (methane sulphonic acid), was applied to four model materials, namely cotton linters, spruce wood, eucalyptus wood and Chinese silver grass. The process contains only four steps, the milling, the glycolysis reaction, centrifugation and final rinsing with an organic solvent. The nanocrystalline cellulose recovery was between 56% and 75%. The crystallinity index was greater than that of the starting materials due to the liquefaction of lignin, hemicelluloses and amorphous cellulose. The final product was a stable, highly concentrated nanocrystalline cellulose suspension in the organic medium. The liquid residue, after the liquefaction of the cotton linters contained significant quantities of levulinic acid. Different sugars were identified in the liquid residues that were derived from cellulose and hemicelluloses during the liquefaction reaction.

Liquefied Wood as Inexpensive Precursor-Feedstock for Bio-Mediated Incorporation of (R)-3-Hydroxyvalerate into Polyhydroxyalkanoates.

Liquefied wood (LW) prepared in a microwave process was applied as a novel; inexpensive precursor feedstock for incorporation of (R)-3-hydroxyvalerate (3HV) into polyhydroxyalkanoate (PHA) biopolyesters in order to improve the biopolyester's material quality; Cupriavidus necator was applied as microbial production strain. For proof of concept, pre-experiments were carried out on a shake flask scale using different mixtures of glucose and LW as carbon source. The results indicate that LW definitely acts as a 3HV precursor, but, at the same time, displays toxic effects on C. necator at concentrations exceeding 10 g/L. Based on these findings, PHA biosynthesis under controlled conditions was performed using a fed-batch feeding regime on a bioreactor scale. As major outcome, a poly(3HB-co-0.8%-3HV) copolyester was obtained displaying a desired high molar mass of Mw = 5.39 × 105 g/mol at low molar-mass dispersity (DM of 1.53), a degree of crystallinity (Xc) of 62.1%, and melting temperature Tm (176.3 °C) slightly lower than values reported for poly([R]-3-hydroxybutyrate) (PHB) homopolyester produced by C. necator; thus, the produced biopolyester is expected to be more suitable for polymer processing purposes.

Ultrasonically assisted liquefaction of lignocellulosic materials.

In our research, we have utilized high energy ultrasound for the liquefaction of different lignocellulosic materials, wood wastes in particular. We developed a highly efficient way of transforming this biomass waste into valuable chemicals. It was found, that the reaction yield in all experiments was high and that the reaction times were shortened up to nine times when using the ultrasound process with smaller residual particles and with no influence on the hydroxyl number of the final products. The use of the ultrasound process inhibits the formation of the large molecular structures during the liquefaction from the degradation products, by keeping the reactive segments apart and due to such a short reaction time being used. The short reaction time and subsequent low energy consumption for the liquefaction reaction leads to the creation of the new method for the transformation of the wood waste materials into valuable chemicals.

Structural evolution of indomethacin particles upon milling: time-resolved quantification and localization of disordered structure studied by IGC and DSC.

The amorphization of indomethacin was induced by milling. The mass fraction of the amorphous phase in the drug milled for various time intervals was determined with differential scanning calorimetry (DSC). Because the surface fraction amorphized by milling can be much higher than the mass fraction, which can have a large impact on the powder properties, a method for quantification of surface fraction amorphized by milling using inverse gas chromatography (IGC) was developed. A calibration curve was constructed by mixing completely amorphous indomethacin (obtained after milling for 120 min) with various amounts of the initial crystalline sample. Linear part of the curve was then used to quantify the surface amorphous content of samples milled for different time intervals. Surface and mass amorphization kinetics were determined and fitted to a first-order model. It was found that the surface amorphization rate is an order of magnitude higher than the mass amorphization rate. Results confirmed that IGC is a sensitive method for detection and quantification of the fraction of amorphous surface of milled indomethacin powder. If suitably combined with other techniques, this method represents a relatively general approach for the localization and quantification of the surface amorphous fraction in crystalline substances that transform into amorphous ones upon intensive milling.

Application of liquefied wood as a new particle board adhesive system.

Different types of southern European hardwoods and softwoods were subjected to a liquefaction process with glycerol/diethylene glycol. The liquefied spruce wood was reacted in a condensation reaction in the hot press with different melamine-formaldehyde and melamine-urea-formaldehyde resin precursors and used as adhesives for wood particle boards. The mechanical properties of these particle boards and the determination of formaldehyde release, proved that addition of 50% of the liquefied wood to such resin precursors caused the product to meet the European standard quality demands for particle boards. Up to 40% reduction of the formaldehyde emission was achieved. The temperature of the press unit was lowered from 180 degrees C to 160 degrees C with no significant influence on the mechanical properties. On the basis of the presented results it was possible to conclude that liquefied wood can be used as substitute for synthetic resin precursors in adhesives that are used for the particle board production.

Infrared reflection-absorption spectra of metal-effect coatings.

The results of studies of infrared reflection-absorption spectra of metal-effect coatings are presented in this paper. Such coatings consist of metallic flakes that are dispersed in a polymer binder. The spectra show two distinct phenomena. One is due to the polymer matrix. The other is due to metallic flakes that are dispersed inside the layer. The polymer binder causes narrow spectral lines that give a thickness-dependent intensity and position. Metallic flakes change the average baseline of this spectrum over the entire infrared spectral region. This particular effect was evaluated using a simple rough-surface model. Two parameters of the model, the root-mean-square roughness and the correlation length of the rough surface, described the reflection of the partial beams on the metal flake surfaces and scattering on flakes boundaries. The other two parameters are the specular reflectance and the diffuse reflectance of the plane untextured interface between the polymer matrix and the metal flake surface. Various metal-effect coatings within the same polymer binder were analyzed. The effect of each metal flake dispersion was evaluated by the parameters within the rough-surface model. The results were analyzed in terms of the size and the loadings of flakes that were used in the coatings.

Influence of inverse gas chromatography measurement conditions on surface energy parameters of lactose monohydrate.

Surface energy of any powder determined by inverse gas chromatography (IGC) should be independent of the measurement conditions or type of column used. In this study stainless steel and glass columns were filled with lactose powder. Dispersive and polar components of surface free energy were determined at different flow rates of carrier gas using lactose alone or diluted with calcinated diatomite (Chromosorb W). It was found that measurement conditions did not influence the value of the dispersive parameter of surface energy. On the contrary, K(a) and K(d) values were found to be dependent on dilution of lactose with Chromosorb W. The influence of other parameters on the results was found to be much smaller.