Albert Magnin

Starch nanoparticles formation via high power ultrasonication

Nano-sized starch particles (NSP) were prepared from starch granules using a purely physical method of high-intensity ultrasonication. Particle size distribution, Field Effect Scanning Electron Microscopy (FE-SEM), Raman spectroscopy, and Wide-Angle X-ray Diffraction (WAXD) were used to characterize the morphology and crystal structure of the ensuing nanoparticles. The results revealed that ultrasound treatment of the starch suspension in water and at low temperature for 75 min results in the formation of starch nanoparticles between 30 and 100 nm in size. An attempt to explain the generation of starch nanoparticles was made on the basis of WAXD, Raman analysis and FE-SEM observation. Compared to acid hydrolysis, which is the most commonly adopted process, the present approach has the advantage of being quite rapid, presenting a higher yield and not requiring any chemical treatment.

Control of size and viscoelastic properties of nanofibrillated cellulose from palm tree by varying the TEMPO-mediated oxidation time.

The main objective of the present study was to control and optimize the preparation of nanofibrillated cellulose (NFC) from the date palm tree by monitoring the oxidation time (degree of oxidation) of the pristine cellulose and the number of cycles through the homogenizer. The oxidation was monitored by TEMPO (1-oxo-2,2,6,6-tétraméthylpipyridine 1-oxyle) mediated oxidation. Evidence of the successful isolation of NFC was given by FE-SEM observation revealing fibrils with a width in the range 20-30nm, depending of the oxidation time. The evolution of the transparency of the aqueous NFC suspension and carboxylic content according to the degree of oxidation and number of cycles were also analyzed by UV-vis transmittance, Fourier-transform infrared spectroscopy (FT-IR), conductimetry, and X-ray diffraction analysis. A significant NFC length reduction occurred during the TEMPO-mediated oxidation. The rheological properties of NFC suspensions were characterized as function of the oxidation time. Dynamic rheology showed that the aqueous suspension behavior changed from liquid to gel depending on the concentration. The highest concentration studied was 1wt% and the modulus reached 1MPa which was higher than for non-oxidized NFC. An explanation of the gel structure evolution with the oxidation time applied to the NFC (NFC length) was proposed. The gel structure evolves from an entanglement-governed gel structure to an immobilized water molecule-governed one.

Bio-based polyurethane reinforced with cellulose nanofibers: A comprehensive investigation on the effect of interface

Novel bio-based polyurethane (PU) nanocomposites composed of cellulose nanofiller extracted from the rachis of date palm tree and polycaprolactone (PCL) diol based PU were prepared by casting/evaporation. Two types of nanofiber were used: cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs). The mechanical and thermal properties of the nanocomposite films were studied by DMA, DSC, and tensile tests and the morphology was investigated by SEM. Bionanocomposites presented good mechanical properties in comparison to neat PU. While comparing both nanofillers, the improvement in mechanical and thermal properties was more pronounced for the nanocomposites based on CNF which could be explained, not only by the higher aspect ratio of CNF, but also by their better dispersion in the PU matrix. Calculation of the solubility parameters of the nanofiller surface polymers and of the PU segments portend a better interfacial adhesion for CNF based nanocomposites compared to CNC.

Starch Nanocrystal Stabilized Pickering Emulsion Polymerization for Nanocomposites with Improved Performance

Latex/starch nanocrystal (SNC) nanocomposite dispersions were successfully synthesized via a one-step surfactant-free Pickering emulsion polymerization route using SNC as the sole stabilizer. The effect of the SNC content, initiator type and comonomer on the particle size, colloidal stability, and film properties were investigated. Both HCl and H2SO4-hydrolysed starch nanocrystals, each bearing different surface charges, were used as Pickering emulsion stabilizing nanoparticles. SNCs from HCl hydrolysis were found to provide a better stabilization effect, giving rise to a polymer dispersion with a lower average particle size. The mechanistic aspects of the Pickering emulsion polymerization were also discussed. Nanocomposites formed by film-casting the polymer Pickering emulsions showed better mechanical properties and optical transparency than those obtained by blending the polymer emulsion with a nanocrystal dispersion, showing the one-pot route to nanocomposite precursors to be doubly advantageous. Therefore, this in situ polymerization technique not only facilitates the use of SNC nanoparticles, it also provides a valuable nanocomposite with enhanced mechanical properties and high transparency level.

Alumina interaction with AMPS–MPEG random copolymers: I. Adsorption and electrokinetic behavior

Adsorption of brush copolymers, bearing sulfonate groups and polyethylene glycol segments, on to alumina particles in suspension in water has been investigated. Study of the adsorption isotherms revealed that the copolymers displayed a strong affinity for the surface of the alumina regardless of the fraction of ionic groups on the polymer. For poly(ethylene glycol) content greater than 50%, the adsorption isotherms revealed an initial adsorption plateau followed by a second one. The shape of the adsorption isotherms was interpreted in terms of the polymer configuration at the solid-to-liquid interface. The effects of the pH and the ionic force on adsorption were studied and connected to the effects of interaction between chain segments at the surface of the alumina particles. Changes in the electrokinetic properties of the alumina particles after addition of the copolymers were investigated by following the zeta potential of particles as a function of pH. In the presence of the copolymer continuous shift of the isoelectric point IEP to a more acidic values was observed. Beyond a certain concentration the zeta potential remained negative regardless of the pH.

Alumina interaction with AMPS-MPEG copolymers produced by RAFT polymerization: stability and rheological behavior.

Different copolymers of 2-acrylamido-2-methylpropanesulfonic acid sodium salt (AMPS), methoxypolyethyleneglycol methacrylate (MPEG), were prepared using two methods of radical polymerization: classical and RAFT-controlled radical polymerization. The effect of polymer structure and architecture on the adsorption behavior, electrokinetic and rheological properties of the alumina suspensions was investigated. Adsorption isotherms showed that copolymer interaction depended not only on the ratio of the monomers and their distribution within the macromolecular backbone, but also on the method of copolymerization. Electrokinetic analysis indicated that adsorption of the copolymer is accompanied by a shift in the isoelectric point (IEP) towards acid pH values. Above a certain concentration, of the order of 1 wt%, the absolute value of the zeta-potential reaches a saturation plateau. At this stage, the maximum zeta-potential value (in absolute value) depends on both the ratio of the monomers for statistical copolymer and the length of the two blocks in the case of block distribution. The rheological behavior is greatly affected in the presence of added polymer; the viscosity of the alumina suspension decreases and reaches an optimum, which depends on both the ratio of the monomers and their distribution within the macromolecular backbone. The viscoelastic properties of the suspensions were found to be functions of both the structure and the architecture of the copolymer. Adding AMPS-MPEG copolymer increases the stability of the suspension via electrostatic effects, but also via steric effects induced by the polyethylene glycol (PEG) segments. The steric contribution to the stabilization process is much important in the presence of block distribution, which is more efficient as dispersant for concentrated alumina suspensions.

Starch nanocrystals and starch nanoparticles from waxy maize as nanoreinforcement: A comparative study

The morphological, structural and thermal behavior of starch nanocrystals (SNCs) extracted from waxy maize starch through an acid hydrolysis were compared with those of starch nanoparticles (SNPs) obtained through an ultrasound treatment starting from the same waxy maize starch. The SNPs were found to be completely amorphous, slightly smaller and had no surface charge, whereas the SNCs had the expected platelet-like morphology with a negative surface charge introduced as a result of the use of sulphuric acid in the acid hydrolysis step. SNCs also showed better thermal stability than SNPs in the presence of water. As a result of their platelet-like morphology, the SNCs performed better in reinforcing a polymer film. On the other hand, SNPs reduced the transparency of the nanocomposite films to a lesser extent than the SNCs due to their smaller size.

Electric field alignment of nanofibrillated cellulose (NFC) in silicone oil: impact on electrical properties.

This work aims to study how the magnitude, frequency, and duration of an AC electric field affect the orientation of two kinds of nanofibrillated cellulose (NFC) dispersed in silicone oil that differ by their surface charge density and aspect ratio. In both cases, the electric field alignment occurs in two steps: first, the NFC makes a gyratory motion oriented by the electric field; second, NFC interacts with itself to form chains parallel to the electric field lines. It was also observed that NFC chains become thicker and longer when the duration of application of the electric field is increased. In-situ dielectric properties have shown that the dielectric constant of the medium increases in comparison to the randomly dispersed NFC (when no electric field is applied). The optimal parameters of alignment were found to be 5000 Vpp/mm and 10 kHz for a duration of 20 min for both kinds of NFC. The highest increase in dielectric constant was achieved with NFC oxidized for 5 min (NFC-O-5 min) at the optimum conditions mentioned above.

Starch nanoparticles produced via ultrasonication as a sustainable stabilizer in Pickering emulsion polymerization

Pickering emulsion polymerizations using starch nanoparticles (SNPs) as the sole stabilizer and persulfate as initiator have been successfully accomplished. The SNPs were prepared in water via high-power ultrasonication without the addition of any chemical reagent. The polymer dispersion stabilized by SNPs proved to be stable for several months, when the SNP content was above 4 wt% relative to the monomer phase. As the SNP loading increased, the particle sizes of the polymer dispersion decreased steadily, confirming the key role of the SNPs in the stabilization process. On the basis of the zeta-potential measurement and change in polymer particle size during emulsion polymerization, a mechanistic aspect of the Pickering emulsion polymerization is proposed. The film-formation properties of the nanocomposite dispersion and the optical properties of the ensuing films are also discussed. It was shown that nanocomposites prepared via the Pickering emulsion route displayed better optical transparency than that obtained by an ex situ mixing route.

Ultrasonic assisted production of starch nanoparticles: Structural characterization and mechanism of disintegration

In this paper, the disintegration of starch (waxy and standard starch) granules into nanosized particles under the sole effect of high power ultrasonication treatment in water/isopropanol is investigated, by using wide methods of analysis. The present work aims at a fully characterization of the starch nanoparticles produced by ultrasonication, in terms of size, morphology and structural properties, and the proposition of a possible mechanism explaining the top-down generation of starch nanoparticles (SNPs) via high intensity ultrasonication. Dynamic light scattering measurements have indicated a leveling of the particle size to about 40nm after 75min of ultrasonication. The WAXD, DSC and Raman have revealed the amorphous character of the SNPs. FE-SEM. AFM observations have confirmed the size measured by DLS and suggested that SNPs exhibited 2D morphology of platelet-like shapes. This morphology is further supported by SAXS. On the basis of data collected from the different characterization techniques, a possible mechanism explaining the disintegration process of starch granules into NPs is proposed.