Rubber materials from elastomers and nanocellulose powders: filler dispersion and mechanical reinforcement.

Rubber materials with well-dispersed fillers and large mechanical reinforcement have been obtained by melt-processing a diene elastomer matrix and tailored nanocellulose powders having both a high specific surface area and a modified interface. Such filler powders with a specific surface area of 180 m2 g-1 and 100 m2 g-1 have been obtained by freeze-drying suspensions of short needle-like cellulose nanocrystals (CNCs) and entangled networks of microfibrillated cellulose (MFC) in tert-butanol/water, respectively. A quantitative and toposelective filler surface esterification was performed using a gas-phase protocol either with palmitoyl chloride (PCl) to obtain a hydrophobic but non-reactive nanocellulose interface, or with 3,3'-dithiopropionic acid chloride (DTACl) to introduce reactive groups that can covalently bind the nanocellulose interface to the dienic matrix in a subsequent vulcanization process.

Versatile gas-phase reactions for surface to bulk esterification of cellulose microfibrils aerogels.

Aqueous suspensions of microfibrillated cellulose obtained by a high pressure homogenization process were freeze-dried after solvent exchange into tert-butanol. The resulting aerogels, which displayed a remarkable open morphology with a surface area reaching 100 m(2)/g, were subjected to a gas-phase esterification with palmitoyl chloride. Under these conditions, variations of the reaction temperature from 100 to 200 °C, of the reaction time from 0.

Conversion of a non-water soluble potato starch waste into reducing sugars under non-conventional technologies.

In this exploratory work, the comparison of the utilisation of different non-conventional technologies (ultrasound and microwave irradiations) for the depolymerisation of a complex industrial starch-based waste into reducing sugars was investigated. Reducing sugars could then be converted into higher value-added compounds such as higher alcohols. The experiments were performed on three different starting materials named as 'Potato flour', 'Wet potato sludge' and 'Dry potato sludge'.

Reinforcing mechanisms of starch nanocrystals in a nonvulcanized natural rubber matrix.

A phenomenological modeling approach was developed to try to understand the reinforcing mechanism of starch nanocrystals in a nonvulcanized natural rubber matrix. Natural rubber was not cross-linked to maintain the biodegradability of the biosourced materials. Nonlinear dynamic mechanical experiments highlighted the significant reinforcing effect of starch nanocrystals and the presence of the Mullins and Payne effects.

Gas-phase surface esterification of cellulose microfibrils and whiskers.

A new and highly efficient synthetic method has been developed for the surface esterification of model cellulosic substrates of high crystallinity and accessibility, namely, freeze-dried tunicin whiskers and bacterial cellulose microfibrils dried by the critical point method. The reaction, which is based on the gas-phase action of palmitoyl chloride, was monitored by solid-state CP-MAS (13)C NMR. It was found that the grafting density not only depended on the experimental conditions, but also on the nature and conditioning of the cellulose samples.

The molecular structure of waxy maize starch nanocrystals.

The insoluble residues obtained by submitting amylopectin-rich native starch granules from waxy maize to a mild acid hydrolysis consist of polydisperse platelet nanocrystals that have retained the allomorphic type of the parent granules. The present investigation is a detailed characterization of their molecular composition. Two major groups of dextrins were found in the nanocrystals and were isolated.

Processing and characterization of waxy maize starch films plasticized by sorbitol and reinforced with starch nanocrystals.

Nanocomposites films have been processed from a filler and a matrix having the same nature, i.e. waxy maize starch.

Thermoplastic starch-waxy maize starch nanocrystals nanocomposites.

Waxy maize starch nanocrystals obtained by hydrolysis of native granules were used as a reinforcing agent in a thermoplastic waxy maize starch matrix plasticized with glycerol. Compared to our previous studies on starch nanocrystals reinforced natural rubber (NR) [Macromolecules 2005, 38, 3783; 2005, 38, 9161], the present system presents two particularities: (i) thermoplastic starch is a polar matrix, contrarily to NR, and (ii) the chemical structures of the matrix and the filler are similar. The influence of the glycerol content, filler content, and aging on the reinforcing properties of waxy maize starch nanocrystals (tensile tests, DMA) and crystalline structure (X-ray diffraction) of materials were studied.

Surface chemical modification of waxy maize starch nanocrystals.

The surface of waxy maize starch nanocrystals obtained from sulfuric acid hydrolysis of native waxy maize starch granules was chemically modified using two different reagents, namely, alkenyl succinic anhydride and phenyl isocyanate. The occurrence of chemical modification was evaluated by FTIR and X-ray photoelectron spectroscopies. Contact angle measurements from which the surface energy of the materials under investigation was deduced showed that chemical modification led to more hydrophobic particles.

Optimization of the preparation of aqueous suspensions of waxy maize starch nanocrystals using a response surface methodology.

Response surface methodology was used to investigate the effect of five selected factors on the selective H(2)SO(4) hydrolysis of waxy maize starch granules. These predictors were temperature, acid concentration, starch concentration, hydrolysis duration, and stirring speed. The goal of this study was to optimize the preparation of aqueous suspensions of starch nanocrystals, i.

Platelet nanocrystals resulting from the disruption of waxy maize starch granules by acid hydrolysis.

Colloidal aqueous suspensions of starch nanocrystals were prepared by submitting native granules from A-type amylopectin-rich waxy maize to a hydrochloric acid hydrolysis. The insoluble residue contains polydisperse and more or less individualized platelet nanocrystals corresponding to the lamellae formed by the association of amylopectin side branches into parallel arrays of double helices. After 2 weeks of hydrolysis, 5-7 nm thick lamellae still connected by alpha(1-->6) linkages were seen edge-on using transmission electron microscopy.