María A. Bertuzzi

Water barrier properties of starch films reinforced with cellulose nanocrystals obtained from sugarcane bagasse

Water transport in edible films based on hydrophilic materials such as starch, is a complex phenomenon due to the strong interaction of sorbed water molecules with the polymeric structure. Cellulose nanocrystals (CNC) were obtained from sugarcane bagasse. Starch and starch/CNC films were formulated and their water barrier properties were studied. The measured film solubility, contact angle, and water sorption isotherm indicated that reinforced starch/CNC films have a lower affinity to water molecules than starch films. The effects that the driving force and the water activity (aw) values at each side of the film have on permeability were analyzed. Permeability, diffusivity, and solubility coefficients indicated that the permeation process depends mostly on the tortuous pathway formed by the incorporation of CNC and therefore were mainly controlled by water diffusion. The interaction between CNC and starch chain is favoured by the chemical similarities of both molecules.

Water barrier properties of starch-clay nanocomposite films

The functional properties of corn starch based films were improved by incorporating nanoclay (Montmorillonite). Nanoclay was incorporated in the polymer matrix using two different methodologies and the films were formed by casting. The effect of film preparation methodology and of the nanoclay concentration on the physicochemical properties of the films was studied. Depending on film preparation method used, intercalated or exfoliated nanocomposite films were obtained. The FTIR spectra showed a strong interaction between the montmorillonite and the starch molecules. Opacity was dependent on the nanoclay dispersion method used. Water vapor solubility and permeability decreased with increasing montmorillonite content and were affected by the dispersion method. Water diffusion was only dependent on the nanoclay content due to the increase in tortuosity of the diffusion path, caused by the nanoparticles. The results showed that the incorporation of 5% of montmorillonite using an adequate dispersion method, improved the water resistance and barrier properties of corn starch based films. Nanoparticles reduced the damage caused to the properties of these hydrophilic films by the increase in moisture content.

A phenomenological and thermodynamic study of the water permeation process in corn starch/MMT films.

Water transport in edible films of starch based products is a complex phenomenon due to the strong interaction of sorbed water molecules with the polymeric structure of starch. Moisture sorption isotherms of starch and starch/MMT films were obtained. The results indicated that nanoclay incorporation produces a decrease of water uptake at all temperatures analysed. Thermodynamic parameters showed that sorption process is less favourable when MMT is incorporated into the starch matrix. Effect of driving force and water activity (aw) values at each side of the film on permeability and diffusivity coefficients were analysed. The effect of the tortuous pathway generated by MMT incorporation was significant only in the middle and lower range of aw. At high aw range the plasticizing effect of water dominated and MMT incorporation had little effect on the water barrier properties of these films.

Mechanical properties of a high amylose content corn starch based film, gelatinized at low temperature Propriedades mecânicas de filme a base de amido de milho de alto teor de amilose gelatinizado em baixa temperatura

Summary In the present study, a better knowledge of the influence of plasticizer content, storage relative humidity and film thickness on the mechanical properties of high amylose corn starch based films gelatinized at low temperature, is presented. The mechanical properties, tensile strength and percentage of elongation at break of high amylose corn starch films plasticized with glycerol were evaluated using tension tests. The films exhibited an increase in elongation and a decrease in tensile strength with increasing plasticizer concentration. When the glycerol level was high, some fissures were detected in the dry films, possible due to phase separation (starch-glycerol) phenomena. Film crystallinity is related to the reorganization capacity of the polymer chain, and thus the relative film crystallinity should increase with plasticizer content (glycerol and water). The mechanical properties were found to be strongly dependent on the water content due to the hydrophilic nature of starch films. The influence of moisture sorption on tensile strength was similar to that of plasticization with glycerol. The relationship between polymer chain mobility and water content explained this behavior. Elongation suffered a different effect and maximum values were reached at 45% relative humidity. The final drop in elongation was due to a softening of the structure at high relative humidity. The thicker the film the longer the drying time required, leading to greater relative crystallinity due to the corresponding increase in the possibility for chain reorganization. As a consequence, linear increases in tensile strength and elongation were observed with film thickness over the whole range studied (30 to 100 µm).