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1.
Langmuir ; 28(30): 11206-14, 2012 Jul 31.
Article in English | MEDLINE | ID: mdl-22765289

ABSTRACT

In this paper, the preparation and characterization of oxygen barrier pullulan sodium montmorillonite (Na(+)-MMT) nanocomposite coatings are presented for the first time. Full exfoliation of platelets during preparation of the coating water dispersions was mediated by ultrasonic treatment, which turned out to be a pivotal factor in the oxygen barrier performance of the final material even at high relative humidity (RH) conditions [oxygen permeability coefficients ~1.43 ± 0.39 and 258.05 ± 13.78 mL·µm·m(-2)·(24 h)(-1)·atm(-1) at 23 °C and 0% RH and 70% RH, respectively]. At the micro- and nanoscale, the reasons are discussed. The final morphology of the coatings revealed that clay lamellae were stacked on top of one another, probably due to the forced confinement of the platelets within the coating thickness after solvent evaporation. This was also confirmed by modeling the experimental oxygen permeability data with the well-known Nielsen and Cussler permeation theoretical models, which suggested a reasonable aspect ratio (α) of ~100. Electron microscopic analyses also disclosed a peculiar cell-like arrangement of the platelets. The stacking of the clay lamellae and the cell-like arrangement create the excellent oxygen barrier properties. Finally, we demonstrated that the slight haze increase in the bionanocomposite coating materials arising from the addition of the clays depends on the clay concentration but not so much on the sonication time, due to the balance of opposite effects after sonication (an increase in the number of scattering centers but a reduction in their size).


Subject(s)
Bentonite/chemistry , Nanocomposites/chemistry , Oxygen/chemistry , Glucans/chemistry , Nanotechnology/methods , Permeability , Sonication , Surface Properties
2.
ACS Appl Mater Interfaces ; 4(7): 3378-86, 2012 Jul 25.
Article in English | MEDLINE | ID: mdl-22663184

ABSTRACT

Hemicelluloses represent a largely unutilized resource for future bioderived films in packaging and other applications. However, improvement of film properties is needed in order to transfer this potential into reality. In this context, sepiolite, a fibrous clay, was investigated as an additive to enhance the properties of rye flour arabinoxylan. Composite films cast from arabinoxylan solutions and sepiolite suspensions in water were transparent or semitransparent at additive loadings in the 2.5-10 wt % range. Scanning electron microscopy showed that the sepiolite was well dispersed in the arabinoxylan films and sepiolite fiber aggregation was not found. FT-IR spectroscopy provided some evidence for hydrogen bonding between sepiolite and arabinoxylan. Consistent with these findings, mechanical testing showed increases in film stiffness and strength with sepiolite addition and the effect of poly(ethylene glycol) methyl ether (mPEG) plasticizer addition. Incorporation of sepiolite did not significantly influence the thermal degradation or the gas barrier properties of arabinoxylan films, which is likely a consequence of sepiolite fiber morphology. In summary, sepiolite was shown to have potential as an additive to obtain stronger hemicellulose films although other approaches, possibly in combination with the use of sepiolite, would be needed if enhanced film barrier properties are required for specific applications.


Subject(s)
Magnesium Silicates/chemistry , Membranes, Artificial , Nanofibers/chemistry , Xylans/chemistry , Food Packaging/methods , Gases/pharmacokinetics , Humans , Mechanical Phenomena , Oxygen/pharmacokinetics , Permeability , Plasticizers/chemistry , Steam , Tensile Strength
3.
ACS Appl Mater Interfaces ; 4(3): 1629-35, 2012 Mar.
Article in English | MEDLINE | ID: mdl-22332837

ABSTRACT

Freeze-dried wheat gluten foams were evaluated with respect to their thermal and fire-retardant properties, which are important for insulation applications. The thermal properties were assessed by differential scanning calorimetry, the laser flash method and a hot plate method. The unplasticised foam showed a similar specific heat capacity, a lower thermal diffusivity and a slightly higher thermal conductivity than conventional rigid polystyrene and polyurethane insulation foams. Interestingly, the thermal conductivity was similar to that of closed cell polyethylene and glass-wool insulation materials. Cone calorimetry showed that, compared to a polyurethane foam, both unplasticised and glycerol-plasticised foams had a significantly longer time to ignition, a lower effective heat of combustion and a higher char content. Overall, the unplasticised foam showed better fire-proof properties than the plasticized foam. The UL 94 test revealed that the unplasticised foam did not drip (form droplets of low viscous material) and, although the burning times varied, self-extinguished after flame removal. To conclude both the insulation and fire-retardant properties were very promising for the wheat gluten foam.


Subject(s)
Flame Retardants/analysis , Glutens/chemistry , Thermal Conductivity , Triticum/chemistry , Calorimetry , Diffusion , Gases , Glutens/ultrastructure , Materials Testing , Temperature , Thermogravimetry , Triticum/ultrastructure
4.
Biomacromolecules ; 12(5): 1707-15, 2011 May 09.
Article in English | MEDLINE | ID: mdl-21413807

ABSTRACT

This Article reports the influence of the protein network structure on the mechanical properties of foams produced from commercial wheat gluten using freeze-drying. Foams were produced from alkaline aqueous solutions at various gluten concentrations with or without glycerol, modified with bacterial cellulose nanosized fibers, or both. The results showed that 20 wt % glycerol was sufficient for plasticization, yielding foams with low modulus and high strain recovery. It was found that when fibers were mixed into the foams, a small but insignificant increase in elastic modulus was achieved, and the foam structure became more homogeneous. SEM indicated that the compatibility between the fibers and the matrix was good, with fibers acting as bridges in the cell walls. IR spectroscopy and SE-HPLC revealed a relatively low degree of aggregation, which was highest in the presence of glycerol. Confocal laser scanning microscopy revealed distinct differences in HMW-glutenin subunits and gliadin distributions for all of the different samples.


Subject(s)
Glutens/chemistry , Triticum/chemistry , Chromatography, Gel , Chromatography, High Pressure Liquid , Materials Testing , Microscopy, Electron, Scanning
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