Biopolymer Blends Research Articles

String phase formation in biopolymer aqueous solution blends

In previous publications it has been shown that the flow-morphology relationships that apply to two-phase polymer blends or solutions, and to immiscible emulsions, also apply to two-phase aqueous solutions of mixed biopolymers, (referred to here as “biopolymer blends”). The relationships in question are classical theories of single drop deformation in shear flow, fibril breakup upon cessation of steady shear flow, and the Palierne model. In this paper, we report the experimental investigation of string phase formation in steady shear as another structural phenomenon which has been observed in polymer blends or polymer solutions, but has not been previously reported for biopolymer blends. The rheological and morphological behavior of gelatin-dextran mixtures was analyzed using conventional rotational rheometry and shear-microscopy techniques. It was found that the development of a string phase depends on the applied shear rate, the viscosity ratio and the phase volume of the minor phase. A rheological model by Kume and Hashimoto (1995) predicting string phase morphology was successfully applied for viscosity ratios not too dissimilar from unity. The application of a further model by Jeon and Hobbie (2001), however, gave ambiguous results with regard to the prediction of string phase formation.

Protein-Polysaccharide Interactions for Stabilization of Food Emulsions

ABSTRACT Proteins, polysaccharides and their blends, as examples of natural biopolymers, are surface active materials. Biopolymers may be considered as amphiphilic macromolecules that play an essential role in stabilizing food formulations (foams, emulsions and dispersions). Under specific conditions (such as protein-to-polysaccharide ratio, pH, ionic strength, temperature, mixing processing), it has been stated that proteins and polysaccharides form hybrids (complexes) with enhanced functional properties in comparison to the proteins and polysaccharides alone. Different protein-polysaccharide pairs are reviewed with particular attention to the emulsification capability of their mixtures. In the case of uncomplexed blends of biopolymers, competitive adsorption onto hydrophobic surfaces is generally reported. Conversely, electrostatic complexation between oppositely charged proteins and polysaccharides allows better anchoring of the new-formed macro-molecular amphiphile onto oil-water interfaces. Moreover, improved thermal stability and increased resistance to external treatment (high pressure) involved in food processing are obtained. This review presents basic and applied knowledge on protein-polysaccharide interactions in aqueous medium and at the oil-water interface in food emulsion systems. Electrostatic interactions and thermodynamic incompatibility in mixed biopolymer solutions are correlated to the functional properties (rheology, surface hydrophobiciry, emulsification power) of these interesting blends. Basic and industrial selected systems of different families of hydrocolloids (as gum Arabic, galactomannans, pectins) and protein (caseins, whey, soya, gelatin) mixtures are reviewed.

Influence of gelation on particle shape in sheared biopolymer blends

The morphology of biopolymer droplets gelled under shear as the dispersed phase of a two-phase mixture of biopolymers in aqueous solution (or “biopolymer blend”) was investigated experimentally. The process involves shearing the liquid biopolymer blend either at a steady stress till gelation, for creation of ellipsoidal gelled particles, or a stress step-up process for creation of high aspect ratio particles. The resulting particle shapes are analyzed and compared against models for affine deformation conditions [Janssen (1997)] and steady shear conditions [Maffetone and Minale (1998)]. Although they are only strictly valid for Newtonian fluid phases, application of these models to a situation where one phase is gelling, has provided insight into the morphological changes occurring in the shear-gelation process.

Correlation between mechanical adhesion and interfacial properties of starch/biodegradable polyester blends

AbstractBiopolymers are preferred ingredients for the manufacture of materials because they are based on abundantly available and renewable raw materials that have benign environmental problems associated with their production, fabrication, use, and disposal; however, the wide use of biopolymers in engineering applications has not been achieved, mainly because of the inferior quality of many biopolymer‐based products. To overcome this limitation, studies have been initiated on blends of biopolymers and biodegradable synthetic polymers. We used the contact angle of probe liquids to measure the surface energy of polystyrene, the biodegradable polyesters polycaprolactone, poly(hydroxybutyrate‐co‐hydroxyvalerate), polylactic acid, polybutylene adipate terephthalate, and adipic poly(hydroxy ester ether), and normal starch. The surface energies were used to estimate the starch/polymer interfacial energy and work of adhesion. The calculated starch/polyester work of adhesion showed mixed correlation with published starch/polyester mechanical properties, indicating that factors other than interfacial properties might be dominant in determining the mechanical properties of some starch/polyester blends. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 920–930, 2001

FTIR microspectroscopy study of composition fluctuations in extruded amylopectin–gelatin blends

The spatial variation in the composition of nonexpanded biopolymer blends prepared by extrusion of mixtures of gelatin with either native or pregelatinized waxy maize starch was studied using a 30-microm aperture FTIR microspectroscopy technique. The ratio of the areas of the "saccharide" bands (953-1180 cm(-1)) and the amide I and II bands (1483-1750 cm(-1)) was used to monitor the relative distributions of the two components of the blend. Two calibration methods were used to obtain amylopectin concentration values from the ratios of the IR bands. The results suggested a high degree of heterogeneity in these blends, despite the thorough mixing expected by twin-screw extrusion processing. The concentration fluctuations were greater for the blends produced by extruding gelatin and native waxy maize starch mixtures. This was in agreement with the reduced degree of conversion of the starch granules when extruded in the presence of gelatin. The FTIR 2-dimensional maps obtained suggested that in the blends produced from either native or pregelatinized starch at all concentrations studied (25/75, 50/50, and 75/25 amylopectin/gelatin) the gelatin constituted the continuous phase. The effect of the spatial resolution on the FTIR microspectroscopy results was considered and the proposed interpretation was verified by the use of polarized light microscopy and FTIR microspectroscopy acquired at higher spatial resolution (10 microm).

Surface Composition of Biopolymer Blends Biospan-SP/Phenoxy and Biospan-F/Phenoxy Observed with SFG, XPS, and Contact Angle Goniometry

The surface compositions of two biopolymer blends, Biospan-SP/Phenoxy (BSP/PHE) and Biospan-F/Phenoxy (BF/PHE), have been studied using sum frequency generation (SFG), X-ray photoemission spectroscopy (XPS), and contact angle goniometry. BSP and BF are polyurethanes capped with poly(dimethylsiloxane) (PDMS) and fluoroalkyl (-(-CF{sub 2}-){sub n}-) as end groups, respectively. With contact angle goniometry, the surface tensions of pure BSP, BF, and PHE were found to be 26, 16, and 45 dyne/cm. For each of the blends, the polymer component with a lower surface concentration of the surface-active component increases sharply as its bulk concentration increases. For BSP/PHE (and BF/PHE) in air, the surface of the polymer blend is fully covered by BSP (and BF) at a bulk concentration of 3.5 wt % (and 1 wt %). The contact angle measurements and the XPS studies yield compatible results. Comparison of results for BSP/PHE, BS/PHE (published before), and BF/PHE polymer blends shows that the lower the surface energy of the surface-active component (surface tension: BF < BS < BSP), the easier it is for the component to segregate to the surface (the minimum bulk concentration to saturate the surface is BF (1 wt %) < BS (1.7 wt %) < BSP (3.5 wt %)). Aftermore » exposure to water, SFG spectra indicate that the surface layer of a polymer blend could be restructured. For BSP (3.5 wt %)/PHE, the hydrophobic end groups of BSP submerge while the hydrophilic polyurethane backbone emerges. For BF (1 wt %)/PHE, PHE emerges at the surface after exposure to water, but for BF (5 wt %)/PHE, the BF component dominates the surface in both air and water. Their results demonstrate the bifunctionality of polymer blends and show that the surface chemistry of polymer blends may be dominated by a minor component, while the mechanical stability of the polymer is controlled by the major component.« less

Rheological, Thermal and Microstructural Properties of Whey Protein‐Cassava Starch Gels

ABSTRACTMixed gels of cassava starch (CS) and a whey protein isolate (WPI), obtained by heating solutions of 10% total solids, pH 5.75 to 85°C, were characterized as a function of the starch fraction, θs, by axial compression, small‐amplitude oscillatory rheometry, differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Gelation did not occur for θs &gt; 0.7. In the range 0&lt;θs &lt; 0.4 mixed gels showed higher mechanical (E, elastic modulus) and rheological (G′, storage modulus) properties than pure gels, with maximum values for θs= 0.2–0.3. Viscoelastic measurements as a function of time showed that gels containing higher levels of WPI developed a larger G. Blends of both biopolymers showed independent thermal transitions in DSC measurements, related to gelatinization and denaturation. Microstructure of a mixed gel formed at θs= 0.2 showed a continuous matrix formed by strands of WPI particle aggregates and an independent CS phase.