Kevin M. Kit

Morphological and Surface Properties of Electrospun Chitosan Nanofibers

Nonwoven fiber mats of chitosan with potential applications in air and water filtration were successfully made by electrospinning of chitosan and poly(ethyleneoxide) (PEO) blend solutions. Electrospinning of pure chitosan was hindered by its limited solubility in aqueous acids and high degree of inter- and intrachain hydrogen bonding. Nanometer-sized fibers with fiber diameter as low as 80 +/- 35 nm without bead defects were made by electrospinning high molecular weight chitosan/PEO (95:5) blends. Fiber formation was characterized by fiber shape and size and was found to be strongly governed by the polymer molecular weight, blend ratios, polymer concentration, choice of solvent, and degree of deacetylation of chitosan. Weight fractions of polymers in the electrospun nonwoven fibers mats were determined by thermal gravimetric analysis and were similar to ratio of polymers in the blend solution. Surface properties of fiber mats were determined by measuring the binding efficiency of toxic heavy metal ions like chromium, and they were found to be related with fiber composition and structure.

Fabrication, functionalization, and application of electrospun biopolymer nanofibers.

The use of novel nanostructured materials has attracted considerable interest in the food industry for their utilization as highly functional ingredients, high-performance packaging materials, processing aids, and food quality and safety sensors. Most previous application interest has focused on the development of nanoparticles. However, more recently, the ability to produce non-woven mats composed of nanofibers that can be used in food applications is beginning to be investigated. Electrospinning is a novel fabrication technique that can be used to produce fibers with diameters below 100 nm from (bio-) polymer solutions. These nanofibers have been shown to possess unique properties that distinguish them from non-woven fibers produced by other methods, e.g., melt-blowing. This is because first the process involved results in a high orientation of polymers within the fibers that leads to mechanically superior properties, e.g., increased tensile strengths. Second, during the spinning of the fibers from polymer solutions, the solvent is rapidly evaporated allowing the production of fibers composed of polymer blends that would typically phase separate if spun with other processes. Third, the small dimensions of the fibers lead to very high specific surface areas. Because of this the fiber properties may be greatly influenced by surface properties giving rise to fiber functionalities not found in fibers of larger sizes. For food applications, the fibers may find uses as ingredients if they are composed solely of edible polymers and GRAS ingredients, (e.g., fibers could contain functional ingredients such as nutraceuticals, antioxidants, antimicrobials, and flavors), as active packaging materials or as processing aids (e.g., catalytic reactors, membranes, filters (Lala et al., 2007), and sensors (Manesh et al., 2007; Ren et al., 2006; Sawicka et al., 2005). This review is therefore intended to introduce interested food and agricultural scientists to the concept of nano-fiber manufacturing with a particular emphasis on the use of biopolymers. We will review typical fabrication set-ups, discuss the influence of process conditions on nanofiber properties, and then review previous studies that describe the production of biopolymer-based nanofibers. Finally we briefly discuss emerging methods to further functionalize fibers and discuss potential applications in the area of food science and technology.

Nanofibers as Carrier Systems for Antimicrobial Microemulsions. Part I: Fabrication and Characterization

Antimicrobial nanofibers were prepared by solubilizing an antimicrobial essential oil (eugenol; 0.75-1.5 wt %) in surfactant micelles (Surfynol 465; 5-10 wt %) to form eugenol-containing microemulsions. Microemulsions were mixed with a nonionic synthetic polymer (poly(vinyl alcohol), PVA; M(w) = 130 kDa, degree of hydrolysis approximately 87%) and solutions subjected to electrospinning to induce nanofiber formation. Solution properties, fiber morphology, and composition of nanofibers were determined. The surface conductivity and viscosity of the polymer solutions increased, while surface tension decreased as both surfactant and eugenol concentration increased. Material deposited on the collector plate consisted primarily of nanofibers with a circular cross section with some surface roughness, although some bead defects were observed. The mean fiber diameters ranged from 57 to 126 nm with fibers having a broad diameter distribution (10-280 nm). The mean diameter of the nanofibers decreased with increasing surfactant concentration and decreasing eugenol concentration. Transmission electron microscopy indicated that microemulsion droplets were homogenously dispersed throughout the nanofibers. Results suggest that electrospun nanofibers may serve as carrier vehicles for microemulsions containing solubilized lipophilic functional compounds such as bioactives, antimicrobials, antioxidants, flavors, and pharmaceuticals.

A possible explanation for nonlinear spherulitic growth rates

Nonlinear growth of polymer spherulites has been repeatedly reported in blends containing a low-molecular weight amorphous polymer. A new explanation for this behaviour is proposed. Results of numerical simulations of the growth of lamellar stacks are presented. The model incorporates diffusion of amorphous polymer and assumes that the lamellar growth rate is depressed by the presence of amorphous chains at the growth front. It is shown that steady-state growth is reached only after long times when the diffusion coefficient of amorphous chains is large or when the lamellar growth rate is small. It is proposed that nonlinear growth in blends containing a low-molecular weight amorphous polymer (large diffusion coefficient) is, in some cases, due to the long times needed for a steady state to be reached and not a diffusion-limiting process.

Two-step etching procedures for binary polymer blends

Two-step etching procedures have been developed for binary polymer blends of linear low density polyethylene (LLDPE) with high density polyethylene (HDPE), and for blends of atactic and syndiotactic polystyrene. For both cases, two different etchants have been identified for the component neat polymers; sequential etching has been employed to reveal the distribution of the component polymers within the blend. It is believed that similar procedures may be applicable to other blend systems.