Peter J. Halley

Understanding vitrification during cure of epoxy resins using dynamic scanning calorimetry and rheological techniques

The gelation and vitrification transitions during cure of an epoxy-amine system are examined using rheological, modulated differential scanning calorimetry (DSC) and FTIR techniques. The results from dynamic mechanical analysis show that gelation is observed before vitrification at all temperatures where it can be rheologically defined. By comparing different rheological criteria for vitrification, it is seen that the vitrification transition is a gradual process that extends over a large part of cure at all temperatures where it occurs. Results from modulated DSC measurements show that the calorimetric vitrification times are longer than the vitrification times obtained from rheological measurements at cure temperatures above 100°C, but that at lower temperatures calorimetric vitrification occurs before, or at the same time as, rheological vitrification. Theoretical gelation times, estimated from FTIR conversion data, were found to be consistently shorter than the observed gelation times. Theoretical vitrification times agreed well with the observed times. The magnitude of the vitrification transition, expressed either as amount of change in heat capacity or as maximum value of loss tangent, was found to decrease approximately linearly with increasing cure temperature.

Application of the Williams–Landel–Ferry model to the viscosity–temperature relationship of Australian honeys

The rheological behaviour of nine unprocessed Australian honeys was investigated for the applicability of the Williams-Landel-Ferry (WLF) model. The viscosity of the honeys was obtained over a range of shear rates (0.01-40 s(-1)) from 2degrees to 40 degreesC, and all the honeys exhibited Newtonian behaviour with viscosity reducing as the temperature was increased. The honeys with high moisture were of lower viscosity, The glass transition temperatures of the honeys, as measured with a differential scanning calorimeter (DSC), ranged from -40degrees to -46 degreesC, and four models (WLF. Arrhenius, Vogel-Tammann-Fulcher (VTF), and power-law) were investigated to describe the temperature dependence of the viscosity. The WLF was the most suitable and the correlation coefficient averaged 0.999 +/- 0.0013 as against 0.996 +/- 0.0042 for the Arrhenius model while the mean relative deviation modulus was 0-12% for the WLF model and 10-40% for the Arrhenius one. With the universal values for the WLF constants, the temperature dependence of the viscosity was badly predicted. From non-linear regression analysis, the constants of the WLF models for the honeys were obtained (C-1 = 13.7-21.1: C-2 = 55.9-118.7) and are different from the universal values. These WLF constants will be valuable for adequate modeling of the rheology of the honeys, and they can be used to assess the temperature sensitivity of the honeys

How Thick Is Thick? Multicenter Study of the Rheological and Material Property Characteristics of Mealtime Fluids and Videofluoroscopy Fluids

Abstract Objective rheological assessment of fluids given to dysphagic patients at mealtime and during videofluoroscopy was carried out using a multicenter format. Thin, quarter-thick, half-thick and full-thick fluids were examined for the degree of correlation between mealtime fluids and their allegedly matched videofluoroscopy counterparts. The study was carried out to determine whether perceived subjective differences between mealtime fluids and videofluoroscopy fluids could be quantified using the rheological parameters of viscosity, density, and yield stress. The results showed poor correlation between mealtime fluids and videofluoroscopy fluids over all parameters. In general, the videofluoroscopy fluids were more viscous, more dense, and showed higher yield stress values than their mealtime counterparts. Given these results, it is reasonable to assume that the fluids used during videofluoroscopy do not provide an accurate indication of swallowing ability at mealtime. Therefore, it is suggested that clinicians use objective methods to rheologically match videofluoroscopy fluids to mealtime fluids.

Effects of starch synthase IIa gene dosage on grain, protein and starch in endosperm of wheat

Starch synthases (SS) are responsible for elongating the α-1,4 glucan chains of starch. A doubled haploid population was generated by crossing a line of wheat, which lacks functional ssIIa genes on each genome (abd), and an Australian wheat cultivar, Sunco, with wild type ssIIa alleles on each genome (ABD). Evidence has been presented previously indicating that the SGP-1 (starch granule protein-1) proteins present in the starch granule in wheat are products of the ssIIa genes. Analysis of 100 progeny lines demonstrated co-segregation of the ssIIa alleles from the three genomes with the SGP-1 proteins, providing further evidence that the SGP-1 proteins are the products of the ssIIa genes. From the progeny lines, 40 doubled haploid lines representing the eight possible genotypes for SSIIa (ABD, aBD, AbD, ABd, abD, aBd, Abd, abd) were characterized for their grain weight, protein content, total starch content and starch properties. For some properties (chain length distribution, pasting properties, swelling power, and gelatinization properties), a progressive change was observed across the four classes of genotypes (wild type, single nulls, double nulls and triple nulls). However, for other grain properties (seed weight and protein content) and starch properties (total starch content, granule morphology and crystallinity, granule size distribution, amylose content, amylose–lipid dissociation properties), a statistically significant change only occurred for the triple nulls, indicating that all three genes had to be missing or inactive for a change to occur. These results illustrate the importance of SSIIa in controlling grain and starch properties and the importance of amylopectin fine structure in controlling starch granule properties in wheat.

Developing biodegradable mulch films from starch-based polymers

This paper examines the development of starch-based plastics for use as biodegradable mulch film. A variety of starch-based polymers are blended with high performance biodegradable polyester polymers in order to determine the applicability of films to be processed on a film blowing line and to perform well in mulch film field trials. The process of material formulation, film blowing processing and scale-up and performance properties are highlighted for a successful material. Insights into future developments of starch-derived biodegradable polymers are given.

The anaerobic degradability of thermoplastic starch: polyvinyl alcohol blends: potential biodegradable food packaging materials.

A systematic study on the anaerobic degradability of a series of starch:polyvinyl alcohol (TPS:PVOH) blends was performed to determine their fate upon disposal in either anaerobic digesters or bioreactor landfills. The aims of the study were to measure the rate and extent of solubilisation of the plastics. The extent of substrate solubilisation on a COD basis reached 60% for a 90:10 (w/w) blend of TPS:PVOH, 40% for 75:25, 30% for 50:50 and 15% for PVOH only. The rate of substrate solubilisation was most rapid for the 90:10 blend (0.041 h(-1)) and decreased with the amount of starch in the blend in the following order 0.034 h(-1)(75:25); 0.023 h(-1)(50:50). The total solids that remained after 900 h were 10 wt.% (90:10); 23 wt.% (75:25); 55 wt.% (50:50); 90 wt.% (0:100). Starch containing substrates produced a higher concentration of volatile fatty acids (VFAs) and biogas, compared to the 0:100 substrate. The major outcome was that PVOH inhibited the degradation of the starch from the blend.

Effect of the ionic liquid 1-ethyl-3-methylimidazolium acetate on the phase transition of starch: Dissolution or gelatinization?

This work revealed that the interactions between starch, the ionic liquid 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]), and water might contribute to the phase transition (gelatinization, dissolution, or both) of native starch at reduced temperature. Using mixtures of water and [Emim][OAc] at certain ratios (7.2/1 and 10.8/1 mol/mol), both the gelatinization and dissolution of the starch occur competitively, but also in a synergistic manner. At lower [Emim][OAc] concentration (water/[Emim][OAc] molar ratio≥25.0/1), mainly gelatinization occurs which is slightly impeded by the strong interaction between water and [Emim][OAc]; while at higher [Emim][OAc] concentration (water/[Emim][OAc] molar ratio≤2.8/1), the dissolution of starch is the major form of phase transition, possibly restricted by the difficulty of [Emim][OAc] to interact with starch.

A review of drainage and spontaneous rupture in free standing thin films with tangentially immobile interfaces.

A review of spontaneous rupture in thin films with tangentially immobile interfaces is presented that emphasizes the theoretical developments of film drainage and corrugation growth through the linearization of lubrication theory in a cylindrical geometry. Spontaneous rupture occurs when corrugations from adjacent interfaces become unstable and grow to a critical thickness. A corrugated interface is composed of a number of waveforms and each waveform becomes unstable at a unique transition thickness. The onset of instability occurs at the maximum transition thickness, and it is shown that only upper and lower bounds of this thickness can be predicted from linear stability analysis. The upper bound is equivalent to the Frenkel criterion and is obtained from the zeroth order approximation of the H3 term in the evolution equation. This criterion is determined solely by the film radius, interfacial tension and Hamaker constant. The lower bound is obtained from the first order approximation of the H3 term in the evolution equation and is dependent on the film thinning velocity. A semi-empirical equation, referred to as the MTR equation, is obtained by combining the drainage theory of Manev et al. [J. Dispersion Sci. Technol., 18 (1997) 769] and the experimental measurements of Radoev et al. [J. Colloid Interface Sci. 95 (1983) 254] and is shown to provide accurate predictions of film thinning velocity near the critical thickness of rupture. The MTR equation permits the prediction of the lower bound of the maximum transition thickness based entirely on film radius, Plateau border radius, interfacial tension, temperature and Hamaker constant. The MTR equation extrapolates to Reynolds equation under conditions when the Plateau border pressure is small, which provides a lower bound for the maximum transition thickness that is equivalent to the criterion of Gumerman and Homsy [Chem. Eng. Commun. 2 (1975) 27]. The relative accuracy of either bound is thought to be dependent on the amplitude of the hydrodynamic corrugations, and a semi-empirical correlation is also obtained that permits the amplitude to be calculated as a function of the upper and lower bound of the maximum transition thickness. The relationship between the evolving theoretical developments is demonstrated by three film thickness master curves, which reduce to simple analytical expressions under limiting conditions when the drainage pressure drop is controlled by either the Plateau border capillary pressure or the van der Waals disjoining pressure. The master curves simplify solution of the various theoretical predictions enormously over the entire range of the linear approximation. Finally, it is shown that when the Frenkel criterion is used to assess film stability, recent studies reach conclusions that are contrary to the relevance of spontaneous rupture as a cell-opening mechanism in foams.

Confectionery Gels: A Review on Formulation, Rheological and Structural Aspects

A confectionery gel (CG) consists of high sugar components of sucrose and glucose syrup, combined with gelling components such as starch, gelatin, or pectin, along with food acid, flavourings and colourings. Common CG products include “jelly snakes,” “jelly babies,” “jelly beans,” and form a portion of the lucrative confectionery market; however, there are continual consumer demands for more interesting and innovative products that have new and exciting textures, flavors and appearances. Improving or modifying CG textures can meet these demands, but first an understanding of how the behaviour and structure of the gel is developed must be achieved. Companies that will gain a competitive advantage in the confectionery market will be those able to actively manipulate and control sensory properties to meet exacting customer demands. This paper is a review of literature available on confectionery gels, their components, and factors that may affect their microstructure, texture, and rheology.

Thickened Fluids and Water Absorption in Rats and Humans

Individuals with dysphagia are commonly provided with oral fluids thickened to prevent aspiration. Most thickening agents are either gum-based (guar or xanthan) or are derived from modified starches. There is evidence, predominantly anecdotal, that dysphagic individuals are subclinically dehydrated. Dysphagia has a particular impact on elderly individuals and there is justifiable concern for dehydration in this population. It has been speculated that dehydration may, in part, be the result of the water-holding capacity of these thickening agents decreasing water absorption from the gut. The aim of this study was to determine the rate of intestinal absorption of water from thickened fluids. The method used was a laboratory tracer study in rats and humans in vivo. We found that there were no significant differences in water absorption rates between thickened fluids or pure water irrespective of thickener type (modified maize starch, guar gum, or xanthan gum). These data provide no support for the view that the addition of thickening agents, irrespective of type, to orally ingested fluids significantly alters the absorption rate of water from the gut.