Dynamic shear modulus of isotropic elastomers

We have investigated the dynamic mechanical behavior of two cross-linked polymer networks with very different topologies: one made of backbones randomly linked along their length; the other with fixed-length strands uniformly cross-linked at their ends. The samples were analyzed using oscillatory shear, at very small strains corresponding to the linear regime. This was carried out at a range of frequencies, and at temperatures ranging from the glass plateau, through the glass transition, and well into the rubbery region. Through the glass transition, the data obeyed the time-temperature superposition principle, and could be analyzed using WLF treatment. At higher temperatures, in the rubbery region, the storage modulus was found to deviate from this, taking a value that is independent of frequency. This value increased linearly with temperature, as expected for the entropic rubber elasticity, but with a substantial negative offset inconsistent with straightforward enthalpic effects. Conversely, the loss modulus continued to follow time-temperature superposition, decreasing with increasing temperature, and showing a power-law dependence on frequency.

Effects of high pressure on functional properties of soy protein

Simultaneous measurement of the effects of low soy protein concentration, pH and high pressure treatment at room temperature on solubility, emulsifying properties and rheological properties (loss modulus, G '') of soy protein isolate (SPI) were evaluated. Central composite rotatable designs (2(3)) were employed over two pH ranges (2.66-4.34 and 5.16-6.84) with SPI concentration (0.32-3.68%) and pressure (198-702 MPa) as the other independent variables. The surface responses were obtained for protein solubility, emulsifying activity index (EAI) and G ''. The samples with the highest effect on protein solubility, EAI and G '' values were evaluated, as well, by electrophoresis and free sulphydryl determination. The pH was the main factor that affected protein solubility, with solubility at a maximum at pH < 3 or pH > 6. Increasing SPI concentration and decreasing/increasing the pH away from the isoelectric point both caused a reduction in EAI. Loss modulus (G '') was found to increase with SPI concentration in both pH ranges. (c) 2006 Elsevier Ltd. All rights reserved.

Viscoelastic properties of high pressure and heat induced tofu gels

Tofu gels were rheologically examined to determine their storage or elastic (G′) and loss or viscous (G″) moduli as a function of frequency within their linear viscoelastic limits. The tofu gels were made using either glucono-δ-lactone (GDL) or calcium sulphate (CaSO4·2H2O), followed by either heat treatment (heated soymilk at 97 °C prior to coagulation and subsequently held at 70 °C for 60 min, HT) or high pressure treatment (400 MPa at 20 °C for 10 min, HP). The overall moduli values of the GDL gels and CaSO4·2H2O gels of both physical treatments were similar, each gave frequency profiles expected for weak viscoelastic materials. However, although both temperature and high pressure treatments could be used to produce tofu gels, the final products were not the same. Pressure formed gels, despite having a higher overall “consistency” (increasing values of their moduli), had a proportionately higher contribution from the loss modulus (increased tan δ). Differences could also be observed using confocal scanning laser microscopy. While such treatment may give rise to differing systems/structures, with new or modified organoleptic properties, the more “open” structures obtained by pressure treatment may well cause processing difficulties if subsequent reworking or moulding is required.

Viscoelastic properties of high pressure and heat induced tofu gels

Tofu gels were rheologically examined to determine their storage or elastic (G') and loss or viscous (G '') moduli as a function of frequency within their linear viscoelastic limits. The tofu gels were made using either glucono-delta-lactone (GDL) or calcium sulphate (CaSO4 center dot 2H(2)O), followed by either heat treatment (heated soymilk at >= 97 degrees C prior to coagulation and subsequently held at 70 degrees C for 60 min, HT) or high pressure treatment (400 MPa at 20 degrees C for 10 min, HP). The overall moduli values of the GDL gels and CaSO4 center dot 2H(2)O gels of both physical treatments were similar, each gave frequency profiles expected for weak viscoelastic materials. However, although both temperature and high pressure treatments could be used to produce tofu gels, the final products were not the same. Pressure formed gels, despite having a higher overall "consistency" (increasing values of their moduli), had a proportionately higher contribution from the loss modulus (increased tan delta). Differences could also be observed using confocal scanning laser microscopy. While such treatment may give rise to differing systems/structures, with new or modified organoleptic properties, the more "open" structures obtained by pressure treatment may well cause processing difficulties if subsequent reworking or moulding is required. (c) 2007 Elsevier Ltd. All rights reserved.

Effects of variation in the palm stearin: palm olein ratio on the crystallisation of a low-trans shortening

Changes in the theological properties during crystallisation and in the crystal size and morphology of blends containing rapeseed oil with varying percentages of palm stearin (POs) and palm olein (POf) have been studied. The crystals formed from all three blends were studied by confocal laser scanning microscopy, light microscopy and environmental scanning electron microscopy, which revealed the development of clusters of 3-5 individual elementary "spherulites" in the early stages of crystallisation. The saturated triacylglycerol content of the solid crystals separated at the onset of crystallisation was much greater than that in the total fat. Fat blends with a higher content of palm stearin had a more rapid nucleation rate when observed by light microscopy, and this caused an earlier change in the rheological properties of the fat during crystallisation. Using a low torque amplitude (0.005 Pa, which was within the linear viscoelastic region of all samples studied) and a frequency of 1 Hz, the viscoelastic properties of melted fat during cooling were studied. All samples, prior to crystallisation, showed weak viscoelastic liquid behaviour (G '', loss modulus >G', storage modulus). After crystallisation a more "solid like" behaviour was observed (G' similar to or greater than G ''). The blend having the highest concentration of POs was found to have the earliest onset of crystallisation (27% w/w POs; 12 mins, 22% w/w POs; 13.5 mins, 17% w/w POs, 15 mins, respectively). However, there were no significant differences in the time to the point when G' became greater than G' among the three blends. (c) 2006 Elsevier Ltd. All rights reserved.

Effects of composition on fat rheology and crystallisation

The crystallisation behaviour of three fat blends, comprising a commercial shortening, a blend of fats with a very low trans fatty acid content ("low-trans") and a blend including hardened rapeseed oil with a relatively high trans fatty acid content ("high-trans") was studied. Molten fats were lowered to a temperature of 31 degrees C and stirred for 0, 15, 30, 45 and 60 min. Samples were removed and their rheological properties studied, using a controlled stress rheometer, employing a frequency sweep procedure. Effects of the progressive crystallisation at 31 degrees C on the melting profile of fat samples removed from the stirred vessel and solidified at -20 degrees C were also studied by differential scanning calorimetry (DSC). The rheological profiles obtained suggested that all of the fats studied had weak viscoelastic "liquid" structures when melted, but these changed to structures perceived by the rheometer as weak viscoelastic "gels" in the early stages of crystallisation (G' (storage modulus) > G" (loss modulus) over most of the measured frequency range). These subsequently developed into weak viscoelastic semi-solids, showing frequency dependent behaviour on further crystallisation. These changes in behaviour were interpreted as changes from a small number of larger crystals "cross-linking" in a liquid matrix to a larger number of smaller crystals packed with a "slip plane" of liquid oil between them. The rate of crystallisation of the three fats was in the order high trans > low-trans > commercial shortening. Changes in the DSC melting profile due to fractionation of triacylglycerols during the crystallisation at 31 degrees C were evident for all three fats. (c) 2006 Elsevier Ltd. All rights reserved.

Squeeze flow viscoelasticity of electrorheological fluids based on microcrystalline cellulose

Dynamic viscoelasticity of electrorheological fluids based on microcrystalline cellulose/castor oil suspensions was experimentally investigated in squeeze flow. The dependence of storage modulus G' and loss modulus G" parallel to external electric field on electric fields and strain amplitudes is presented. The experiments show that, when external electric field is higher than the critical field, the viscoelasticity of the ER fluids converts from linear to nonlinear, and the ER fluids transfer from solid-like state to fluid state with the growth of strain amplitude. The influences of strain amplitude and oscillatory frequency on the nonlinearity of viscoelasticity were also studied.

The Phosphorus Indicators Tool: a simple model of diffuse P loss from agricultural land to water

The Phosphorus Indicators Tool provides a catchment-scale estimation of diffuse phosphorus (P) loss from agricultural land to surface waters using the most appropriate indicators of P loss. The Tool provides a framework that may be applied across the UK to estimate P loss, which is sensitive not only to land use and management but also to environmental factors such as climate, soil type and topography. The model complexity incorporated in the P Indicators Tool has been adapted to the level of detail in the available data and the need to reflect the impact of changes in agriculture. Currently, the Tool runs on an annual timestep and at a 1 km(2) grid scale. We demonstrate that the P Indicators Tool works in principle and that its modular structure provides a means of accounting for P loss from one layer to the next, and ultimately to receiving waters. Trial runs of the Tool suggest that modelled P delivery to water approximates measured water quality records. The transparency of the structure of the P Indicators Tool means that identification of poorly performing coefficients is possible, and further refinements of the Tool can be made to ensure it is better calibrated and subsequently validated against empirical data, as it becomes available.

Variation in dynamic elastic shear modulus of sandstone upon fluid saturation and substitution

Experimental acoustic measurements on sandstone rocks at both sonic and ultrasonic frequencies show that fluid saturation can cause a noticeable change in both the dynamic bulk and shear elastic moduli of sandstones. We observed that the change in dynamic shear modulus upon fluid saturation is highly dependent on the type of saturant, its viscosity, rock microstructure, and applied pressures. Frequency dispersion has some influence on dynamic elastic moduli too, but its effect is limited to the ultrasonic frequency ranges and above. We propose that viscous coupling, reduction in free surface energy, and, to a limited extent, frequency dispersion due to both local and global flow are the main mechanisms responsible for the change in dynamic shear elastic modulus upon fluid saturation and substitution, and we quantify influences.

Sonic to ultrasonic Q of sandstones and limestones: Laboratory measurements at in situ pressures

Laboratory measurements of the attenuation and velocity dispersion of compressional and shear waves at appropriate frequencies, pressures, and temperatures can aid interpretation of seismic and well-log surveys as well as indicate absorption mechanisms in rocks. Construction and calibration of resonant-bar equipment was used to measure velocities and attenuations of standing shear and extensional waves in copper-jacketed right cylinders of rocks (30 cm in length, 2.54 cm in diameter) in the sonic frequency range and at differential pressures up to 65 MPa. We also measured ultrasonic velocities and attenuations of compressional and shear waves in 50-mm-diameter samples of the rocks at identical pressures. Extensional-mode velocities determined from the resonant bar are systematically too low, yielding unreliable Poisson's ratios. Poisson's ratios determined from the ultrasonic data are frequency corrected and used to calculate the sonic-frequency compressional-wave velocities and attenuations from the shear- and extensional-mode data. We calculate the bulk-modulus loss. The accuracies of attenuation data (expressed as 1000/Q, where Q is the quality factor) are +/- 1 for compressional and shear waves at ultrasonic frequency, +/- 1 for shear waves, and +/- 3 for compressional waves at sonic frequency. Example sonic-frequency data show that the energy absorption in a limestone is small (Q(P) greater than 200 and stress independent) and is primarily due to poroelasticity, whereas that in the two sandstones is variable in magnitude (Q(P) ranges from less than 50 to greater than 300, at reservoir pressures) and arises from a combination of poroelasticity and viscoelasticity. A graph of compressional-wave attenuation versus compressional-wave velocity at reservoir pressures differentiates high-permeability (> 100 mD, 9.87 X 10(-14) m(2)) brine-saturated sandstones from low-permeability (< 100 mD, 9.87 X 10 (14) m(2)) sandstones and shales.

The effects of difficulty and gain versus loss on vocal physiology and acoustics

To examine the basis of emotional changes to the voice, physiological and electroglottal measures were combined with acoustic speech analysis of 30 men performing a computer task in which they lost or gained points under two levels of difficulty. Predictions of the main effects of difficulty and reward on the voice were not borne out by the data. Instead, vocal changes depended largely on interactions between gain versus loss and difficulty. The rate at which the vocal folds open and close (fundamental frequency; f0) was higher for loss than for gain when difficulty was high, but not when difficulty was low. Electroglottal measures revealed that f0 changes corresponded to shorter glottal open times for the loss conditions. Longer closed and shorter open phases were consistent with raised laryngeal tension in difficult loss conditions. Similarly, skin conductance indicated higher sympathetic arousal in loss than gain conditions, particularly when difficulty was high. The results provide evidence of the physiological basis of affective vocal responses, confirming the utility of measuring physiology and voice in the study of emotion.

The imminent availability of a potent weight-loss medicine in pharmacies: public perception of effectiveness

Orlistat is an effective weight-loss medicine, which will soon be available for purchase in pharmacies. We used a factorial experiment and found that informing people about the availability for purchase of this medicinal product previously only available on prescription resulted in higher ratings of perceived value and effectiveness compared to a natural health supplement even though we used the same statement about effectiveness. This positive perception of orlistat was not impaired by the provision of side-effect information. Orlistat will soon be available in pharmacies. Health professionals must act to prevent its misuse by those not overweight.

Dispersal capacity and diet breadth modify the response of wild bees to habitat loss

Habitat loss poses a major threat to biodiversity, and species-specific extinction risks are inextricably linked to life-history characteristics. This relationship is still poorly documented for many functionally important taxa, and at larger continental scales. With data from five replicated field studies from three countries, we examined how species richness of wild bees varies with habitat patch size. We hypothesized that the form of this relationship is affected by body size, degree of host plant specialization and sociality. Across all species, we found a positive species–area slope (z ¼ 0.19), and species traits modified this relationship. Large-bodied generalists had a lower z value than small generalists. Contrary to predictions, small specialists had similar or slightly lower z value compared with large specialists, and small generalists also tended to be more strongly affected by habitat loss as compared with small specialists. Social bees were negatively affected by habitat loss (z ¼ 0.11) irrespective of body size. We conclude that habitat loss leads to clear shifts in the species composition of wild bee communities.

Formulation of a live bacterial vaccine for stable room temperature storage results in loss of acid, bile and bile salt resistance

Live bacterial vaccines have great promise both as vaccines against enteric pathogens and as heterologous antigen vectors against diverse diseases. Ideally, room temperature stable dry formulations of live bacterial vaccines will allow oral vaccination without cold-chain storage or injections. Attenuated Salmonella can cross the intestinal wall and deliver replicating antigen plus innate immune activation signals directly to the intestinal immune tissues, however the ingested bacteria must survive firstly gastric acid and secondly the antimicrobial defences of the small intestine. We found that the way in which cells are grown prior to formulation markedly affects sensitivity to acid and bile. Using a previously published stable storage formulation that maintained over 10% viability after 56 days storage at room temperature, we found dried samples of an attenuated S. typhimurium vaccine lost acid and bile resistance compared to the same bacteria taken from fresh culture. The stable formulation utilised osmotic preconditioning in defined medium plus elevated salt concentration to induce intracellular trehalose accumulation before drying. Dried bacteria grown in rich media without osmotic preconditioning showed more resistance to bile, but less stability during storage, suggesting a trade-off between bile resistance and stability. Further optimization is needed to produce the ultimate room-temperature stable oral live bacterial vaccine formulation.