Ultrasonic study of the gelation of gelatin: phase diagram, hysteresis and kinetics

We map the ultrasonic (8 MHz) speed and attenuation of edible-grade gelatin in water, exploring the key dependencies on temperature, concentration and time. The ultrasonic signatures of the sol-gel transition, confirmed by rheological measurements, and incomplete gel formation at low concentrations, enable a phase diagram of the system to be constructed. Sensitivity is also demonstrated to the kinetics of gel formation and melting, and associated hysteresis effects upon cyclic temperature sweeps. Furthermore, simple acoustic models of the sol and gel state enable estimation of the speed of sound and compressibility of gelatin. Our results demonstrate the potential of ultrasonic measurements to characterise the structure and visco-elasticity of gelatin hydrogels.Comment: 15 pages, 8 figure

Measurement of the lower explosive limit of combustible dust clouds in a 20-litre spherical chamber

Call number: LD2668 .T4 1985 S562Master of Scienc

Two Contributions to the Ac Conductivity of Alkali Oxide Glasses

Although the frequency dependent conductivity of ion-containing glasses often displays scale invariant power law dispersion at high temperatures, the exponent increases to unity at lower temperatures. We report measurements of the conductivity of a series of alkali metaphosphate glasses including a mixed alkali composition and demonstrate that this temperature dependence results from the superposition of two power law dispersions originating from separate mechanism, and does not indicate any intrinsic change in scaling of the process which dominates at high temperatures. © 1995 The American Physical Society

Anomalous-diffusion Model of Ionic Transport in Oxide Glasses

The power-law frequency dependence of both the conductivity, (), and permittivity, (), of ion-conducting materials suggests that self-similar or scale-invariant behavior influences the transport of ions at high frequencies. Using an anomalous-diffusion model, we derive relevant power-law expressions for () and () and compare these with measurements performed on LiPO3 glass. Superior fits to the measured data are obtained compared to the commonly used Kohlrausch-Williams-Watts (KWW) description of the electrical modulus, most particularly in the notorious high-frequency regime. Evaluation of our results in terms of an anomalous-diffusion model suggests the dominance of interaction-based constraints to diffusion. © 1995 The American Physical Society

Scaling Parallels in the Non-Debye Dielectric Relaxation of Ionic Glasses and Dipolar Supercooled Liquids

We compare the dielectric response of ionic glasses and dipolar liquids near the glass transition. Our work is divided into two parts. In the first section we examine ionic glasses and the two prominent approaches to analyzing the dielectric response. The conductivity of ion-conducting glasses displays a power law dispersion σ(ω)∞ωn, where n≈0.67, but frequently the dielectric response is analyzed using the electrical modulus M*(ω) = 1/ε*(ω), where ε*(ω) = ε(ω) - iσ(ω)/ω is the complex permittivity. We reexamine two specific examples where the shape of M*(ω) changes in response to changes in (a) temperature and (b) ion concentration, to suggest fundamental changes in ion dynamics are occurring. We show, however, that these changes in the shape of M*(ω) occur in the absence of changes in the scaling properties of σ(ω), for which n remains constant. In the second part, we examine the dielectric relaxation found in dipolar liquids, for which ε*(ω) likewise exhibits changes in shape on approach to the glass transition. Guided by similarities of M*(ω) in ionic glasses and ε*(ω) in dipolar liquids, we demonstrate that a recent scaling approach proposed by Dixon and co-workers for ε*(ω) of dipolar relaxation also appears valid for M*(ω) in the ionic case. While this suggests that the Dixon scaling approach is more universal than previously recognized, we demonstrate how the dielectric response can be scaled in a linear manner using an alternative data representation

Regarding the Correlation of Nuclear Spin Relaxation and Electrical Conductivity Relaxation in Ionic Glasses

Much attention has been focused recently on the apparent differences between ion dynamics in ion-containing glasses as probed by electrical conductivity relaxation (ECR) and by nuclear spin relaxation (NSR) techniques. In both relaxation processes, a power law frequency dependence is observed. Based upon fluctuation-dissipation arguments, the power law exponents should be equivalent. However, experimentally, it appears that the conductivity exponent is generally smaller than the NSR exponent. While an explanation for this discrepancy based upon fundamental differences in the correlation functions probed by the two techniques has been proffered, we show how this discrepancy may simply arise from differing analyses of the ac conductivity. We review several cases taken from the literature in which the conductivity exponent was obtained from analysis of the electrical modulus. We demonstrate how this analysis approach generally underestimates the conductivity exponent. When we instead determine the exponent directly from the ac conductivity, we find near equivalence between the NSR and ECR exponents

Fundamental questions relating to ion conduction in disordered solids

A number of basic scientific questions relating to ion conduction in homogeneously disordered solids are discussed. The questions deal with how to define the mobile ion density, what can be learned from electrode effects, what is the ion transport mechanism, the role of dimensionality, and what are the origins of the mixed-alkali effect, of time-temperature superposition, and of the nearly-constant loss. Answers are suggested to some of these questions, but the main purpose of the paper is to draw attention to the fact that this field of research still presents several fundamental challenges.Comment: Reports on Progress in Physics, to appea

Isotopic substitution experiments in the hydrogenation of mandelonitrile over a carbon supported Pd catalyst: a nuclear magnetic resonance study

A mechanistic exploration of the liquid phase hydrogenation of the aromatic cyanohydrin mandelonitrile (C6H5CH(OH)CH2CN) over a carbon supported Pd catalyst to produce the primary amine, phenethylamine (C6H5CH2CH2NH2) is conducted. Prior examination showed the reaction to involve the production of the ketone intermediate 2-aminoacetophenone (C6H5C(O)CH2NH2), formed as a consequence of the presence of an acid catalysed tautomeric side reaction. The corresponding deuteration reaction, reported here and analysed by multinuclear NMR spectroscopy and mass spectrometry, is employed to further investigate accessible pathways. Examination of the resultant product distribution of the deuteration, and the location of deuterium incorporation establishes the role of a hydroxy-imine species as a key reaction intermediate. In addition, the acid catalysed tautomerism to the ketone is shown to be a reversible side reaction, but also a contributor to desired product formation. Moreover, an order for the three critical hydrogen consuming steps in phenethylamine formation is established. Hydrogenation of the nitrile functionality to afford the hydroxy-imine precedes hydrogenolysis of the hydroxyl group, with the final step being hydrogenation of the imine to form the target product, phenethylamine

Increased Radiative Lifetime of Rare Earth-doped Zinc Oxyhalide Tellurite Glasses

We have investigated the structural and optical properties of rare earth-doped zinc tellurite glasses modified by the substitution of ZnF2. Raman and phonon sideband spectroscopies were employed to characterize changes in the glass structure as well as to probe vibrational behavior in the immediate vicinity of the rare earth ion. These measurements are combined with photoluminescence and optical absorption to monitor the effect of halide substitution upon the optical behavior of the rare earth dopant. A substantial increase in the intrinsic radiative lifetime of Nd3+ is observed with increasing halide concentration

Investigating discrepancies between experimental solid-state NMR and GIPAW calculation : NC–N 13C and OH⋯O 1H chemical shifts in pyridinium fumarates and their cocrystals

An NMR crystallography analysis is presented for four solid-state structures of pyridine fumarates and their cocrystals, using crystal structures deposited in the Cambridge Crystallographic Data Centre, CCDC. Experimental one-dimensional, one-pulse 1H and 13C cross-polarisation (CP) magic-angle spinning (MAS) nuclear magnetic resonance (NMR) and two-dimensional 14N–1H heteronuclear multiple-quantum coherence MAS NMR spectra are compared with gauge-including projector augmented wave (GIPAW) calculations of the 1H and 13C chemical shifts and the 14N shifts that additionally depend on the quadrupolar interaction. Considering the high ppm (>10 ppm) 1H resonances, while there is good agreement (within 0.4 ppm) between experiment and GIPAW calculation for the hydrogen-bonded NH moieties, the hydrogen-bonded fumaric acid OH resonances are 1.2–1.9 ppm higher in GIPAW calculation as compared to experiment. For the cocrystals of a salt and a salt formed by 2-amino-5-methylpyridinium and 2-amino-6-methylpyridinium ions, a large discrepancy of 4.2 and 5.9 ppm between experiment and GIPAW calculation is observed for the quaternary ring carbon 13C resonance that is directly bonded to two nitrogens (in the ring and in the amino group). By comparison, there is excellent agreement (within 0.2 ppm) for the quaternary ring carbon 13C resonance directly bonded to the ring nitrogen for the salt and cocrystal of a salt formed by 2,6-lutidinium and 2,5-lutidine, respectively