Melanie M. Britton

Transition to shear banding in pipe and Couette flow of wormlike micellar solutions

We used both conventional rheometry and nuclear magnetic resonance (NMR) velocimetry to study shear banding in a solution of 200 mM cetylpyridinium chloride and 120 mM sodium salicylate in 0.5 M sodium chloride. The solution behaved as a Maxwell fluid up to frequencies of 10 Hz. Theoretical predictions of critical strain rate and shear stress were in good agreement with measurements obtained using controlled strain rate rheometry. Using NMR velocimetry, we observed convincing evidence of shear banding in capillary flow with a band of very high, approximately constant, shear rate next to the wall that grew in thickness with increasing apparent shear rate. We believe that the shear rate in this band (∼600 s−1) marks the beginning of the hypothesized high shear rate limb of the flow curve. We also observed shear banding in both the cylindrical Couette and cone-and-plate geometries. Shear banding started at shear rates that were approximately the same as the critical shear rate measured with the mechanical rh...

Nuclear magnetic resonance visualization of anomalous flow in cone-and-plate rheometry

We demonstrate the use of nuclear magnetic resonance (NMR) microscopy to image the velocity distribution for fluids sheared within the gaps (4° and 7°) of cone-and-plate rheometers. These measurements employ a specially constructed rheogoniometer, which fits within the NMR probe system. While the uniform shear rate assumption is verified in the case of simple Newtonian and non-Newtonian fluids, a range of anomalous behavior (apparent slip, shear banding, and fracture) is observed in other systems, including wormlike surfactants, semidilute solutions of 18 MDa polyacrylamide, and dispersed silica in silicone grease.

Magnetic resonance imaging of chemistry

Magnetic resonance imaging (MRI) has long been recognized as one of the most important tools in medical diagnosis and research. However, MRI is also well placed to image chemical reactions and processes, determine the concentration of chemical species, and look at how chemistry couples with environmental factors, such as flow and heterogeneous media. This tutorial review will explain how magnetic resonance imaging works, reviewing its application in chemistry and its ability to directly visualise chemical processes. It will give information on what resolution and contrast are possible, and what chemical and physical parameters can be measured. It will provide examples of the use of MRI to study chemical systems, its application in chemical engineering and the identification of contrast agents for non-clinical applications. A number of studies are presented including investigation of chemical conversion and selectivity in fixed-bed reactors, temperature probes for catalyst pellets, ion mobility during tablet dissolution, solvent dynamics and ion transport in Nafion polymers and the formation of chemical waves and patterns.

Sizing of reverse micelles in microemulsions using NMR measurements of diffusion.

This paper reports the size of reverse micelles (RMs) in AOT/octane/H(2)O and CTAB/hexanol/H(2)O microemulsions using magnetic resonance (MR) pulsed field gradient (PFG) measurements of diffusion. Diffusion data were measured using the pulsed gradient stimulated echo (PGSTE) experiment for surfactant molecules residing in the RM interface. Inverse Laplace transformation of these data generated diffusion coefficients for the RMs, which were converted into hydrodynamic radii using the Stokes-Einstein relation. This technique is complementary to those previously used to size RMs, such as dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS), but also offers several advantages, which are discussed. RM sizes, determined using the PGSTE method, in the AOT (sodium bis(2-ethylhexyl) sulfosuccinate) and CTAB (cetyltrimethylammonium bromide) microemulsions were compared with previous DLS and SAXS data, showing good agreement. Methods for determining number distributions from the PGSTE data, through the use of scaling factors, were investigated.

In situ magnetic resonance measurement of conversion, hydrodynamics and mass transfer during single- and two-phase flow in fixed-bed reactors

In recent years there has been increasing interest in applying magnetic resonance (MR) techniques in areas of engineering and chemical technology. The science that underpins many of these applications is the physics and chemistry of transport and reaction processes in porous materials. Key to the exploitation of MR methods will be our ability to demonstrate that MR yields information that cannot be obtained using conventional measurement techniques in engineering research. This article describes two case studies that highlight the power of MR to give new insights to chemical engineers. First, we demonstrate the application of MR techniques to explore both mass transfer and chemical conversion in situ within a fixed bed of catalyst, and we then use these data to identify the rate-controlling step of the chemical conversion. Second, we implement a rapid imaging technique to study the stability of the gas-liquid distribution in the low- and high-interaction two-phase flow regimes in a trickle-bed reactor.

De Novo Design of Ln(III) Coiled Coils for Imaging Applications

A new peptide sequence (MB1) has been designed which, in the presence of a trivalent lanthanide ion, has been programmed to self-assemble to form a three stranded metallo-coiled coil, Ln(III)(MB1)3. The binding site has been incorporated into the hydrophobic core using natural amino acids, restricting water access to the lanthanide. The resulting terbium coiled coil displays luminescent properties consistent with a lack of first coordination sphere water molecules. Despite this the gadolinium coiled coil, the first to be reported, displays promising magnetic resonance contrast capabilities.

NMR MICROSCOPY AND THE NON-LINEAR RHEOLOGY OF FOOD MATERIALS

The non‐linear viscosities of a number of different food products were examined using NMR microscopy. These materials included xanthan gum–water solutions, cream, semi‐soft butter, egg white, cornflour–water mixtures and two different varieties of tomato sauce. The non‐linear rheology is manifest in the velocity profiles measured across pipe, cylindrical Couette cell and cone‐and‐plate geometries. The properties observed included apparent slip, shear thinning, shear thickening, shear banding and yield stress behaviour. The results show that accurate, non‐invasive velocity profiling is essential if the results of mechanical rheometric measurements are to be interpreted correctly. They also illustrate the power of NMR both to demonstrate the existence of and, potentially, to investigate the particulate or molecular origins of complex rheological properties in food materials.

Detection of pH in Microemulsions, without a Probe Molecule, Using Magnetic Resonance

Proton NMR relaxation times have been used to probe the pH of water inside reverse micelles of a cetyltrimethylammonium bromide (CTAB)-hexanol-aq microemulsion. T(2) relaxation times were found to change with pH; however, T(1) relaxation times remained unaffected. This behavior was attributed to acid-catalyzed exchange between protons of water and hydroxyl protons of the cosurfactant hexanol. The rate of exchange and its influence on the T(2) relaxation time of water, inside the reverse micelle, were investigated as a function of water-to-surfactant ratio (ω(0)) and ionic strength. This exchange behavior and pH-dependent T(2) relaxation time were also observed for two other microemulsions--CTAB-hexane-pentanol-aq and Triton X-100-cyclohexane-hexanol-aq. Using this pH-dependent T(2) relaxation time, it was possible to monitor pH changes in the bromate-sulfite reaction inside a CTAB-hexanol-aq microemulsion.

Mapping B1-induced eddy current effects near metallic structures in MR images: A comparison of simulation and experiment

Magnetic resonance imaging (MRI) in the presence of metallic structures is very common in medical and non-medical fields. Metallic structures cause MRI image distortions by three mechanisms: (1) static field distortion through magnetic susceptibility mismatch, (2) eddy currents induced by switched magnetic field gradients and (3) radio frequency (RF) induced eddy currents. Single point ramped imaging with T1 enhancement (SPRITE) MRI measurements are largely immune to susceptibility and gradient induced eddy current artifacts. As a result, one can isolate the effects of metal objects on the RF field. The RF field affects both the excitation and detection of the magnetic resonance (MR) signal. This is challenging with conventional MRI methods, which cannot readily separate the three effects. RF induced MRI artifacts were investigated experimentally at 2.4 T by analyzing image distortions surrounding two geometrically identical metallic strips of aluminum and lead. The strips were immersed in agar gel doped with contrast agent and imaged employing the conical SPRITE sequence. B1 mapping with pure phase encode SPRITE was employed to measure the B1 field around the strips of metal. The strip geometry was chosen to mimic metal electrodes employed in electrochemistry studies. Simulations are employed to investigate the RF field induced eddy currents in the two metallic strips. The RF simulation results are in good agreement with experimental results. Experimental and simulation results show that the metal has a pronounced effect on the B1 distribution and B1 amplitude in the surrounding space. The electrical conductivity of the metal has a minimal effect.

Magnetic resonance imaging of electrochemical cells containing bulk metal.

The development of improved energy-storage devices, as well as corrosion prevention and metal-electrofinishing technologies, requires knowledge of local composition and transport behaviour in electrolytes near bulk metals, in situ and in real time. It remains a challenge to acquire such data and new analytical methods are required. Recent work shows that magnetic resonance imaging (MRI) is able to map concentration gradients and visualise electrochemical processes in electrochemical cells containing bulk metals. This recent work, along with the challenges, and solutions, associated with MRI of these electrochemical cells are reviewed.