The first dimeric trioganotin fluoride : stabilization by unsymmetrically oriented menthyl substituents

In the solid state, (-)-tris([1R,2S,5R]-menthyl)tin fluoride, Men₃SnF (6), exhibits a dimeric structure in which one tin atom is four-coordinate and the other five-coordinate. This novel dimeric association mode is attributed to the orientation of the unsymmetrical menthyl groups, which are arranged to allow a minimum Sn···Sn separation of 4.84 Å within the dimer. The exocyclic isopropyl groups of the menthyl groups point in opposite directions on each tin atom of the dimer, thus preventing further association (Sn···Sn separation outside the dimer 10.49 Å). ¹¹⁹Sn and ¹⁹F MAS NMR spectroscopy were utilized to probe the diverse coordination numbers found by X-ray crystallography for the geometries of the two tin and fluorine sites. In solution, 6 is a monomer at both room temperature and -100 °C. However, upon addition of Bu₄NF, 6 is in equilibrium with [(Men₃SnF)₂F]- (6a), [Men₃SnF₂]^- (6b), and noncoordinating fluoride anions.

Fluoride-assisted synthesis of mullite (Al5.65 Si0.35 O9.175) nanowires

Novel silicon-deficient mullite (Al_5.65Si_0.35O_9.175) single crystal nanowires were synthesized in large quantities on mica substrates assisted by the intermediate fluoride species. The nanowires have diameters in the range 50–100 nm and typical lengths of several µm. Aligned nanowires were observed at the substrate edge. The nanowires have strong photoluminescence (PL) emission bands at 310, 397, 452 and 468 nm.

Absorption and desorption characteristics of fluoride in the calcareous and siliceous sand sheet aquifers of south-west Victoria, Australia

This study assessed the sustainability of utilising groundwater systems to
manage an aluminium smelter's fluoridated trade wastewater stream. Replacing ocean discharge of the wastewater with land irrigation is one option. Using a groundwater model (developed using MODFLOW incorporating parameter estimation software (PEST-ASP)), we found that most of the groundwater flow takes place through surface sands. Fluoride is adsorbed in these sands during the drier summer months, but desorption is rapid when winter rain flushes the aquifer. Underlying clays and other layers prevent significant contamination of the deeper aquifer.

Aluminium smelter wastewater : groundwater fluoride fate

This study assessed the viability of utilising groundwater systems to manage Portland Aluminium's trade waste water stream. A mathematical groundwater model was created to assess laboratory and field results. Fluoride was modelled for spatio-temporal longevity in the system. All models indicate that fluoride will ultimately exit the site to the seaward boundary.

Enhancement of ion dynamics in PMMA-based gels with addition of TiO2 nano-particles

Solvent and ion dynamics in PMMA based gels have been investigated as a function of the loading of nanosized TiO₂ particles. The gels have a molar ratio of 46.5:19:4.5:30 of ethylene carbonate (EC), propylene carbonate (PC), lithium perchlorate and PMMA, respectively. A series of samples with 0, 4, 6 and 8 wt.% TiO₂ filler were investigated. The diffusion coefficients for the lithium ions and for the two solvents (EC and PC) were investigated by pfg-NMR. It was shown that the addition of filler to the gel electrolytes enhances the diffusion of the cations, while the diffusion of the solvents remains constant. Raman measurements show no significant changes in ion–ion interactions with the addition of fillers, while the ionic conductivity is seen to decrease. However, the sample with 8 wt.% TiO₂ had a conductivity close to that of the unfilled sample.

The enhancement of lithium ion dissociation in polyelectrolyte gels on the addition of ceramic nano-fillers

Nano-particle oxide fillers including TiO₂, SiO₂ and Al₂O₃ have previously been shown to have a significant affect on the properties of both polymer and polymer gel electrolytes. In some cases, conductivity increases of one order of magnitude have been reported in crystalline PEO–base complexes. In this work, we report the effects of TiO₂ and SiO₂ on a poly(Li-AMPS)-based gel polyelectrolyte. Impedance spectroscopy and pfg-NMR spectroscopy indicates an increase in the number of available charge carriers with the addition of filler. An ideal amount of ceramic filler has been identified, with additional filler only saturating the system and reducing the conductivity below that of the pristine polyelectrolyte system. SEM micrographs suggest a model whereby the filler interacts readily with the sulfonate group; the surface area of the filler being an important factor.

Enhancement of ion dissociation in polyelectrolyte gels

High conductivity in single ion conducting polymer electrolytes is still the ultimate aim for many electrochemical devices such as secondary lithium batteries. Achieving effective ion dissociation in these cases remains a challenge since the active ion tends to remain in close proximity to the backbone charge as a result of a low degree of ion dissociation. A unique aspect of this dissociation problem in polyelectrolytes is the repulsion between the backbone charges created by dissociation. One way of enhancing ion dissociation in polyelectrolyte systems is to use copolymers in which only a fraction (<20%) of the mer units are charged and where the comonomer is itself chosen to be polar and preferably to be compatible with potential solvents. We have also found that certain dissociation enhancers based on ionic liquids or boroxine ring compounds can lead to high ionic conductivity. In the cases where an ionic liquid is used as the solvent in a polyelectrolyte gel, the viscosity of the ionic liquid and its hydrophilicity are critical to achieving high conductivity. Compounds based on the dicyanamide anion appear to be very effective ionic solvents; polyelectrolyte gels incorporating such ionic liquids exhibit conductivities as high as 10⁻² S/cm at room temperature. In the case of boroxine ring dissociation enhancers, gels based on poly(lithium-2-acrylamido-2-methyl-1-propanesulfonate) and ethylene carbonate produce conductivities approaching 10⁻³ S/cm. This paper will discuss these approaches for achieving higher conductivity in polyelectrolyte materials and suggest future directions to ensure single ion transport.

Ionic conductivity of polymer gels deriving from alkali metal ionic liquids and negatively charged polyelectrolytes

We have prepared polymer gel electrolytes with alkali metal ionic liquids (AMILs) that inherently contain alkali metal ions. The AMIL consisted of sulfate anion, imidazolium cation, and alkali metal cation. AMILs were mixed directly with poly(3-sulfopropyl acrylate) lithium salt or poly(2-acrylamido-2-methylpropanesulfonic acid) lithium salt to form polymer gels. The ionic conductivity of these gels decreased with increasing polymer fraction, as in general ionic liquid/polymer mixed systems. At low polymer concentrations, these gels displayed excellent ionic conductivity of 10⁻⁴ to 10⁻³ S cm⁻¹ at room temperature. Gelation was found to cause little change in the ⁷Li diffusion coefficient of the ionic liquid, as measured by pulse-field-gradient NMR. These data strongly suggest that the lithium cation migrates in successive pathways provided by the ionic liquids.

Zwitterion effect in polyelectrolyte gels based on lithium methacrylate-N,N-dimethyl acrylamide copolymer

Zwitterionic compounds such as those based on 1-butylimidazolium-3-(n-butanesulfonate) have previously been shown to have positive effects on the transport properties of polyelectrolytes. The addition of the zwitterion has been found to, in some cases, increase the dissociation of the lithium ion and enhance the conductivity by almost an order of magnitude. In this work, we report the effects of adding the above-mentioned zwitterion into the polyelectrolyte gel system poly(lithium methacrylate-co-N,N-dimethyl acrylamide); the anionic group being a stronger base leads to different behaviour for this copolymer compared to previous work. Polyelectrolyte gels based on dimethyl sulfoxide and polyether solvents were investigated to determine the breadth of applicability of the zwitterion in improving lithium ion transport. Impedance spectroscopy and pulse field gradient-NMR diffusion indicate an increase in the number of available charge carriers with zwitterion addition in some gel systems, however, the effect is not universal.

Properties of a carbon-fibre composite modified by electrospun poly (vinylidene fluoride)

The interlaminar toughening of a carbon-fibre reinforced composite by incorporation of electrospun polyvinylidene fluoride (PVDF) nanofibrous membranes was explored in this work. The nanofibres were electrospun directly onto commercial pre-impregnated carbon fibre materials under optimised conditions and PVDF was found to primarily crystallise in its β phase polymorphic form. There is strong evidence from DMTA analysis to suggest that a partial miscibility between the amorphous phases of the PVDF nanofibres and the epoxy exists. The improved plastic deformation at the crack tip after inclusion of the nanofibres was directly translated to a 57% increase in the mode II interlaminar fracture toughness (in-plane shear failure). Conversely, the fracture toughness in mode I (opening failure) was slightly lower than the reference by approximately 20%, and the results were interpreted from the complex micromechanisms of failure arising from the changes in polymorphism of the PVDF.

Architecture of fiber network : from understanding to engineering of molecular gels

A new approach of engineering of molecular gels was established on the basis of a nucleation-initiated network formation mechanism. A variety of gel network structures can be obtained by regulating the starting temperature of the sol−gel transition. This enables us to tune the network from the spherulitic domains pattern to the extensively interconnected fibrillar network. As the consequence of fibrous network structure turning, desirable rheological and other in-use properties of the materials can be obtained accordingly. This approach of micro-/nanostructural fabrication may open up a new route for micro-/nanofunctional materials engineering in general.