A 13C NMR study of the role of plasticizers in the conduction mechanism of solid polymer electrolytes

The addition of low molecular weight solvents such as dimethyl formamide (DMF) and propylene carbonate (PC) to urethane crosslinked polyethers results in enhancement of polymer segmental motion, as determined in this work from polymer ¹³C spin lattice relaxation measurements (T₁) and glass transition temperatures. The formation of salt-polyether complexes results in a decrease in T₁, even in the presence of the plasticizer, indicating that the polymer ether molecules are still involved in the alkali metal coordination. In a polymer electrolyte containing 1 mol kg⁻¹ LiClO₄ the addition of DMF and PC have significantly different affects on the polymer mobility, although they both enhance the conductivity. The conductivity enhancement therefore is not solely the result of an increased solvent mobility.

pH-detachable polymer brushes formed using titanium−diol coordination chemistry and living radical polymerization (RAFT)

pH-detachable poly(styrene) brushes formed on indium−tin oxide (ITO) glass substrates using metal complex chemistry and reversible addition−fragmentation chain transfer (RAFT) polymerization was described. These pH-detachable polymeric brushes were generated using both “graft-from” and “graft-to” methodologies. The methodologies involved either the surface self-assembly of catechol-functional RAFT agents (graft-from) or catechol-terminal polymer chains (graft-to) onto the ITO substrate via titanium−diol coordination. The stepwise functionalization of the ITO glass surfaces was characterized successfully using X-ray photoelectron spectroscopy (XPS) and contact angle measurement. Poly(styrene) brushes generated using the “graft-from” method were denser than those generated using the “graft-to” method, as exemplified by atom force microscopy (AFM) and quantified using cyclic voltammetry. Poly(styrene) brushes assembled using both methods could be detached easily by manipulating the pH of the brush environment. Cyclic voltammetry was utilized to calculate precisely the surface coverage of the RAFT functionality and polymeric brush density.

Wire coil needleless electrospinning of polymer nanofibers

Elcctrospinning is a very useful technique to produce polymeric nanofibers for diverse applications. The conventional needle-based electrospinning system has VCIY limited fiber productivity and a key challenge has been to develop electrospinning systems that can produce uniform nanofibcrs on a large scale l-3.
In this study, we have demonstrated that a rotating metal wire coil can be used as a nozzle to eiectrospin nanofibers on a large-scale. Without using any needles, the rotating wire coil, partially immersed in a polymer solution reservoir, can pick up a thin layer of charged polymer solution and generate a large number of nanofibers from the wire surface simultaneously. This arrangement significantly increases the nanofiber productivity.
The fiber productivity was found to be determined by the coil dimensions, such as wire diameter, coil radius and distance, and coil length. The effects of applied voltage, the distance bctv,lcen the coil nozzle and collector, and polymer concentration on the fiber
morphology were examined. The dependency of fiber diameter on the polymer concentration showed a similar trend to that for a conventional electrospinning system using a syringe needle nozzle, but the diameter distribution was narrower for the
coil electrospun fibers.
The profiles of electric fIeld strength in coil electrospinning was calculated and showed
concentrated electrical field intensity on the top wire surface. This novel concept of using wire coil as the electrospinning nozzle will contribute to the further development of new large-scale needleless electrospinning systems for nanofiber production.

Recent developments in corrosion inhibitors based on rare earth metal compounds

Rare earth organic compounds can provide an environmentally safe and non-toxic alternative to chromates as corrosion inhibitors for some steel and aluminium applications. For steel lanthanum 4-hydroxy cinnamate offers corrosion protection and reduces the susceptibility to hydrogen embrittlement. Recent work has also indicated that it inhibits the corrosion of steel in environments containing high levels of carbon dioxide. For aluminium alloys, cerium diphenyl phosphate provides excellent corrosion inhibition in chloride environments, and reduces susceptibly to stress corrosion cracking. Furthermore, for both steel and aluminium alloys filiform corrosion can be suppressed when rare earth inhibitor compounds are added as pigments to polymer coatings. The levels of inhibition observed are thought to be due to synergistic effects between the rare earth and organic parts of these novel compounds, and are related to the various species that may be present in the complex chemical conditions that develop in solution close to a metal surface. This paper reviews some of the published research conducted by the group at Deakin University over recent years.

Recent developments in corrosion inhibitors based on rare earth metal compounds

Rare earth organic compounds can provide an environmentally safe and non-toxic alternative to chromates as corrosion inhibitors for some steel and aluminium applications. For steel lanthanum 4-hydroxy cinnamate offers corrosion protection and reduces the susceptibility to hydrogen embrittlement. Recent work has also indicated that it inhibits the corrosion of steel in environments containing high levels of carbon dioxide. For aluminium alloys, cerium diphenyl phosphate provides excellent corrosion inhibition in chloride environments, and reduces susceptibly to stress corrosion cracking. Furthermore, for both steel and aluminium alloys filiform corrosion can be suppressed when rare earth inhibitor compounds are added as pigments to polymer coatings. The levels of inhibition observed are thought to be due to synergistic effects between the rare earth and organic parts of these novel compounds, and are related to the various species that may be present in the complex chemical conditions that develop in solution close to a metal surface. This paper reviews some of the published research conducted by the group at Deakin University over recent years.©2014 Institute of Materials, Minerals and Mining.

Nonlinear dynamic modeling of ionic polymer conductive network composite actuators using rigid finite element method

Ionic polymer conductive network composite (IPCNC) actuators are a class of electroactive polymer composites that exhibit some interesting electromechanical characteristics such as low voltage actuation, large displacements, and benefit from low density and elastic modulus. Thus, these emerging materials have potential applications in biomimetic and biomedical devices. Whereas significant efforts have been directed toward the development of IPMC actuators, the establishment of a proper mathematical model that could effectively predict the actuators' dynamic behavior is still a key challenge. This paper presents development of an effective modeling strategy for dynamic analysis of IPCNC actuators undergoing large bending deformations. The proposed model is composed of two parts, namely electrical and mechanical dynamic models. The electrical model describes the actuator as a resistive-capacitive (RC) transmission line, whereas the mechanical model describes the actuator as a system of rigid links connected by spring-damping elements. The proposed modeling approach is validated by experimental data, and the results are discussed. © 2014 Elsevier B.V. All rights reserved.

Qualitative spectroscopic characterization of the matrix-silane coupling agent interface across metal fibre reinforced ion exchange resin composite membranes

The characterization of novel metal reinforced electro-dialysis ion exchange membranes, for water desalination, by attenuated total reflectance Fourier transform infrared spectroscopy mapping is presented in this paper. The surface of the porous stainless steel fibre meshes was treated in order to enhance the amount of surface oxide groups and increase the material hydrophilicity. Then, the metal membranes were functionalized through a sol-gel reaction with silane coupling agents to enhance the affinity with the ion exchange resins and avoid premature metal oxidation due to redox reactions at the metal-polymer interface. Polished cross sections of the composite membranes embedded into an epoxy resin revealed interfaces between metallic frameworks and the silane layer at the interface with the ion exchange material. The morphology of the metal-polymer interface was investigated with scanning electron microscopy and Fourier transform infrared micro-spectroscopy. Fourier transform infrared mapping of the interfaces was performed using the attenuated total reflectance mode on the polished cross-sections at the Australian Synchrotron. The nature of the interface between the metal framework and the ion exchange resin was shown to be homogeneous and the coating thickness was found to be around 1 μm determined by Fourier transform infrared micro-spectroscopy mapping. The impact of the coating on the properties of the membranes and their potential for water desalination by electro-dialysis are also discussed.

Supplementing cold plasma with heat enables doping and nano-structuring of metal oxides

Nitrogen doped SnO2 polycrystalline nanostructures were produced from commercial SnO powders in a new system that combines a low-temperature plasma with heating. The method has the potential to improve the initial efficiency and the cycling performance of SnO2 anodes in Li-ion batteries. With this system, the temperature of the SnO to SnO2 conversion was lowered from 430 to 320 °C, up to 5 at% of doped nitrogen was detected and a nano-scale polycrystalline structure was observed in the product. Combining heat and low-pressure plasma is a promising approach for the production and treatment of enhanced energy storage materials.

Ionic transport through a composite structure of N-ethyl-N-methylpyrrolidinium tetrafluoroborate organic ionic plastic crystals reinforced with polymer nanofibres

The incorporation of polyvinylidene difluoride (PVDF) electrospun nanofibres within N-ethyl-N-methylpyrrolidinium tetrafluoroborate, [C2mpyr][BF4] was investigated with a view to fabricating self-standing membranes for various electrochemical device applications, in particular lithium metal batteries. Significant improvement in mechanical properties and ionic conduction was demonstrated in a previous study, which also demonstrated the remarkably high performance of the lithium-doped composite material in a device. We now seek a fundamental understanding of the role of fibres within the matrix of the plastic crystal, which is essential for optimizing device performance through fine-tuning of the composite material properties. The focus of the current study is therefore a thorough investigation of the phase behaviour and conduction behaviour of the pure and the lithium-doped (as LiBF4) plastic crystal, with and without incorporation of polymer nanofibres. Analysis of the structure of the plastic crystal, including the effects of lithium ions and the incorporation of PVDF fibres, was conducted by means of synchrotron XRD. Ion dynamics were evaluated using VT solid-state NMR spectroscopy. ATR-FTIR spectroscopy was employed to gain insights into the molecular interactions of doped lithium ions and/or the PVDF nanofibres in the matrix of the [C2mpyr][BF4] composites. Preliminary measurements using PALS were conducted to probe structural defects within the pure materials. It was found that ion transport within the plastic crystal was significantly altered by doping with lithium ions due to the precipitation of a second phase in the structure. The incorporation of the fibres activated more mobile sites in the systems, but restricted ion mobility with different trends being observed for each ion species in each crystalline phase. In the presence of the fibres a strong interaction observed between the Li ion and the pyrrolidinium ring disappeared and formation of the second phase was prevented. As a result, an increased number of mobile lithium ions are released into the solid solution structure of the matrix, simultaneously removing the blocking effect of the second phase. Thus, ion conduction was remarkably improved within the Li-doped composite compared to the neat Li-doped plastic crystal.