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At least 1,171 records · Page 65

Relationship between microporous structure and light gas transport through glassy polymeric membranes revealed by molecular simulations

Microporous glassy polymers are attractive materials for gas separation membranes, due to their high permeability and tailorable selectivity, provided physical aging can be delayed. The archetypal microporous glassy polymer, PTMSP, can be blended with a hyper-crosslinked isatin–triptycene porous polymer network (PPN) to delay physical aging. However, while PPN is effective at reducing physical aging, it also affects the permeability of light gases through PTMSP. Molecular dynamics simulations were used here to shed fundamental light on the mechanisms responsible for these effects. Atomistic models are developed that satisfactorily reproduce experimental observations such as matrix density and cavity size distributions for neat PTMSP as well as for PTMSP–PPN blends. Analysis of the simulation results suggests that physical aging is delayed because the PPN inclusions slow down PTMSP relaxation while reducing the connectivity between free volume pockets. To understand how PPN inclusions affect light gas permeability, the atomistic models developed are used to probe CO 2 and CH 4 diffusion and sorption. These simulations are conducted for PTMSP matrices exhibiting varying density, towards reproducing experimental permeability data. Interrogating the simulation trajectories, it is discovered that while CH 4 travels preferentially through the free volume cavities, CO 2 preferentially interacts with the available surfaces, especially in the presence of PPN. These differences help interpret experimental observations. The transport of C 2 H 6 and H 2 S through PTMSP matrices was also investigated. These gases, and in particular H 2 S, were found to absorb within PTMSP, yielding very low diffusion coefficients. The ability to predict differences in diffusion pathways for various natural gas components unveils the possibility of engineering membranes to control permeability and selectivity towards large-scale applications.

Bao Le, Tran Thi [Univ. of Oklahoma, Norman, OK (U↗

A new approach to the design of surface subsystems of polymeric insulators for HV and MV apparatus under AC voltage

The design of high voltage and medium voltage AC and DC standoff insulators, and, in general, of insulation systems where surface and interface properties are predominant factors, is based on specifications and standards that rely upon long-term experiences and lab testing. Surface insulating properties depend on electrical and thermal stresses, besides environmental factors, and the inception of extrinsic ageing phenomena, such as partial discharges, can be already a cause of reduced reliability and premature failure (for organic insulating materials). An innovative approach, based on field simulation, discharge modelling, and partial discharge inception measurements is presented by the authors, which can establish a solid basis to optimise insulation design for any type of supply voltage waveform. This method, the three-leg approach, is applied here to a cable system under AC sinusoidal voltage, but it can work for any type of insulation system, such as bushings, switch gears, transformers, rotating machines, and power electronics boards.

42 ENGINEERING↗

Development of silver and zinc oxide decorated nanoclay containing polymeric composites for water disinfection applications

Contaminated drinking water has serious implications to the human health that could lead to death. The rapid growth of bacterial contamination in drinking water is alarming, and yet a robust and cost effective method with less limitation has not been developed. The current study is aimed at evaluating the performance of nanoclay composites dispersed in chitosan biopolymer as an antibacterial material. The performances of the composites were evaluated using the batch kinetic studies. Three composites of Ag-CtsB, ZnO-CtsB and Ag/ZnO-CtsB were prepared and evaluated against gram negative Escherichia coli and gram positive Enterococcus faecalis bacteria. The composites were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive spectroscopy and BET surface area measurements. Antibacterial activity results showed that the composites can be a potent bactericide material for water disinfection as they are highly effective against both gram negative and gram positive bacteria tested. Whereas both Ag-CtsB and ZnO-CtsB composites showed good antibacterial activity against bacteria with removal efficiency from 51%, best antibacterial activity was observed with Ag/ZnO-CtsB composite with removal efficiency from 78%. The results revealed that Ag/ZnO-CtsB composite is a promising bactericide that is highly effective against both gram negative and gram positive bacteria tested.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preparation and characterization of polymeric nanoparticles from Gadong starch

Dioscorea hispida (Gadong tuber) was seldom used and forgotten as a food source due to their toxicity. In contrast to that, the Gadong tuber can be a source of polysaccharides which can be manipulated as an alternative source for industrial applications. This research reported on how to synthesize starch nanoparticles from Gadong tuber by using a simple acid hydrolysis process. The yield of starch nanoparticles obtained from seven days of acid hydrolysis was reduced to 13%. The X-ray diffraction measurements showed that the native Gadong starch particle is of the C-crystalline type, and that the synthesized nanoparticles showed an increase in crystallinity compared to the native particles. Transmission electron microscopy results demonstrated that the starch particle morphologies were either round or irregular shape, with diameters ranging from 96-110 nm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymer stabilization of the smectic C-alpha* liquid crystal phase—Over tenfold thermal stabilization by confining networks of photo-polymerized reactive mesogens

The smectic C*-alpha (SmC{sub α}*) phase is one of the sub-phases of ferroelectric liquid crystals that has drawn much interest due to its electro-optical properties and ultrafast switching. Generally observed above the ferroelectric SmC* phase in temperature, the SmC{sub α}* commonly shows only very narrow phase temperature range of a few degree Celsius. To broaden the SmC{sub α}* phase, polymer stabilization was investigated for thermal phase stabilization. Two different reactive monomers were tested in three mixtures, and all three broadened the temperature range of the SmC{sub α}* phase from 3 °C to 39 °C. The current reversal method was used to determine the phase existence versus temperature. Moreover, the texture and network structure was studied by polarized optical microscopy and scanning electron microscopy, with the latter revealing the confinement of the smectic layer structure within the porous polymer network.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A self-adjustable four-point probing system using polymeric three dimensional coils and non-toxic liquid metal

This paper describes a self-adjustable four-point probe (S4PP) system with a square configuration. The S4PP system consists of 3D polymer coil springs for the independent operation of each tungsten (W) probe, microfluidic channels filled with a nontoxic liquid metal, and a LabView-based control system. The 3D coil springs made by PMMA are fabricated with a 3D printer and are positioned in a small container filled with the non-toxic liquid metal. This unique configuration allows independent self-adjustment of the probe heights for precise measurements of the electrical properties of both flexible and large-step-height microsamples. The feasibility of the fabricated S4PP system is evaluated by measuring the specific resistance of Cr and Au thin films deposited on silicon wafers. The system is then employed to evaluate the electrical properties of a Au thin film deposited onto a flexible and easily breakable silicon diaphragm (spring constant: ∼3.6 × 10{sup −5} N/m). The resistance of the Cr thin films (thickness: 450 nm) with step heights of 60 and 90 μm is also successfully characterized. These experimental results indicate that the proposed S4PP system can be applied to common metals and semiconductors as well as flexible and large-step-height samples.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Insights into the variability of nucleated amyloid polymerization by a minimalistic model of stochastic protein assembly

Self-assembly of proteins into amyloid aggregates is an important biological phenomenon associated with human diseases such as Alzheimer’s disease. Amyloid fibrils also have potential applications in nano-engineering of biomaterials. The kinetics of amyloid assembly show an exponential growth phase preceded by a lag phase, variable in duration as seen in bulk experiments and experiments that mimic the small volumes of cells. Here, to investigate the origins and the properties of the observed variability in the lag phase of amyloid assembly currently not accounted for by deterministic nucleation dependent mechanisms, we formulate a new stochastic minimal model that is capable of describing the characteristics of amyloid growth curves despite its simplicity. We then solve the stochastic differential equations of our model and give mathematical proof of a central limit theorem for the sample growth trajectories of the nucleated aggregation process. These results give an asymptotic description for our simple model, from which closed form analytical results capable of describing and predicting the variability of nucleated amyloid assembly were derived. We also demonstrate the application of our results to inform experiments in a conceptually friendly and clear fashion. Our model offers a new perspective and paves the way for a new and efficient approach on extracting vital information regarding the key initial events of amyloid formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct laser writing of polymeric nanostructures via optically induced local thermal effect

We demonstrate the fabrication of desired structures with feature size below the diffraction limit by use of a positive photoresist. The direct laser writing technique employing a continuous-wave laser was used to optically induce a local thermal effect in a positive photoresist, which then allowed the formation of solid nanostructures. This technique enabled us to realize multi-dimensional sub-microstructures by use of a positive photoresist, with a feature size down to 57 nm. This mechanism acting on positive photoresists opens a simple and low-cost way for nanofabrication.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Electrohydrodynamic printing of organic polymeric resistors on flat and uneven surfaces

In materials printing applications, the ability to generate fine droplets is critical for achieving high-resolution features. Other desirable characteristics are high print speeds, large stand-off distances, and minimal instrumentation requirements. In this work, a tunable electrohydrodynamic (EHD) printing technique capable of generating micron-sized droplets is reported. This method was used to print organic resistors on flat and uneven substrates. These ubiquitous electronic components were built using the commercial polymer-based conductive ink poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS), which has been widely used in the manufacturing of organic electronic devices. Resistors with widths from 50 to 500 μm and resistances from 1 to 70 Ω/μm were created. An array of emission modes for EHD printing was identified. Among these, the most promising is the microdripping mode, where droplets 10 times smaller than the nozzle's inner diameter were created at frequencies in excess of 5 kHz. It was found that the ink flow rate, applied voltage, and stand-off distance all significantly influence the droplet generation frequency. In particular, the experimental results reveal that the frequency increases nonlinearly with the applied voltage. The non-Newtonian shear thinning behavior of PEDOT:PSS strongly influenced the droplet frequency. Finally, the topology of a 3-dimensional target substrate had a significant effect on the structure and function of a printed resistor.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Structure and dynamics of short-chain polymerized ionic liquids

Combining experimental results obtained with X-ray scattering and field-gradient nuclear magnetic resonance (NMR) and an assessment of new and previous dielectric and rheology data, our study focuses on the molecular weight (M w ) evolution of local structure and dynamics in a homologous series of covalently bonded ionic liquids. Performed on a family of electrolytes with a tailored degree of ionic decoupling, this study reveals the differences between monomeric and oligomeric melts with respect to their structural organization, mass and charge transport, and molecular diffusion. Our work demonstrates that for the monomeric compound, the broadband conductivity and mechanical spectra reflect the same underlying distribution of activation barriers and that the Random Barrier Model describes fairly well both the ionic and structural relaxation processes in these materials. Moreover, the oligomers with chains comprising ten segments only exhibit both structural and dynamical fingerprints of a genuine polymer. A comparison of conductivity levels estimated using the self-diffusion coefficients probed via NMR and those probed directly with dielectric spectroscopy reflects the emerging of ion correlations which are affecting the macroscopic charge transport in these materials in a chain-length dependent manner.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗