Jill S. Wheeler

Thermally Programmable pH Buffers.

Many reactions in both chemistry and biology rely on the ability to precisely control and fix the solution concentrations of either protons or hydroxide ions. In this report, we describe the behavior of thermally programmable pH buffer systems based on the copolymerization of varying amounts of acrylic acid (AA) groups into N-isopropylacrylamide polymers. Because the copolymers undergo phase transitions upon heating and cooling, the local environment around the AA groups can be reversibly switched between hydrophobic and hydrophilic states affecting the ionization behavior of the acids. Results show that moderate temperature variations can be used to change the solution pH by two units. However, results also indicate that the nature of the transition and its impact on the pH values are highly dependent on the AA content and the degree of neutralization.

High temperature polymer dielectrics from the ring opening metathesis polymerization (ROMP)

Recently much research has focused on the development of new polymer dielectric materials to fabricate capacitors for use in the inverters of next generation hybrid electric vehicles (HEV). The capacitors used in HEVs inverters will be required to operate at 150 °C, 600V, and have an energy density of 0.9 J/cm3. Polymer based thin film capacitors are ideal for this application due to their relatively high energy density, low cost, and high dielectric breakdown strength. We have polymerized several ring strained monomers using ring opening metathesis polymerization (ROMP) and have identified a promising polymer system based on N-Phenyl-7-oxanorbornene-5,6-dicarboximide (PhONDI). Several of its copolymers with norbornene have been evaluated for possible use as next generation high temperature polymer dielectrics in thin film capacitors. The copolymers were cast into thin films and Au electrodes were deposited on the polymer film. The electrical properties were evaluated as a function of temperature. The polymer system exhibited very good high temperature dielectric properties and is potentially useful as a high temperature capacitor dielectric.

Supramolecular Assembly of Asymmetric Self-neutralizing Amphiphilic Peptide Wedges.

Mimicking the remarkable dynamic and multifunctional utility of biological nanofibers, such as microtubules, is a challenging and technologically attractive objective in synthetic supramolecular chemistry. Understanding the complex molecular interactions that govern the assembly of synthetic materials, such as peptides, is key to meeting this challenge. Using molecular dynamics simulations to guide molecular design, we explore here the self-assembly of structurally and functionally asymmetric wedge-shaped peptides. Supramolecular assembly into nanofiber gels or multilayered lamellar structures was determined by cooperative influences of hydrogen bonding, amphiphilicity (hydrophilic asymmetry), and the distribution of electrostatic charges on the aqueous self-assembly of asymmetric peptides. Molecular amphiphilicity and β-sheet forming capacity were both identified as necessary, but not independently sufficient, to form supramolecular nanofibers. Imbalances in positive and negative charges prevented nanofiber assembly, while the asymmetric distribution of balanced charges within a peptide is believed to affect peptide conformation and subsequent self-assembly into either nanofibers or lamellar structures. Insights into cooperative molecular interactions and the effects of molecular asymmetry on assembly may aid the development of next-generation supramolecular nanomaterial assemblies.

Enhanced alkaline stability in a hafnium-substituted NaSICON ion conductor

We present here a multi-length scale integration of compositionally tailored NaSICON-based Na+ conductors to create a high Na+ conductivity system resistant to chemical attack in strongly alkaline aqueous environments. Using the Pourbaix Atlas as a generalized guide to chemical stability, we identify NaHf2P3O12 (NHP) as a candidate NaSICON material for enhanced chemical stability at pH > 12, and demonstrate the stability of NHP powders under accelerated aging conditions of 80 °C and pH = 13–15 for a variety of alkali metal cations. To compensate for the relatively low ionic conductivity of NHP, we develop a new low temperature (775 °C) alkoxide-based solution deposition chemistry to apply dense NHP thin films onto both platinized silicon wafers and bulk, high Na+ conductivity Na3Zr2Si2PO12 (NZSP) pellets. These NHP films display Na+ conductivities of 1.35 × 10−5 S cm−1 at 200 °C and an activation energy of 0.53 eV, similar to literature reports for bulk NHP pellets. Under aggressive conditions of 10 M KOH at 80 °C, NHP thin films successfully served as an alkaline-resistant barrier, extending the lifetime of NZSP pellets from 4.26 to 36.0 h. This integration of compositionally distinct Na+ conductors across disparate length scales (nm, mm) and processing techniques (chemically-derived, traditional powder) represents a promising new avenue by which Na+ conducting systems may be utilized in alkaline environments previously thought incompatible with ceramic Na+ conductors.

Aerosol filtration testing for enhanced performance of radionuclide monitoring stations

Aerosol filtration was studied to improve U.S. Radionuclide Monitoring Station (RMS) performance for Nuclear-Treaty-Verification. We characterized the performance of three filter materials which employed electrostatically charged filter fibers to enhance nanoparticle collection. Particle-pre-charging, a well-established industrial technique, was tested and enhanced aerosol collection efficiencies. Test results indicated it may be possible to reduce baseline radionuclide sensitivity to approximately 55–60% of current values by increasing the volume of air sampled. Engineering analysis suggested that particle-pre-charging may be a viable technical approach for fielded RMS systems.

Lightning arrestor connector lead magnesium niobate qualification pellet test procedures.

Enhanced knowledge preservation for DOE DP technical component activities has recently received much attention. As part of this recent knowledge preservation effort, improved documentation of the sample preparation and electrical testing procedures for lead magnesium niobate--lead titanate (PMN/PT) qualification pellets was completed. The qualification pellets are fabricated from the same parent powders used to produce PMN/PT lightning arrestor connector (LAC) granules at HWF&T. In our report, the procedures for fired pellet surface preparation, electrode deposition, electrical testing and data recording are described. The dielectric measurements described in our report are an information only test. Technical reasons for selecting the electrode material, electrode size and geometry are presented. The electrical testing is based on measuring the dielectric constant and dissipation factor of the pellet during cooling from 280 C to 220 C. The most important data are the temperature for which the peak dielectric constant occurs (Curie Point temperature) and the peak dielectric constant magnitude. We determined that the peak dielectric constant for our procedure would be that measured at 1 kHz at the Curie Point. Both the peak dielectric constant and the Curie point parameters provide semi-quantitative information concerning the chemical and microstructural homogeneity of the parent material used for the production of PMN/PT granules for LACs. Finally, we have proposed flag limits for the dielectric data for the pellets. Specifically, if the temperature of the peak dielectric constant falls outside the range of 250 C {+-} 30 C we propose that a flag limit be imposed that will initiate communication between production agency and design agency personnel. If the peak dielectric constant measured falls outside the range 25,000 {+-} 10,000 we also propose that a flag limit be imposed.