We present nanometer-scale resolution, ballistic electron emission microscopy (BEEM) studies of Au/octanedithiol/n-GaAs (001) diodes. The presence of the molecule dramatically increases the BEEM threshold voltage and displays an unusual transport signature as compared to reference Au/GaAs diodes. Furthermore, BEEM images indicate laterally inhomogeneous interfacial structure. We present calculations that address the role of the molecular layer at the interface. Our results indicate that spatially resolved measurements add new insight to studies using conventional spatial-averaging techniques.
The enthalpies of formation of hydrotalcite-like phases containing Mg and Al and intercalated with NO{sub 3}{sup -}, Cl{sup -}, I{sup -}, ReO{sub 4}{sup -}, or CO{sub 3}{sup 2-} were determined using high-temperature oxide melt and room-temperature acid solution calorimetry. The relative stability of phases bearing the various anions was gauged by comparing the enthalpy of formation from the single-cation components ({Delta}{sub f}H{sup scc}). Trends relating {Delta}{sub f}H{sup scc} to the nature of intercalating anions (halides, NO{sub 3}{sup -}, and CO{sub 3}{sup 2-}) show small stabilization from the mechanical mixtures of single-cation components. The aim of this study was to relate the enthalpy of formation to the nature of interlayer bonding in hydrotalcite-like compounds (HTLCs) bearing various anions, to uncover trends in the relative aqueous solubilities of these phases. The entropy of formation of these compounds was estimated using an approximation based on third-law entropy measurements for the compound Mg{sub 0.74}Al{sub 0.26}(OH){sub 2}(CO{sub 3}){sub 0.13} {center_dot} 0.39H{sub 2}O which were performed in a previous study. This approximation for the third-law entropy was combined with the enthalpy data from our calorimetric measurements performed in this work in order to calculate the standard-state free energy of formation for the HTLCs. The solubility products for the compounds investigated in this study were calculated from these free energies of formation and were used in geochemical calculations. The results of these calculations support our previous hypothesis that carbonate-intercalated HTLCs are less soluble than phases bearing other anions such as nitrates and halides. We suspect that the solubilities of HTLCs bearing anions other than carbonate may correspond to the solubilities of single-cation phases bearing the same anions.
A finite control volume numerical model was used to estimate the relative magnitude of natural convection and radiation in small enclosures with a cylindrical obstruction. The enclosure had a height of 2.54 cm, widths between 5.08 cm and 10.16 cm, depth of 5.08 cm, and obstruction diameters between 0.51 cm and 1.52 cm. Temperatures ranging from 310 K to 1275 K were placed on the right boundary. These temperatures represented heating from a pool fuel fire. Simulations were run for an hour to determine the temperature response inside the enclosure and obstruction. Another simulation was run where the right boundary temperature was stepped by 40 K/min to represent a transient temperature ramp up from a fire. When two conditions are met, natural convection can be ignored, and only enclosure radiation is necessary for reaching a solution within 10% of results when all heat transfer modes are included. These conditions are when the right boundary temperatures are continuously above 800 K or when the temperature change was 40 K/min or more.
Molecular electronic based chemical vapor sensors were assembled using noble metal nanoparticles and short conjugated phenylene ethynylene (PE) based molecules. Sacrificial capping ligands on the nanoparticles were replaced by tighter binding PE ligands. The films were assembled between pairs of electrodes by iteratively exposing the substrates to solutions of the nanoparticles and PE crosslinking bridging ligands. Some of the conjugated bridging molecules contained an electron deficient phenol to provide a simple platform for developing sensor applications. The phenol is calculated to have a significant change in its HOMO/LUMO gap in the presence of specific analytes. Judicious combination of nanoparticle size and ligand structure provides a film in which the organic bridging ligands dramatically affect film conductance. Specifically, π-conjugated ligands lower resistance more in films with smaller nanoparticles. Thus the sensing mechanism of these films is not based on the typical swelling mechanism but rather on the modulation of the molecular electronic structure of the conducting PE bridging ligands.
Proceedings of SPIE - The International Society for Optical Engineering
Lasater, Matthew S.; Kelley, C.T.; Salinger, Andrew G.; Woolard, Dwight; Zhao, Peiji
Resonant tunneling diodes (RTDs) are ultra-small semiconductor devices that have potential as very high frequency oscillators. To describe the electron transport within these devices, the Wigner-Poisson Equations are used. These equations incorporate quantum mechanics to describe how the electron distribution changes in time due to kinetic energy, potential energy, and scattering effects. To study the RTD, we apply numerical continuation methods to calculate the steady-state electron distribution as the voltage difference across the RTD varies. To implement the continuation methods, the RTD simulator is interfaced to LOCA (Library of Continuation Algorithm), a software library that is a part of Sandia National Laboratories' parallel solver package, Trilinos. With more sophisticated numerical solvers, we are able to calculate solutions on finer grids that were previously too computationally intensive. This is very important to allow for detailed studies of correlation effects which may dramatically influence oscillatory behavior in RTD-based devices. The more accurate results derived from this work reveal new physical effects that were absent in prior studies. Hence, these physics-based and more refined numerical simulations will provide new insights and greatly facilitate the future optimization of RTD-based oscillator sources and thus has important relevance to THz-frequency-regime based spectroscopic sensing technology.
An AlGaN Light-emitting diode (LED) emitting with a peak wavelength at 291 nm and a radiant power of 0.5 mW @ 100 mA was fabricated on a sapphire substrate. A compact gated fluorescence detection system was built using this LED as the excitation light source. We demonstrate that it provides sufficient power using Terbium enhanced fluorescence to detect subnanomolar concentrations of dipicolinic acid (DPA, 2, 6-pyridinedicarboxylic acid), a substance uniquely present in bacterial spores such as that from B. anthracis, providing a basis for convenient early warning detectors. We also describe initial results from a novel approach for biological aerosol detection using long lived fluorescence from a Europium tagged dye that binds to proteins.
Laser Engineered Net Shaping (LENS) is being evaluated for use as a metal component repair/modification process for the NWC. An aspect of the evaluation is to better understand the characteristics of the interface between LENS deposited material and the substrate on which it is deposited. A processing and metallurgical evaluation was made on LENS processed material fabricated for component qualification tests. A process parameter evaluation was used to determine optimum build parameters and these parameters were used in the fabrication of tensile test specimens to study the characteristics of the interface between LENS deposited material and several types of substrates. Analyses of the interface included mechanical properties, microstructure, and metallurgical integrity. Test samples were determined for a variety of geometric configurations associated with interfaces between LENS deposited material and both wrought base material and previously deposited LENS material. Thirteen different interface configurations were fabricated for evaluation representing a spectrum of deposition conditions from complete part build, to hybrid substrate-LENS builds, to repair builds for damaged or re-designed housings. Good mechanical properties and full density were observed for all configurations. When tested to failure, fracture occurred by ductile microvoid coalescence. The repair and hybrid interfaces showed the same metallurgical integrity as, and had properties similar to, monolithic LENS deposits.
We present a novel class of dynamic neural networks that is capable of learning, in an unsupervised manner, attractors that correspond to generalities in a data set. Upon presentation of a test stimulus, the networks follow a sequence of attractors that correspond to subsets of increasing size or generality in the original data set. The networks, inspired by those of the insect antennal lobe, build upon a modified Hopfield network in which nodes are periodically suppressed, global inhibition is gradually strengthened, and the weight of input neurons is gradually decreased relative to recurrent connections. This allows the networks to converge on a Hopfield network's equilibrium within each suppression cycle, and to switch between attractors in between cycles. The fast mutually reinforcing excitatory connections that dominate dynamics within cycles ensures the robust error-tolerant behavior that characterizes Hopfield networks. The cyclic inhibition releases the network from what would otherwise be stable equilibriums or attractors. Increasing global inhibition and decreasing dependence on the input leads successive attractors to differ, and to display increasing generality. As the network is faced with stronger inhibition, only neurons connected with stronger mutually excitatory connections will remain on; successive attractors will consist of sets of neurons that are more strongly correlated, and will tend to select increasingly generic characteristics of the data. Using artificial data, we were able to identify configurations of the network that appeared to produce a sequence of increasingly general results. The next logical steps are to apply these networks to suitable real-world data that can be characterized by a hierarchy of increasing generality and observe the network's performance. This report describes the work, data, and results, the current understanding of the results, and how the work could be continued. The code, data, and preliminary results are included and are available as an archive.
Relationships to determine the probability that a weak link (WL)/strong link (SL) safety system will fail to function as intended in a fire environment are investigated. In the systems under study, failure of the WL system before failure of the SL system is intended to render the overall system inoperational and thus prevent the possible occurrence of accidents with potentially serious consequences. Formal developments of the probability that the WL system fails to deactivate the overall system before failure of the SL system (i.e., the probability of loss of assured safety, PLOAS) are presented for several WWSL configurations: (i) one WL, one SL, (ii) multiple WLs, multiple SLs with failure of any SL before any WL constituting failure of the safety system, (iii) multiple WLs, multiple SLs with failure of all SLs before any WL constituting failure of the safety system, and (iv) multiple WLs, multiple SLs and multiple sublinks in each SL with failure of any sublink constituting failure of the associated SL and failure of all SLs before failure of any WL constituting failure of the safety system. The indicated probabilities derive from time-dependent temperatures in the WL/SL system and variability (i.e., aleatory uncertainty) in the temperatures at which the individual components of this system fail and are formally defined as multidimensional integrals. Numerical procedures based on quadrature (i.e., trapezoidal rule, Simpson's rule) and also on Monte Carlo techniques (i.e., simple random sampling, importance sampling) are described and illustrated for the evaluation of these integrals. Example uncertainty and sensitivity analyses for PLOAS involving the representation of uncertainty (i.e., epistemic uncertainty) with probability theory and also with evidence theory are presented.
Several ingredients being considered by the U.S. Army for the development of new insensitive munitions have been examined. One set of ingredients consists of 2,4-dinitrophenylhydrazine (DNPH) and hexahydro-1,3,5-trinitro-s-triazine (RDX). In this set, the decomposition of the mixture was examined to determine whether adding DNPH to RDX would generate a sufficient quantity of gas to rupture the case of a munition prior to the onset of the rapid reaction of RDX, thus mitigating the violence of reaction. The second set of ingredients consists of three different reduced sensitivity RDX (RS-RDX) powders manufactured by SNPE and Dyno-Nobel. In this set, the objective was to determine properties of RS-RDX powders that may distinguish them from normal RDX powder and may account for their reduced shock sensitivity. The decomposition reactions and sublimation properties of these materials were examined using two unique instruments: the simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) instrument and the Fourier Transform ion cyclotron resonance (FTICR) mass spectrometry instrument. These instruments provide the capability to examine the details of decomposition reactions in energetic materials. DNPH does not appear to be a good candidate to mitigate the violence of the RDX reaction in a munition. DNPH decomposes between 170 C and 180 C. When mixed with RDX it decomposes between 155 C and 170 C. It decomposes to form 1,3-dintrobenzene (DNB), ammonia, water and nitrogen. Of these compounds only nitrogen and ammonia are capable of generating high pressures within a munition. When DNPH is mixed with RDX, the DNB formed in the decomposition of DNPH interacts with RDX on the surface of the RDX powder leading to a higher rate of formation of CH2O and N2O. The CH2O is consumed by reaction with DNPH to form 2-methylene-1-(2,4-dintrophenyl)hydrazine. As a result, DNPH does not generate a large quantity of gas that will lead to rupture of a munition case. Another compound to consider as an additive is 2-oxo-1,3,5-trinitro-1,3,5-triazacyclohexane (K-6), which generates more gas in the required temperature range. Examination of several different RS-RDX materials has shown that their sublimation rates and decomposition behavior differ from Holston grade RDX. The results suggest that insensitive RDX materials from both SNPE and Dyno-Nobel may have a shell-like structure of RDX on the surface of the particles that is less stable and more reactive than the material in the core of the particles. The origin of this shell-like RDX structure is uncertain, but may be due to some aspect of the manufacturing process. It is possible that this less stable RDX on the surface of the particles may be more fluid than the interior of the particles, allowing more slip between the surface of the particles under impact or shock. This may play a role in the reduced shock sensitivity of the insensitive RDX materials. The results of over 50 experiments with DNPH, mixtures of DNPH and RDX and insensitive RDX are presented. The results characterize the decomposition behavior of each of these materials.
We developed an Augmented Musculature Device (AMD) that assists the movements of its wearer. It has direct application to aiding military and law enforcement personnel, the neurologically impaired, or those requiring any type of cybernetic assistance. The AMD consists of a collection of artificial muscles, each individually actuated, strategically placed along the surface of the human body. The actuators employed by the AMD are known as 'air muscles' and operate pneumatically. They are commercially available from several vendors and are relatively inexpensive. They have a remarkably high force-to-weight ratio--as high as 400:1 (as compared with 16:1 typical of DC motors). They are flexible and elastic, even when powered, making them ideal for interaction with humans.
An initial cost analysis of a proposed desalination process was performed. The proposed process utilizes tailored inorganic ion exchangers, hydrotalcite and permutite, to sequester anions and cations from a brackish water solution. Three different process scenarios were considered: (1) disposal of the spent exchangers as dry waste (2) conventional chemical regeneration, and (3) acid regeneration of permutite coupled with thermal (550 C) regeneration of hydrotalcite. Disposal of the resin and conventional regeneration are not viable options from an economic standpoint. Applying limited data and optimistic assumptions to the third scenario yielded an estimate of $2.34/kgal of product water. Published values for applying conventional reverse osmosis to similar water streams range from $0.70 to $2.65/kgal. Consistent with these baseline values, the Water Treatment Estimation Routine, WaTER, developed by the United States Department of the Interior, Bureau of Reclamation produced a cost estimate of $1.16/kgal for brackish water reverse osmosis.
The challenge of modeling the organization and function of biological membranes on a solid support has received considerable attention in recent years, primarily driven by potential applications in biosensor design. Affinity-based biosensors show great promise for extremely sensitive detection of BW agents and toxins. Receptor molecules have been successfully incorporated into phospholipid bilayers supported on sensing platforms. However, a collective body of data detailing a mechanistic understanding of membrane processes involved in receptor-substrate interactions and the competition between localized perturbations and delocalized responses resulting in reorganization of transmembrane protein structure, has yet to be produced. This report describes a systematic procedure to develop detailed correlation between (recognition-induced) protein restructuring and function of a ligand gated ion channel by combining single molecule fluorescence spectroscopy and single channel current recordings. This document is divided into three sections: (1) reported are the thermodynamics and diffusion properties of gramicidin using single molecule fluorescence imaging and (2) preliminary work on the 5HT{sub 3} serotonin receptor. Thirdly, we describe the design and fabrication of a miniaturized platform using the concepts of these two technologies (spectroscopic and single channel electrochemical techniques) for single molecule analysis, with a longer term goal of using the physical and electronic changes caused by a specific molecular recognition event as a transduction pathway in affinity based biosensors for biotoxin detection.
A mesoscale low-loss LIGA-micromachined conductor-backed coplanar waveguide is presented. The 517 {micro}m lines are the tallest uniplanar LIGA-fabricated microwave transmission lines to date, as well as the first to be constructed of copper rather than nickel. The conductor-backed micromachined CPW on quartz achieves a measured attenuation of 0.064 dB/cm at 15.5 GHz.