Publications

Hydrolysis and condensation of organically bridged bis-triethoxysilanes, (EtO){sub 3}Si-R-Si(OEt){sub 3}, results in the formation of three dimensional organic/inorganic hybrid networks (Equation 1). Properties of these materials, including porosity, are dependent on the nature of the bridging group, R. Flexible groups (akylene-spacers longer than five carbons in length) polymerize under acidic conditions to give non-porous materials. Rigid groups (such as arylene-, alkynylene-, or alkenylene) form non-porous, microporous, and macroporous gels. In many cases the pore size distributions are quite narrow. One of the motivations for preparing hybrid organic-inorganic materials is to extend the range of properties available with sol-gel systems by incorporating organic groups into the inorganic network. For example, organically modified silica gels arc either prepared by co-polymerizing an organoalkoxysilane with a silica precursor or surface silylating the inorganic gel. This can serve to increase hydrophobicity or to introduce some reactive organic functionality. However, the type and orientation of these organic functionalities is difficult to control. Furthermore, many organoalkoxysilanes can act to inhibitor even prevent gelation, limiting the final density of organic functionalities. We have devised a new route for preparing highly functionalized pores in hybrid materials using bridging groups that are thermally converted into the desired functionalities after the gel has been obtained. In this paper, we present the preparation and characterization of bridged polysilsesquioxanes with Diels-Alder adducts as the bridging groups from the sol-gel polymerization of monomers 2 and 4. The bridging groups are constructed such that the retro Diela-Alder reaction releases the dienes and leaves the dienophiles as integral parts of the network polymers. In the rigid architecture of a xerogel, this loss of organic functionality should liberate sufficient space to modify the overall porosity. Furthermore, the new porosity will be functionalized with the dienophilic olefin bridging group. We also demonstrate that by changing the type of Diels-Alder adduct used as the bridging group, we can change the temperature at which the retro-Diels-Alder reaction will occur.

This paper describes the model and method used to obtain the periodically estimated uncertainties for measurement of the scattering parameters S{sub 11} and S{sub 22} on a Vector Network Analyzer (VNA). A thru-reflect-line (TRL) method is employed as a second tier calibration to obtain uncertainty estimates using an NIST-calibrated standard. An example of tabulated listings of these uncertainty estimates is presented and the uncertainties obtained for a VNA with 7 mm, 3.5 mm, and type N coaxial interfaces used in the laboratory over several years are summarized.

The study of ecology is taking on increasing global importance as the value of well-functioning ecosystems to human well-being becomes better understood. However, the use of technological systems for the study of ecology lags behind the use of technologies in the study of other disciplines important to human well-being, such as medicine, chemistry and physics. The authors outline four different kinds of large-scale data needs required by land managers for the development of sustainable land use strategies, and which can be obtained with current or future technological systems. They then outline a hypothetical resource management scenario in which data on all those needs are collected using remote and in situ technologies, transmitted to a central location, analyzed, and then disseminated for regional use in maintaining sustainable grazing systems. They conclude by highlighting various data-collection systems and data-sharing networks already in operation.

Laser induced fluorescence has been used to measure the spatial distribution of the two lowest energy argon excited states, 1s{sub 5} and 1s{sub 4}, in inductively driven plasmas containing argon, chlorine and boron trichloride. The behavior of the two energy levels with plasma conditions was significantly different, probably because the 1s{sub 5} level is metastable and the 1s{sub 4} level is radiatively coupled to the ground state but is radiation trapped. The argon data is compared with a global model to identify the relative importance of processes such as electron collisional mixing and radiation trapping. The trends in the data suggest that both processes play a major role in determining the excited state density. At lower rfpower and pressure, excited state spatial distributions in pure argon were peaked in the center of the discharge, with an approximately Gaussian profile. However, for the highest rfpowers and pressures investigated, the spatial distributions tended to flatten in the center of the discharge while the density at the edge of the discharge was unaffected. The spatially resolved excited state density measurements were combined with previous line integrated measurements in the same discharge geometry to derive spatially resolved, absolute densities of the 1s{sub 5} and 1s{sub 4} argon excited states and gas temperature spatial distributions. Fluorescence lifetime was a strong fi.mction of the rf power, pressure, argon fraction and spatial location. Increasing the power or pressure resulted in a factor of two decrease in the fluorescence lifetime while adding Cl{sub 2} or BCl{sub 3} increased the fluorescence lifetime. Excited state quenching rates are derived from the data. When Cl{sub 2} or BCl{sub 3} was added to the plasma, the maximum argon metastable density depended on the gas and ratio. When chlorine was added to the argon plasma, the spatial density profiles were independent of chlorine fraction. While it is energetically possible for argon excited states to dissociate some of the molecular species present in this discharge, it does not appear to be a significant source of dissociation. The major source of interaction between the argon and the molecular species BCl{sub 3} and Cl{sub 2} appears to be through modification of the electron density.

Electron and negative ion densities have been measured in inductively coupled discharges containing C{sub 2}F{sub 6} and CHF{sub 3}. Line integrated electron density was determined using a microwave interferometer, negative ion densities were inferred using laser photodetachment spectroscopy, and electron temperature was determined using a Langmuir probe. For the range of induction powers, pressures and bias power investigated, the electron density peaked at 9 x 10{sup 12} cm{sup -2} (line-integrated) or approximately 9 x 10{sup 11} cm{sup -3}. The negative ion density peaked at approximately 1.3 x 10{sup 11} cm{sup -3}. A maximum in the negative ion density as a function of induction coil power was observed. The maximum is attributed to a power dependent change in the density of one or more of the potential negative ion precursor species since the electron temperature did not depend strongly on power. The variation of photodetachment with laser wavelength indicated that the dominant negative ion was F{sup -}. Measurement of the decay of the negative ion density in the afterglow of a pulse modulated discharge was used to determine the ion-ion recombination rate for CF{sub 4}, C{sub 2}F{sub 6} and CHF{sub 3} discharges.

The load mitigation and energy capture characteristics of twist-coupled HAWT blades that are mounted on a variable speed rotor are investigated in this paper. These blades are designed to twist toward feather as they bend with pretwist set to achieve a desirable twist distribution at rated power. For this investigation, the ADAMS-WT software has been modified to include blade models with bending-twist coupling. Using twist-coupled and uncoupled models, the ADAMS software is exercised for steady wind environments to generate C{sub p} curves at a number of operating speeds to compare the efficiencies of the two models. The ADAMS software is also used to generate the response of a twist-coupled variable speed rotor to a spectrum of stochastic wind time series. This spectrum contains time series with two mean wind speeds at two turbulence levels. Power control is achieved by imposing a reactive torque on the low speed shaft proportional to the RPM squared with the coefficient specified so that the rotor operates at peak efficiency in the linear aerodynamic range, and by limiting the maximum RPM to take advantage of the stall controlled nature of the rotor. Fatigue calculations are done for the generated load histories using a range of material exponents that represent materials from welded steel to aluminum to composites, and results are compared with the damage computed for the rotor without twist-coupling. Results indicate that significant reductions in damage are achieved across the spectrum of applied wind loading without any degradation in power production.

The behavior of H in p-GaN(Mg) at temperatures >400 C is modeled by using energies and vibrational frequencies from density-functional theory to parameterize transport and reaction equations. Predictions agree semiquantitatively with experiment for the solubility, uptake, and release of the H when account is taken of a surface barrier. Hydrogen is introduced into GaN during growth by metal-organic chemical vapor deposition (MOCVD) and subsequent device processing. This impurity affects electrical properties substantially, notably in p-type GaN doped with Mg where it reduces the effective acceptor concentration. Application of density-functional theory to the zincblende and wurtzite forms of GaN has indicated that dissociated H in interstitial solution assumes positive, neutral, and negative charge states. The neutral species is found to be less stable than one or the other of the charged states for all Fermi energies. Hydrogen is predicted to form a bound neutral complex with Mg, and a local vibrational mode ascribed to this complex has been observed. The authors are developing a unified mathematical description of the diffusion, reactions, uptake, and release of H in GaN at the elevated temperatures of growth and processing. Their treatment is based on zero-temperature energies from density functional theory. One objective is to assess the consistency of theory with experiment at a more quantitative level than previously. A further goal is prediction of H behavior pertinent to device processing. Herein is discussed aspects relating to p-type GaN(Mg).

We present a microscopic theory of the excitonic Stokes and anti-Stokes energy transfer mechanisms between two widely separated unequal quantum wells with a large energy mismatch ({Delta}) at low temperatures (T). Exciton transfer through dipolar coupling, photon-exchange coupling and over-barrier ionization of the excitons through exciton-exciton Auger processes are examined. The energy transfer rate is calculated as a function of T and the center-to-center distance d between the two wells. The rates depend sensitively on T for plane-wave excitons. For located excitons, the rates depend on T only through the T-dependence of the localization radius.

This paper discusses the application of multiple characterization methods to radioactive wastes generated by the Sandia National Laboratories/New Mexico (SNL/NM) Environmental Restoration (ER) Project during the excavation of buried materials at the Classified Waste Landfill (CWLF) and the Radioactive Waste Landfill (RWL). These waste streams include nuclear weapon components and other refuse that are surface contaminated or contain sealed radioactive sources with unknown radioactivity content. Characterization of radioactive constituents in RWL and CWLF waste has been problematic, due primarily to the lack of documented characterization data prior to burial. A second difficulty derives from the limited information that ER project personnel have about weapons component design and testing that was conducted in the early days of the Cold War. To reduce the uncertainties and achieve the best possible waste characterization, the ER Project has applied both project-specific and industry-standard characterization methods that, in combination, serve to define the types and quantities of radionuclide constituents in the waste. The resulting characterization data have been used to develop waste profiles for meeting disposal site waste acceptance criteria.

The presence of damage in the form of microcracks can increase the permeability of salt. In this paper, an analytical formulation of the permeability of damaged rock salt is presented for both initially intact and porous conditions. The analysis shows that permeability is related to the connected (i.e., gas accessible) volumetric strain and porosity according to two different power-laws, which may be summed to give the overall behavior of a porous salt with damage. This relationship was incorporated into a constitutive model, known as the Multimechanism Deformation Coupled Fracture (MDCF) model, which has been formulated to describe the inelastic flow behavior of rock salt due to coupled creep, damage, and healing. The extended model was used to calculate the permeability of rock salt from the Waste Isolation Pilot Plant (WIPP) site under conditions where damage evolved with stress over a time period. Permeability changes resulting from both damage development under deviatoric stresses and damage healing under hydrostatic pressures were considered. The calculated results were compared against experimental data from the literature, which indicated that permeability in damaged intact WIPP salt depends on the magnitude of the gas accessible volumetric strain and not on the total volumetric strain. Consequently, the permeability of WIPP salt is significantly affected by the kinetics of crack closure, but shows little dependence on the kinetics of crack removal by sintering.

This work combines focused ion beam sputtering and ultra-precision machining for microfabrication of metal alloys and polymers. Specifically, micro-end mills are made by Ga ion beam sputtering of a cylindrical tool shank. Using an ion energy of 20 keV, the focused beam defines the tool cutting edges that have submicrometer radii of curvature. We demonstrate 25 μm diameter micromilling tools having 2, 4 and 5 cutting edges. These tools fabricate fine channels, 26-28 microns wide, in 6061 aluminum, brass, and polymethyl methacrylate. Micro-tools are structurally robust and operate for more than 5 hours without fracture.

Hydrogen was ion-implanted into wurtzite-phase GaN, and its transport, bound states, and microstructural effects during annealing up to 980°C were investigated by nuclear-reaction profiling, ion-channeling analysis, transmission electron microscopy, and infrared (IR) vibrational spectroscopy. At implanted concentrations vl at.%, faceted H2 bubbles formed, enabling identification of energetically preferred surfaces, examination of passivating N-H states on these surfaces, and determination of the diffusivity-solubility product of the H. Additionally, the formation and evolution of point and extended defects arising from implantation and bubble formation were characterized. At implanted H concentrations AÜ.1 at.%, bubble formation was not observed, and ion-channeling analysis indicated a defect-related H site located within the [0001] channel. © 1999 Materials Research Society.

We present advances in the application of laser scanning confocal microscopy (LSCM) to image, reconstruct, and characterize statistically the microgeometry of porous geologic and engineering materials. We discuss technical and practical aspects of this imaging technique, including both its advantages and limitations. Confocal imaging can be used to optically section a material, with sub-micron resolution possible in the lateral and axial planes. The resultant volumetric image data, consisting of fluorescence intensities for typically ~50 million voxels in XYZ space, can be used to reconstruct the three-dimensional structure of the two-phase medium. We present several examples of this application, including studying pore geometry in sandstone, characterizing brittle failure processes in low-porosity rock deformed under triaxial loading conditions in the laboratory, and analyzing the microstructure of porous ceramic insulations. We then describe approaches to extract statistical microgeometric descriptions from volumetric image data, and present results derived from confocal volumetric data sets. Finally, we develop the use of confocal image data to automatically generate a three-dimensional mesh for numerical pore-scale flow simulations.

Inertial MEMS sensors such as accelerometers and angular rotation sensing devices continue to improve in performance as advances in design and processing are made. Present state-of-the-art accelerometers have achieved performance levels in the laboratory that are consistent with requirements for successful application in tactical weapon navigation systems. However, sensor performance parameters that are of interest to the designer of inertial navigation systems are frequently not adequately addressed by the MEMS manufacturer. This paper addresses the testing and characterization of a MEMS accelerometer from an inertial navigation perspective. The paper discusses test objectives, data reduction techniques and presents results from the test of a three-axis MEMS accelerometer conducted at Sandia National Laboratories during 1997. The test was structured to achieve visibility and characterization of the accelerometer bias and scale factor stability over time and temperature. Sandia is a multi-program laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under contract DE-AC04-94AL85000.

The solidification behavior and resultant solidification cracking susceptibility of autogenous gas tungsten arc fusion welds in Alloy HR-160 was investigated by Varestraint testing, differential thermal analysis and various microstructural characterization techniques. The alloy exhibited a liquidus temperature of 1387 °C and initiated solidification by a primary L→γ reaction in which Ni, Si and Ti segregated to the interdendritic liquid and cosegregated to the γ dendrite cores. Chromium exhibited no preference for segregation to the solid or liquid phase during solidification. Solidification terminated at ≈1162 °C by a eutectic-type L→[γ+ (Ni,Co)16(Ti,Cr)6Si7] reaction. The (Ni,Co)16(Ti,Cr)6Si7] phase is found to be analogous to the G phase that forms in the Ni-Ti-Si and Co-Ti-Si ternary systems, and similarities are found between the solidification behavior of this commercial multicomponent alloy and the simple Ni-Si and Ni-Ti binary systems. Reasonable agreement is obtained between the calculated and measured volume percent of the [γ+(Ni,Co)16(Ti,Cr)6Si7] eutectic-type constituent with the Scheil equation using experimentally determined k values for Si and Ti from electron microprobe data. The alloy exhibited a very high susceptibility to solidification cracking in the Varestraint test. This is attributed to a large solidification temperature range of 225 °C and the presence of 2-5 vol-% solute-rich interdendritic liquid that preferentially wets the grain boundaries and interdendritic regions.

Wet oxidation of high-Al-content AlGaAs semiconductor layers in vertical cavity surface emitting lasers (VCSELs) has produced devices with record low threshold currents and voltages and with wall-plug efficiencies greater than 50%. Wet oxidation of buried AlGaAs layers has been employed to reduce the problems associated with substrate current leakage in GaAs-oninsulator (GOI) MESFETs. Wet oxidation has also been considered as a route to the long-sought goal of a III-V MIS technology. To continue improving device designs for even higher performance and to establish a truly manufacturable technology based on wet oxidation, the effect of oxidation of a given layer on the properties of the entire device structure must be understood. The oxidation of a given layer can strongly affect the electrical and chemical properties of adjacent layers. Many of these effects are derived from the production of large amounts of elemental As during the oxidation reaction, the resultant generation of point defects, and the diffusion of these defects into adjacent regions. This can modify the chemical and electrical properties of these regions in ways that can impact device design, fabrication, and performance. Current understanding of the problem is discussed here ©1999 Materials Research Society.

The diffuse behavior of penetrants in simple polymer melts was investigated by molecular dynamics simulation. For the case where the polymer melt consisted of pearl-necklace chains, the diffusive behavior of the loose pearl penetrants was seen to be qualitatively different than would be expected in realistic models of polymer melts. In particular, there was little or no "non-Fickian" region; the variation of the diffusion coefficient with the penetrant diameter was what one would expect for diffusion through small molecular liquids; and, finally, the long time tail of the velocity autocorrelation displayed a "-3/2" power law form, also as in the small molecular liquid case. When the chains' backbone motion was further constrained by the introduction of a bond angle potential, the qualitative nature of the penetrant diffusion became more "polymer-like." A non-Fickian region developed; the diffusion coefficient varied more rapidly with penetrant diameter; and the velocity autocorrelation function developed a "-5/2" power law tail. © 1999 American Institute of Physics.

Three-dimensional photonic lattices are engineered 'materials' which are the photonic analogues of semiconductors. These structures were first proposed and demonstrated in the mid-to-late 1980's. However, due to fabrication difficulties, lattices active in the infrared are only just emerging. Wide ranges of structures and fabrication approaches have been investigated. The most promising approach for many potential applications is a diamond-like structure fabricated using silicon microprocessing techniques. This approach has enabled the fabrication of 3-D silicon photonic lattices active in the infrared. The structures display band gaps centered from 12μ down to 1.55μ.

Failure analysis (FA) tools have been applied to analyze failing polysilicon microengines. These devices were stressed to failure under accelerated conditions in both oxidizing and non-oxidizing environments. The dominant failure mechanism of these microengines was identified as wear of rubbing surfaces. This often results in either seized microengines or microengines with broken pin joints. Analysis of these failed polysilicon devices found that wear debris was produced in both oxidizing and non-oxidizing environments. By varying the relative percent humidity (%RH), we observed an increase in the amount of wear debris with decreasing humidity. Plan view imaging using scanning electron microscopy revealed build-up of wear debris on the surface of microengines. Focused ion beam (FIB) cross sections revealed the location and build-up of wear debris within the microengine. Seized regions were also observed in the pin joint area using FIB processing. By using transmission electron microscopy in conjunction with energy dispersive x-ray spectroscopy (EDX) and electron energy loss spectroscopy (EELS), we were able to identify wear debris produced in low (1.8% RH), medium and high (39% RH) humidities.

We have been studying the use of spectral imagery to locate targets in spectrally interfering backgrounds. In making performance estimates for various sensors it has become evident that some calculations are unreliable because of overfitting. Hence, we began a thorough study of the problem of overfitting in multivariate classification. In this paper we present some model based results describing the problem. From the model we know the ideal covariance matrix, the ideal discriminant vector, and the ideal classification performance. We then investigate how experimental conditions such as noise, number of bands, and number of samples cause discrepancies from the ideal results. We also suggest ways to discover and alleviate overfitting.

We discuss an electrostatics problem whose solution must lie in the set script capital L sign of all real n-by-n symmetric matrices with all row sums equal to zero. With respect to the Frobenius norm, we provide an algorithm that finds the member of script capital L sign which is closest to any given n-by-n matrix, and determines the distance between the two. This algorithm makes it practical to find the distances to script capital L sign of finite element approximate solutions of the electrostatics problem, and to reject those which are not sufficiently close. © 1999 Elsevier Science Inc. All rights reserved.

In this paper a hybrid, finite element - boundary element method which can be used to solve for particle advection-diffusion in infinite domains with variable advective fields is presented. In previous work either boundary element, finite element, or difference methods have been used to solve for particle motion in advective-diffusive domains. These methods have a number of limitations. Due to the complexity of computing spatially dependent Green's functions, the boundary element method is limited to domains containing only constant advective fields, and due to their inherent formulation, finite element and finite difference methods are limited to only domains of finite spatial extent. Thus, finite element and finite difference methods are limited to finite space problems for which the boundary element method is not, and the boundary element method is limited to constant advection field problems for which finite element and finite difference methods are not. In this paper it is proposed to split a domain into two subdomains, and for each of these sub domains, apply the appropriate solution method; thereby, producing a method for the total infinite space, variable advective field domain.

The strength and modulus of amorphous diamond, a new material for surface micromachined MEMS and sensors, was tested in uniaxial tension by pulling laterally with a flat tipped diamond in a nanoindenter. Several sample designs were attempted. Of those, only the single layer specimen with a 1 by 2 {micro}m gage cross section and a fixed end rigidly attached to the substrate was successful. Tensile load was calculated by resolving the measured lateral and normal forces into the applied tensile force and frictional losses. Displacement was corrected for machine compliance using the differential stiffness method. Post-mortem examination of the samples was performed to document the failure mode. The load-displacement data from those samples that failed in the gage section was converted to stress-strain curves using carefully measured gage cross section dimensions. Mean fracture strength was found to be 8.5 {+-} 1.4 GPa and the modulus was 831 {+-} 94 GPa. Tensile results are compared to hardness and modulus measurements made using a nanoindenter.

The behavior of MEMS devices is limited by the strength of critical features such as thin ligaments, oxide cuts joining layers, pin joints and hinges. Devices fabricated at Sandia's Microelectronic Development Laboratory have been successfully tested to investigate these features. A series of measurements were performed on samples with gage lengths of 15 to 1000 microns, using conventional and tungsten coated samples as well as samples that include the critical features of standard components in the test section. Specimens have a freely moving pin joint on one end that anchors the sample to the silicon die to allow rotation to reduce effects of bending. Each sample is loaded in uniaxial tension by pulling laterally with a flat tipped diamond in a computer-controlled Nanoindenter. Load is calculated by resolving the measured lateral and normal forces into the applied tensile force and frictional losses. The specimen cross section and gage length dimensions were verified by measuring against a standard in the SEM. Multiple tests can be programmed at one time and performed without operator assistance allowing the collection of significant populations of data.

Sandia National Laboratories is developing polyurethane foam as a chemical grout for lost circulation zones. In past work polyurethane foam was tried with limited success in laboratory tests and GDO sponsored field tests. Goals were that the foam expanded significantly and harden to a drillable firmness quickly. Since that earlier work there have been improvements in polyurethane chemistry and the causes of the failures of previous tests have been identified. Recent success in applying pure solution grouts (proper classification of polyurethane - Naudts) in boreholes encourages reevaluating its use to control lost circulation. These successes include conformance control in the oil patch (e.g. Ng) and dam remediation projects. In civil engineering, polyurethane is becoming the material of choice for sealing boreholes with large voids and high inflows, conditions associated with the worst lost circulation problems. Demonstration of a delivery mechanism is yet to be done in a geothermal borehole.