The goal of this work is to develop novel functionalized block copolymers to promote adhesion at inorganic substrate/polymer interfaces. We envision several potential advantages of functionalized block copolymers over small molecule coupling agents. Greater control over the structure of the interphase region should result through careful design of the backbone of the copolymer. The number of chains per area, the degree of entanglement between the copolymer and the polymer matrix, the number of sites per chain able to attach to the substrate, and the hydrophobicity of the interphase region can all be strongly affected by the choice of block lengths and the monomer sequence. In addition, entanglement between the copolymer and the polymer matrix, if achieved, should contribute significantly to adhesive strength. Our program involves four key elements: the synthesis of suitable functionalized block copolymers, characterization of the conformation of the copolymers at the interface by neutron reflectivity and atomic force microscopy, characterization of the degree of bonding by spectroscopy, and measurement of the mechanical properties of the interface. In this paper we discuss block copolymers designed as adhesion promoters for the copper/epoxy interface. We have synthesized a diblock with one block containing imidazole groups to bond to copper and a second block containing secondary amines to react with the epoxy matrix. We have also prepared a triblock copolymer containing a hydrophobic middle block. Below we describe the synthesis of the block copolymers by living, ring-opening metathesis polymerization (ROMP) and the first characterization data obtained by neutron reflectivity.
New insights into the development of microstructure in sol-gel films have recently been revealed by several diagnostic techniques, including imaging ellipsometry, {open_quotes}chemical imaging{close_quotes} by fluorescent tracers, light scattering from capillary waves, and finite-element modeling. The evolution of porosity during the continuous transition from dilute sol to porous solid in restricted geometries such as films and fibers is becoming clearer through fundamental understanding of evaporation dynamics and capillarity.
This report summarizes the purchasing and transportation activities of the Procurement Organization for FY 1994. Activities for both the New Mexico and California locations are included.
At Sandia Labs` Coyote Canyon Test Complex, it became necessary to develop a precision single station solution to provide time space position information (tspi) when tracking airborne test vehicles. Sandia`s first laser tracker came on line in 1968, replacing the fixed camera technique for producing trajectory data. This system shortened data reduction time from weeks to minutes. Laser Tracker 11 began operations in 1982, replacing the original tracker. It incorporated improved optics and electronics, with the addition of a microprocessor-based real-time control (rtc) system within the main servo loop. The rtc added trajectory prediction with the loss of adequate tracking signal and automatic control of laser beam divergence according to target range. Laser Tracker III, an even more advanced version of the systems, came on line in 1990. Unlike LTII, which is mounted in a trailer and must by moved by a tractor, LTIII is mounted on its own four-wheel drive carrier. This allows the system to be used at even the most remote locations. It also incorporated improved optics and electronics with the addition of absolute ranging, acquisition on the fly, and automatic transition from manual Joystick tracking to laser tracking for aircraft tests. LTIII provides a unique state of the art tracking capability for missile, rocket sled, aircraft, submunition, and parachute testing. Used in conjunction with LTII, the systems together can provide either simultaneous or extended range tracking. Mobility, accuracy, reliability, and cost effectiveness enable these systems to support a variety of testing at Department of Energy and Department of Defense ranges.
The gain-dependent polarization properties of vertical-cavity surface emitting lasers and methods for polarization control and modulation are discussed. The partitioning of power between the two orthogonal eigen polarizations is shown to depend upon the relative spectral alignment of the nondegenerate polarization cavity resonances with the laser gain spectrum. A dominant polarization can thus be maintained by employing a blue-shifted offset of the peak laser gain relative to the cavity resonance wavelength. Alternatively, the polarization can be controlled through use of anisotropic transverse cavity geometries. The orthogonal eigen polarizations are also shown to enable polarization modulation. By exploiting polarization switching transitions in cruciform lasers, polarization modulation of the fundamental mode up to 50 MHz is demonstrated. At lower modulation frequencies, complementary digital polarized output or frequency doubling of the polarized output is obtained. Control and manipulation of vertical-cavity laser polarization may prove valuable for present and future applications.
In conjunction with crosswell seismic surveying being done at the Hanford Site in south-central Washington, four different downhole seismic sources have been tested between the same set of boreholes. The four sources evaluated were the Bolt airgun, the OYO-Conoco orbital vibrator, and two Sandia-developed vertical vibrators, one pneumatically-driven, and the other based on a magnetostrictive actuator. The sources generate seismic energy in the lower frequency range of less than 1000 Hz and have different frequency characteristics, radiation patterns, energy levels, and operational considerations. Collection of identical data sets with all four sources allows the direct comparison of these characteristics and an evaluation of the suitability of each source for a given site and target.
Magnetometers are frequently used to characterize hazardous waste sites. Due to cost and time considerations, data are typically collected on a coarse grid with nodes on 3 to 6 meter (m) centers. Hardware and software are now available which allow the rapid and cost effective collection of information on a much finer sampling grid. In this paper we present and compare total field magnetometery data collected on 3 m centers to total field magnetometery data collected on a grid with centers of 0.5 m or less. We also compare the magnetometery data to time-domain electromagnetic (EM) data collected on a 1 m by 0.2 m grid using the recently introduced Geonics Ltd. EM61 metal detector. All three data sets were collected at an abandoned landfill radioactive Burial Site No. 11 (RB-11) is located on Kirtland Air Force Base near Albuquerque, New Mexico.
We propose an approach, which we call the Transport Processes Investigation or TPI, to identify and verify site-scale transport processes and their controls. The TPI aids in the formulation of an accurate conceptual model of flow and transport, an essential first step in the development of a cost effective site characterization strategy. The TPI is demonstrated in the highly complex vadose zone of glacial tills that underlie the Fernald Environmental Remediation Project (FEMP) in Fernald, Ohio. As a result of the TPI, we identify and verify the pertinent flow processes and their controls, such as extensive macropore and fracture flow through layered clays, which must be included in an accurate conceptual model of site-scale contaminant transport. We are able to conclude that the classical modeling and sampling methods employed in some site characterization programs will be insufficient to characterize contaminant concentrations or distributions at contaminated or hazardous waste facilities sited in such media.
The U.S. Department of Energy`s Office of Technology Development has been developing robotics and automation technologies for the clean-up and handling of hazardous and radioactive waste through one of its major elements, Cross Cutting and Advanced Technology development. CC&AT university research and development programs recognize the strong technology, base resident in the university community and sponsor a focused technology research and development program which stresses close interaction between the university sector and the DOE community. This report contains a compilation of research articles by each of 14 principle investigators supported by CC&AT to develop robotics and automation technologies for the clean-up and handling of hazardous and radioactive waste. This research has led to innovative solutions for waste clean-up problems, and it has moved technology out of university laboratories into functioning systems which has allowed early evaluation by site technologists.
We present a motion planner for the classical mover`s problem in three dimensions that is both resolution-complete and efficient in that it has performance commensurate with task difficulty. It is based on the SANDROS search strategy, which uses a hierarchical, multi-resolution representation of the configuration space along with a generate-and-test paradigm for solution paths. This planner can control the trade-offs between the computation resource and algorithmic completeness/solution path quality, and thus can fully utilize the available computing power. It is useful for navigation of mobile robots, submarines and spacecraft, or part motion feasibility in assembly planning.
A percolation model is developed which accounts for most known features of the process of porous glass membrane preparation by selective dissolution of multi-component glasses. The model is founded within tile framework of the classical percolation theory, wherein the components of a glass are represented by random sites on a suitable lattice. Computer simulation is used to mirror the generation of a porous structure during the dissolution process, reproducing many of the features associated with the phenomenon. Simulation results evaluate the effect of the initial composition of the glass on the kinetics of the leaching process as well as the morphology of the generated porous structure. The percolation model establishes the porous structure as a percolating cluster of unreachable constituents in the glass. The simulation algorithm incorporates removal of both, the accessible leachable components in the glass as well as the independent clusters of unreachable components not attached to the percolating cluster. The dissolution process thus becomes limited by the conventional site percolation thresholds of the unreachable components (which restricts the formation of the porous network), as well as the leachable components (which restricts the accessibility of the solvating medium into the glass). The simulation results delineate the range of compositional variations for successful porous glass preparation and predict the variation of porosity, surface area, dissolution rates and effluent composition with initial composition and time. Results compared well with experimental studies and improved upon similar models attempted in die past.
To address the need for a fast path planner, we present a learning algorithm that improves path planning by using past experience to enhance future performance. The algorithm relies on an existing path planner to provide solutions difficult tasks. From these solutions, an evolving sparse work of useful robot configurations is learned to support faster planning. More generally, the algorithm provides a framework in which a slow but effective planner may be improved both cost-wise and capability-wise by a faster but less effective planner coupled with experience. We analyze algorithm by formalizing the concept of improvability and deriving conditions under which a planner can be improved within the framework. The analysis is based on two stochastic models, one pessimistic (on task complexity), the other randomized (on experience utility). Using these models, we derive quantitative bounds to predict the learning behavior. We use these estimation tools to characterize the situations in which the algorithm is useful and to provide bounds on the training time. In particular, we show how to predict the maximum achievable speedup. Additionally, our analysis techniques are elementary and should be useful for studying other types of probabilistic learning as well.
The contact between an obsidian flow and a steep-walled tuff canyon was examined as an analogue for a high-level waste repository. The analogue site is located in the Valles Caldera in New Mexico, where a massive obsidian flow filled a paleocanyon in the Battleship Rock Tuff. The obsidian flow provided a heat source, analogous to waste panels or an igneous intrusion in a repository, and caused evaporation and migration of water. The tuff and obsidian samples were analyzed for major and trace elements and mineralogy by INAA, XRF, x-ray diffraction, and scanning electron microscopy and electron microprobe. Samples were also analyzed for D/H and {sup 39}Ar/{sup 40}Ar isotopic composition. Overall, the effects of the heating event seem to have been slight and limited to the tuff nearest the contact. There is some evidence of devitrification and migration of volatiles in the tuff within 10 m of the contact, but variations in major and trace element chemistry are small and difficult to distinguish from the natural (pre-heating) variability of the rocks.
The sorption of Cs and Cd on model soil minerals was examined by complementary analytical and experimental procedures. X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonance (NMR) spectroscopy were used to characterize the chemical and physical nature of Cs-reacted soil minerals. Cd and Cs adsorption isotherms for kaolinite were also measured at variable pH and temperature to establish likely reaction stoichiometries, while atomic force microscopy (AFM) was used to characterize the microtopography of the clay surface. XPS analyses of Cs-exchanged samples show that Cs is sorbed at mineral surfaces and at the interlayer site of smectite clays, although the spectral resolution of XPS analyses is insufficient to differentiate between basal, edge or interlayer sites. {sup 133}Cs MAS-NMR results also show that Cs is adsorbed primarily in an interlayer site of montmorillonite and on edge and basal sites for kaolinite. Cd adsorption isotherms on kaolinite were found to be additive using Al{sub 2}0{sub 3} + Si0{sub 2} Cd binding constants. AFM quantification of kaolinite crystallites suggest that edges comprise up to 50% of the BET surface area, and are consistent with NMR and surface charge results that Cs an Cd adsorption occur primarily at edge sites.
Sandia National Laboratories has worked with Synthetica Technologies and Manufacturing and Technology Conversion International (MTCl) to demonstrate the applicability of their commercial steam reforming technologies for treating DOE low-level mixed wastes. Previously, Synthetica successfully demonstrated destruction of a Sandia formulated lab trash simulant. During November 1994 Synthetica did not adequately process the aqueous halogenated organic liquid mixed waste simulant (MWTP-2110) formulated by the DOE Mixed Waste Integrated Program (MWIP). Testing at MTCl is ongoing and initial results appear to be favorable. Approximately 200 lbs each of the MWIP aqueous halogenated organic liquids (MWTP-2110), and absorbed aqueous and organic liquids (MWTP-3113/3114) simulants have been processed. At 1650{degree}F, destruction efficiencies of greater than 99% were obtained for tetrachloroethylene, toluene, and 1,2 dichlorobenzene. Product cases consisted primarily of H{sub 2}, C0{sub 2}, CO, and CH{sub 4} and had higher heating values of up to 355 BTU/SCF. Conclusions concerning the suitability of the MTCI process for treating DOE mixed wastes will be drawn upon the completion of testing.
Public concerns about surface water quality and its impact on health issues have put a premium on the ability to predict surface and groundwater quality in urban areas. The movement of toxins and nutrients in urban areas is largely controlled by interactions with soil and aquifer minerals along hydrologic pathways. Despite progress in theoretical modeling of the effects of these interactions on water chemistry, it is presently impossible to predict overall trends in urban water quality. Determining the controls on stream water chemistry is problematic due to the interplay between different hydrologic reservoirs which cannot be easily observed or measured. Natural tracers, such as dissolved ions and isotopes, provide an indirect method for observing subsurface interactions and are useful for time series analysis of stream water composition. Ionic species are generally nonconservative components because of chemical reactions and are thus useful for discerning the overall discharge chemistry affected by the relationship.
The primary purpose of this paper is to provide a careful evaluation of the diffusion velocity concept with regard to its ability to predict the diffusion of vorticity near a moving wall. A computer code BDIF has been written which simulates the evolution of the vorticity field near a wall of infinite length which is moving in an arbitrary fashion. The simulations generated by this code are found to give excellent results when compared to several exact solutions. We also outline a two-dimensional unsteady viscous boundary layer model which utilizes the diffusion velocity concept and is compatible with vortex methods. A primary goal of this boundary layer model is to minimize the number of vortices generated on the surface at each time step while achieving good resolution of the vorticity field near the wall. Preliminary results have been obtained for simulating a simple two-dimensional laminar boundary layer.
Sol-gel processing has been widely used in the preparation of lead zirconate titanate (PZT) thin films. The authors have applied this methodology to the formation of lead magnesium niobate (PMN) spin-cast deposited thin films. Since there is a limited number of soluble, commercially available compounds, the authors have recently synthesized a series of novel metal alkoxides for use as precursors for generation of PMN thin films and powders. The process for generation of the perovskite phase of these PMN powders and films are reported.
The numerical code TOUGH2 was used to assess alternative conceptual models of fracture flow. The models that were considered included the equivalent continuum model (ECM) and the dual permeability (DK) model. A one-dimensional, layered, unsaturated domain was studied with a saturated bottom boundary and a constant infiltration at the top boundary. Two different infiltration rates were used in the studies. In addition, the connection areas between the fracture and matrix elements in the dual permeability model were varied. Results showed that the two conceptual models of fracture flow produced different saturation and velocity profiles-even under steady-state conditions. The magnitudes of the discrepancies were sensitive to two parameters that affected the flux between the fractures and matrix in the dual permeability model: (1) the fracture-matrix connection areas and (2) the capillary pressure gradients between the fracture and matrix elements.
This paper discusses, in a general way, the influence of technology on the economy. The target audience is engineers who are involved in technology development but who are not especially familiar with economics. The measure used for describing the health of an economy is productivity. The impact of technological developments on productivity is discussed.
Hazardous materials management includes interactions among materials, personnel, facilities, hazards, and processes of various groups within a DOE site`s environmental, safety & health (ES&H) and line organizations. Although each group is charged with addressing a particular aspect of these properties and interactions, the information it requires must be gathered into a coherent set of common data for accurate and consistent hazardous material management and regulatory reporting. It is these common data requirements which the Cradle-to-Grave Tracking and Information System (CGTIS) is designed to satisfy. CGTIS collects information at the point at which a process begins or a material enters a facility, and maintains that information, for hazards management and regulatory reporting, throughout the entire life-cycle by providing direct on-line links to a site`s multitude of data bases to bring information together into one common data model.
The RADTRAN computer code for transportation risk analysis, which has been under continuous development at Sandia National Laboratories since 1977, has evolved from a purely research tool into a publicly available with a variety of applications. This expansion of the user community has substantially increased the need to make the system easier to use without decreasing its capabilities or the quality of output. A large set of modifiable RADTRAN input files has been available via TRANSNET for several years. One approach to assisting the user involves adding annotations/information to each of these files. A second approach is providing additional help in building new/modifying old input files. Keeping the proposed information/annotation files separate from but closely coupled to the modifiable input files within the TRANSNET shell system allows the modifiable input files to remain as regular input files while providing rapid, automatic access to, useful information about the analysis. In this way, the sample input files remain intact as regular RADTRAN input files and any files generated using associated on-line menus or editors may be readily converted into new input files. A single sample file is selected and used as an example to illustrate the prototype help features.
Scenario development for the system performance assessment of the Yucca Mountain Site Characterization Project defines a scenario as a well-posed problem connecting an initiating event with radionuclide release to the accessible environment by a logical and physically possible combination or sequence of features, events, and processes. Drawing on the advice and assistance of the Project`s principal investigators (PIs), a collection of release scenarios initiated by the nominal ground-water flow occurring in the vicinity of the potential Yucca Mountain high-level-waste repository is developed and described in pictorial form. This collection of scenarios is intended to provide a framework to assist PIs in recognizing essential field and calculational analyses, to assist performance assessment in providing guidance to site characterization, and to continue the effort to exhaustively identify all features, events, and processes important to releases. It represents a step in the iterative process of identifying what details of the potential site are important for safe disposal. 67 refs.
Correct operation of an information system requires a balance of ``surety`` domains -- access control (confidentiality), integrity, utility, availability, and safety. However, traditional approaches provide little help on how to systematically analyze and balance the combined impact of surety requirements on a system. The key to achieving information system surety is identifying, prioritizing, and mitigating the sources of risk that may lead to system failure. Consequently, the authors propose a risk assessment methodology that provides a framework to guide the analyst in identifying and prioritizing sources of risk and selecting mitigation techniques. The framework leads the analyst to develop a risk-based system model for balancing the surety requirements and quantifying the effectiveness and combined impact of the mitigation techniques. Such a model allows the information system designer to make informed trade-offs based on the most effective risk-reduction measures.
The agile manufacturing paradigm engenders many new concepts and work approaches for manufacturing operations. A technology often invoked in the concept of agility is modeling and simulation. Few would disagree that modeling and simulation holds the potential to substantially reduce the product development cycle and lead to improve product reliability and performance. Advanced engineering simulation can impact manufacturing in three areas: process design, product design, and process control. However, despite that promise, the routine utilization of modeling and simulation by industry within the design process is very limited. Advanced simulation is still used primarily in a troubleshooting mode examining design or process problems after the fact. Sandia National Laboratories has been engaged in the development of advanced engineering simulation tools for many years and more recently has begun to focus on the application of such models to manufacturing processes important for the defense industry. These efforts involve considerable interaction and cooperative research with US industry. Based upon this experience, this presentation examines the elements that are necessary for advanced engineering simulation to become an integral part of the design process.