Silane adhesion promoters are commonly used to improve the adhesion, durability, and corrosion resistance of polymer-oxide interfaces. The current study investigates a model interface consisting of the natural oxide of 100 Si and an epoxy cured from diglycidyl ether of bisphenol A (DGEBA) and triethylenetetraamine (TETA). The thickness of (3-glycidoxypropyl)trimethoxysilane (GPS) films placed between the two materials provided the structural variable. Five surface treatments were investigated: a bare interface, a rough monolayer film, a smooth monolayer film, a 5 nm thick film, and a 10 nm thick film. Previous neutron reflection experiments revealed large extension ratios (>2) when the 5 and 10 nm thick GPS films were exposed to deuterated nitrobenzene vapor. Despite the larger extension ratio for the 5 nm thick film, the epoxy/Si fracture energy (G{sub c}) was equal to that of the 10 nm thick film under ambient conditions. Even the smooth monolayer exhibited the same G{sub c}. Only when the monolayer included a significant number of agglomerates did the G{sub c} drop to levels closer to that of the bare interface. When immersed in water at room temperature for 1 week, the threshold energy release rate (G{sub th}) was nearly equal to G{sub c} for the smooth monolayer, 5 nm thick film, and 10 nm thick film. While the G{sub th} for all three films decreased with increasing water temperature, the G{sub th} of the smooth monolayer decreased more rapidly. The bare interface was similarly sensitive to temperature; however, the G{sub th} of the rough monolayer did not change significantly as the temperature was raised. Despite the influence of pH on hydrolysis, the G{sub th} was insensitive to the pH of the water for all surface treatments.
Boron carbide displays a rich response to dynamic compression that is not well understood. To address poorly understood aspects of behavior, including dynamic strength and the possibility of phase transformations, a series of plate impact experiments was performed that also included reshock and release configurations. Hugoniot data were obtained from the elastic limit (15-18 GPa) to 70 GPa and were found to agree reasonably well with the somewhat limited data in the literature. Using the Hugoniot data, as well as the reshock and release data, the possibility of the existence of one or more phase transitions was examined. There is tantalizing evidence, but at this time no phase transition can be conclusively demonstrated. However, the experimental data are consistent with a phase transition at a shock stress of about 40 GPa, though the volume change associated with it would have to be small. The reshock and release experiments also provide estimates of the shear stress and strength in the shocked state as well as a dynamic mean stress curve for the material. The material supports only a small shear stress in the shocked (Hugoniot) state, but it can support a much larger shear stress when loaded or unloaded from the shocked state. This strength in the shocked state is initially lower than the strength at the elastic limit but increases with pressure to about the same level. Also, the dynamic mean-stress curve estimated from reshock and release differs significantly from the hydrostate constructed from low-pressure data. Finally, a spatially resolved interferometer was used to directly measure spatial variations in particle velocity during the shock event. These spatially resolved measurements are consistent with previous work and suggest a nonuniform failure mode occurring in the material.
This paper describes an integrated experimental and computational framework for developing 3-D structural models for humic acids (HAs). This approach combines experimental characterization, computer assisted structure elucidation (CASE), and atomistic simulations to generate all 3-D structural models or a representative sample of these models consistent with the analytical data and bulk thermodynamic/structural properties of HAs. To illustrate this methodology, structural data derived from elemental analysis, diffuse reflectance FT-IR spectroscopy, 1-D/2-D {sup 1}H and {sup 13}C solution NMR spectroscopy, and electrospray ionization quadrupole time-of-flight mass spectrometry (ESI QqTOF MS) are employed as input to the CASE program SIGNATURE to generate all 3-D structural models for Chelsea soil humic acid (HA). These models are subsequently used as starting 3-D structures to carry out constant temperature-constant pressure molecular dynamics simulations to estimate their bulk densities and Hildebrand solubility parameters. Surprisingly, only a few model isomers are found to exhibit molecular compositions and bulk thermodynamic properties consistent with the experimental data. The simulated {sup 13}C NMR spectrum of an equimolar mixture of these model isomers compares favorably with the measured spectrum of Chelsea soil HA.
Inertial confinement fusion capsule implosions absorbing up to 35 kJ of x-rays from a {approx}220 eV dynamic hohlraum on the Z accelerator at Sandia National Laboratories have produced thermonuclear D-D neutron yields of (2.6 {+-} 1.3) x 10{sup 10}. Argon spectra confirm a hot fuel with Te {approx} 1 keV and n{sub e} {approx} (1-2) x 10{sup 23} cm{sup -3}. Higher performance implosions will require radiation symmetry control improvements. Capsule implosions in a {approx}70 eV double-Z-pinch-driven secondary hohlraum have been radiographed by 6.7 keV x-rays produced by the Z-beamlet laser (ZBL), demonstrating a drive symmetry of about 3% and control of P{sub 2} radiation asymmetries to {+-}2%. Hemispherical capsule implosions have also been radiographed in Z in preparation for future experiments in fast ignition physics. Z-pinch-driven inertial fusion energy concepts are being developed. The refurbished Z machine (ZR) will begin providing scaling information on capsule and Z-pinch in 2006. The addition of a short pulse capability to ZBL will enable research into fast ignition physics in the combination of ZR and ZBL-petawatt. ZR could provide a test bed to study NIF-relevant double-shell ignition concepts using dynamic hohlraums and advanced symmetry control techniques in the double-pinch hohlraum backlit by ZBL.
Two-dimensional processes of nickel electrodeposition in LIGA microfabrication were modeled using the finite-element method and a fully coupled implicit solution scheme via Newtons technique. Species concentrations, electrolyte potential, flow field, and positions of the moving deposition surfaces were computed by solving the species-mass, charge, and momentum conservation equations as well as pseudo-solid mesh-motion equations that employ an arbitrary Lagrangian-Eulerian (ALE) formulation. Coupling this ALE approach with repeated re-meshing and re-mapping makes it possible to track the entire transient deposition processes from start of deposition until the trenches are filled, thus enabling the computation of local current densities that influence the microstructure and functional/mechanical properties of the deposit.
Using shock wave reverberation experiments, water samples were quasi-isentropically compressed between silica and sapphire plates to peak pressures of 1-5 GPa on nanosecond time scales. Real time optical transmission measurements were used to examine changes in the compressed samples. Although the ice VII phase is thermodynamically favored above 2 GPa, the liquid state was initially preserved and subsequent freezing occurred over hundreds of nanoseconds only for the silica cells. Images detailing the formation and growth of the solid phase were obtained. These results provide unambiguous evidence of bulk water freezing on such short time scales.
Combined XRD/neutron Rietveld refinements were performed on PbZr{sub 0.30}Ti{sub 0.70}O{sub 3} powder samples doped with nominally 4% Ln (where Ln = Ce, Nd, Tb, Y, or Yb). Resulting refined structural parameters indicated that the lattice parameters and volume changes in the tetragonal perovskite unit cell were consistent with A and/or B-site doping of the structure. Ce doping is inconsistent with respect to its rather large atomic radius, but is understood in terms of its oxidation to the Ce{sup +4} oxidation state in the structure. Results of the B-site displacement values for the Ti/Zr site indicate that amphoteric doping of Ln cations in the structure results in superior properties for PLnZT materials.
Blastwalls are often assumed to be the answer for facility protection from malevolent explosive assault, particularly from large vehicle bombs (LVB's). The assumption is made that the blastwall, if it is built strong enough to survive, will provide substantial protection to facilities and people on the side opposite the LVB. This paper will demonstrate through computer simulations and experimental data the behavior of explosively induced air blasts during interaction with blastwalls. It will be shown that air blasts can effectively wrap around and over blastwalls. Significant pressure reduction can be expected on the downstream side of the blastwall but substantial pressure will continue to propagate. The effectiveness of the blastwall to reduce blast overpressure depends on the geometry of the blastwall and the location of the explosive relative to the blastwall.
Poole-Frenkel emission in Si-rich nitride and silicon oxynitride thin films is studied in conjunction with compositional aspects of their elastic properties. For Si-rich nitrides varying in composition from SiN{sub 1.33} to SiN{sub 0.54}, the Poole-Frenkel trap depth ({Phi}{sub B}) decreases from 1.08 to 0.52 eV as the intrinsic film strain ({Epsilon}{sub i}) decreases from 0.0036 to -0.0016. For oxynitrides varying in composition from SiN{sub 1.33} to SiO{sub 1.49}N{sub 0.35}, {Phi}{sub B} increases from 1.08 to 1.53 eV as {Epsilon}{sub i} decreases from 0.0036 to 0.0006. In both material systems, a direct correlation is observed between {Phi}{sub B} and {Epsilon}{sub i}. Compositionally induced strain relief as a mechanism for regulating {Phi}{sub B} is discussed.
Annular wire array implosions on the Sandia Z-machine can produce >200 TW and 1-2 MJ of soft x rays in the 0.1-10 keV range. The x-ray flux and debris in this environment present significant challenges for radiographic diagnostics. X-ray backlighting diagnostics at 1865 and 6181 eV using spherically-bent crystals have been fielded on the Z-machine, each with a {approx}0.6 eVspectral bandpass, 10 {micro}m spatial resolution, and a 4 mm by 20mm field of view. The Z-Beamlet laser, a 2-TW, 2-kJ Nd:glass laser({lambda} = 527 nm), is used to produce 0.1-1 J x-ray sources for radiography. The design, calibration, and performance of these diagnostics is presented.
The purpose of this study was to investigate the impact of instructions on aircraft visual inspection performance and strategy. Forty-two inspectors from industry were asked to perform inspections of six areas of a Boeing 737. Six different instruction versions were developed for each inspection task, varying in the number and type of directed inspections. The amount of time spent inspecting, the number of calls made, and the number of the feedback calls detected all varied widely across the inspectors. However, inspectors who used instructions with a higher number of directed inspections referred to the instructions more often during and after the task, and found a higher percentage of a selected set of feedback cracks than inspectors using other instruction versions. This suggests that specific instructions can help overall inspection performance, not just performance on the defects specified. Further, instructions were shown to change the way an inspector approaches a task.
The dynamic compression of molten metals including Sn is of current interest. In particular, experiments on the compression of molten Sn by Davis and Hayes will be described at this conference. Supporting calculations of the equation of state and structure of molten Sn as a function of temperature and pressure are in progress. The calculations presented are ab initio molecular dynamics simulations based on electronic density functional theory within the local density approximation. The equation of state and liquid structure factors for zero pressure are compared with existing experimental results. The good agreement in this case provides validation of the calculations.
The pulsed-power Z machine, in an isentropic compression experiment (ICE) mode, will allow the dynamic characterization of porous materials - here various ceramic powders, e.g., Al{sub 2}O{sub 3}, WC, ZrO{sub 2} - at roughly half their solid densities. A cylindrical configuration can provide megabar-level loads on an annulus of the sample material. Data will be provided by velocity interferometers that measure free-surface (or possibly interface) particle velocities. Differing sample thicknesses using stepped or conical geometries yield experimental efficiency by allowing multiple data records on single shots. With the p/{alpha} model for porous materials, the one-dimensional Lagrangian hydrocode WONDY provides the needed analyses. Based on static data, both power-law and quadratic crush curves are employed. Within the model constraints, we suggest that the most important parameter for characterizing the material is the crush strength, p{sub s}. With adequate sample thicknesses, the planned velocity measurements differentiate among the various assumptions for p{sub s}.
The first vacuum-ultraviolet spectrum of a polysilylene (chain-type polysilane) with aromatic substituents is presented. Assignments of the absorption bands of the model compound poly(methylphenylsilylene) are based on previous experimental data and theoretical electronic band structure calculations for poly(alkylsilylenes) and on ultraviolet spectra of phenyl-containing monomers and polymers. Although aryl orbitals mix with the {sigma}-conjugated orbitals located along the catenated silicon backbone, some transitions are largely localized on the phenyl groups. These assignments elucidate the nature of the bonding in polysilylenes and should be useful in understanding photodegradation mechanisms and in the design of related new optical materials.
The effect of cross-linker functionality and interfacial bond density on the fracture behavior of highly cross-linked polymer networks bonded to a solid surface is studied using large-scale molecular dynamics simulations. Three different cross-linker functionalities (f = 3, 4, and 6) are considered. The polymer networks are created between two solid surfaces with the number of bonds to the surfaces varying from zero to full bonding to the network. Stress?strain curves are determined for each system from tensile pull and shear deformations. At full interfacial bond density the failure mode is cohesive. The cohesive failure stress is almost identical for shear and tensile modes. The simulations directly show that cohesive failure occurs when the number of interfacial bonds is greater than in the bulk. Decreasing the number of interfacial bonds results in cohesive to adhesive transition consistent with recent experimental results. The correspondence between the stress?strain curves at different f and the sequence of molecular deformations is obtained. The failure stress decreases with smaller f while failure strain increases with smaller f.