We present a combined experimental and theoretical study of submonolayer growth in the presence of predeposited immobile impurities. Scanning tunneling microscopy measurements of Al/Al(1 1 1) epitaxy in the presence of oxygen adsorbates show that immobile O impurities influence all aspects of the early stages of homoepitaxial growth on Al(1 1 1). Possible scenarios for modified growth are investigated using kinetic Monte Carlo simulations. Dependences of island density on temperature, impurity concentration and strength and type of adatom-impurity interaction are compared. The comparison shows that the morphology of the growing Al film cannot result from only one interaction type: attractive or repulsive. An oscillatory interaction, suggested by ab initio calculations, is proposed to explain the behavior of the system.
We have conducted five hydraulic fracturing stress measurement campaigns in Korea, involving 13 test holes ranging in depth from 30 to 250 m, at locations from North Seoul to the southern coast of the peninsula. The measurements reveal consistent crustal stress magnitudes and directions that suggest persistence throughout western and southern Korea. The maximum horizontal stress {sigma}{sub H} is oriented between ENE-WSW and E-W, in accord with plate movement and deformation, and with directions indicated by both focal mechanism solutions from earthquakes inland and offshore as well as borehole breakouts in mainland China close to its eastern coast. With respect to magnitudes, the vertical stress is the overall minimum stress at all tested locations, suggesting a thrust faulting regime within the relatively shallow depths reached by our tests. Typically, such a stress regime becomes one favoring strike-slip at greater depths, as is also indicated by the focal mechanism solutions around Korea.
Alumina/poly(methyl methacrylate) (PMMA) nanocomposites were synthesized by an in situ free-radical polymerization process with 38 and 17 nm diameter {gamma}-alumina nanoparticles. At extremely low filler weight fractions (<1.0 wt % of 38 nm fillers or < 0.5 wt % of 17 nm fillers) the glass-transition temperature (T{sub g}) of the nanocomposites drops by 25 C when compared to the neat polymer. Further additions of filler (up to 10 wt %) do not lead to additional T{sub g} reductions. The thermal behavior is shown to vary with particle size, but this dependence can be normalized with respect to a specific surface area. The nanocomposite T{sub g} phenomenon is hypothesized to be because of nonadhering nanoparticles that serve as templates for a porous system with many internal interfaces that break up the percolating structure of dynamically heterogeneous domains recently suggested by Long, D.; and Lequeux, F. Eur Phys J E 2001, 4, 371 to be responsible for the T{sub g} reductions in polymer ultrathin films. The results also point to a far field effect of the nanoparticle surface on the bulk matrix.
The goal of this research was to develop and demonstrate cooperative 3-D plume tracing algorithms for miniature autonomous underwater vehicles. Applications for this technology include Lost Asset and Survivor Location Systems (L-SALS) and Ship-in-Port Patrol and Protection (SP3). This research was a joint effort that included Nekton Research, LLC, Sandia National Laboratories, and Texas A&M University. Nekton Research developed the miniature autonomous underwater vehicles while Sandia and Texas A&M developed the 3-D plume tracing algorithms. This report describes the plume tracing algorithm and presents test results from successful underwater testing with pseudo-plume sources.
This paper proposes a method for predicting the complexity of meshing computer aided design (CAD) geometries with unstructured, hexahedral, finite elements. Meshing complexity refers to the relative level of effort required to generate a valid finite element mesh on a given CAD geometry. A function is proposed to approximate the meshing complexity for single part CAD models. The function is dependent on a user defined element size as well as on data extracted from the geometry and topology of the CAD part. Several geometry and topology measures are proposed, which both characterize the shape of the CAD part and detect configurations that complicate mesh generation. Based on a test suite of CAD models, the function is demonstrated to be accurate within a certain range of error. The solution proposed here is intended to provide managers and users of meshing software a method of predicting the difficulty in meshing a CAD model. This will enable them to make decisions about model simplification and analysis approaches prior to mesh generation.
We used a regeneratively amplified Ti:sapphire femtosecond laser to create optical birefringence in an isotropic glass medium. Between two crossed polarizers, regions modified by the femtosecond laser show bright transmission with respect to the dark background of the isotropic glass. This observation immediately suggests that these regions possess optical birefringence. The angular dependence of transmission through the laser-modified region is consistent with that of an optically birefringent material. Laser-induced birefringence is demonstrated in different glasses, including fused silica and borosilicate glass. Experimental results indicate that the optical axes of laser-induced birefringence can be controlled by the polarization direction of the femtosecond laser. The amount of laser-induced birefringence depends on the pulse energy level and number of accumulated pulses.
Poly(N-isopropylacrylamide) (PNIPAM) exhibits a lower critical solution temperature (LCST) of {approx}30 C in water that is attributed to alterations in the hydrogen-bonding interactions of the amide group. PNIPAM in various forms has been explored for a variety of applications including controlled drug delivery, solute separation, tissue culture substrates, and controlling the adsorption of proteins, blood cells, and bacteria. Grafting PNIPAM onto surfaces is a promising strategy for creating responsive surfaces, since the physical properties of PNIPAM are readily controlled by changing the temperature. Considerable effort has been devoted to studying variations in chain conformations with temperature (T) in PNIPAM-based materials. Kubota et al. studied conformational changes of PNIPAM free chains with temperature for molecular weights ranging from 1.63 x 10{sup 6} to 2.52 x 10{sup 7} g/mol (M{sub w}/M{sub n} > 1.3) in water using laser light scattering. They reported a decrease in the radius of gyration (R{sub g}) as the solution temperature increased above the LCST. The magnitude of the effect was more pronounced with increasing molecular weight, ranging up to a factor of two for the highest molecular weight sample. In a similar study, Wu et al. observed a decrease in R{sub g} of a factor of seven for a high molecular weight PNIPAM sample with very low polydispersity (M{sub w} = 1.3 x 10{sup 7} g/mol, M{sub w}/M{sub n} < 1.05). Regarding grafted PNIPAM chains, Kidoaki et al. recently employed an iniferter-based graft polymerization method to generate a dense, high molecular weight brush and reported changes in the thickness measured by AFM. The thickness of the grafted layer was obtained from AFM images of the boundary between grafted and nongrafted (ablated by laser light) regions. They found that the swollen film thickness decreased by a factor of {approx}2 with increasing temperature from 25 to 40 C for samples with a range of dry film thickness from 250 to 1500 {angstrom}. More recently, Balamurugan et al. used surface plasmon resonance (SPR) to probe conformational changes in a PNIPAM brush grafted onto a gold layer by atom transfer radical polymerization (ATRP). For a sample with a dry film thickness of 517 {angstrom}, the SPR measurements indicated a significant contraction (extension of the layer with increasing/decreasing) temperature through the transition. Quantification of the change in profile characteristics was not reported, but it was noted that the change in the SPR signal occurred over a much broader range of temperature (15-35 C) than is typical of the transition for free chains in bulk solution. No systematic study of detailed PNIPAM chain conformations has yet been reported as a function of the two critical brush parameters, the surface density and molecular weight. A recent theoretical analysis by Baulin and Halperin has identified the surface density as a critical parameter demarcating different regimes of behavior. This arises from the concentration dependence of the Flory {chi} parameter as obtained from a recent phase behavior study of free chains in solution. Little attention has been paid to the surface density in previous experimental studies of grafted PNIPAM chains. We have begun a systematic study of the temperature-dependent conformational changes of PNIPAM grafted chains in water as a function of surface density and molecular weight using neutron reflection (NR). In previous work, we investigated the conformational changes of PNIPAM chains tethered to silicon oxide using two methods. The first was the 'grafting from' method in which N-isopropylacrylamide monomers were polymerized from the silicon surface with a chain transfer, free-radical technique. In the second method, preformed PNIPAM chains with carboxylic acid end groups associated with terminal hydroxyl groups of a mixed self-assembling monolayer. Detailed concentration profiles of the PNIPAM brushes were determined in D{sub 2}O as a function of temperature and also in d-acetone at room temperature. Profiles were obtained in the two solvents in order to investigate the role of the solvent in mediating interactions. The profiles in D{sub 2}O were bilayers, composed of a very thin layer with higher concentration at the surface and a low concentration layer extending well into the subphase. The very thin, higher concentration surface layer was attributed to attractive segment-surface interactions. The profiles in acetone were smoothly decaying single-layer profiles. The low segment concentration at the surface in acetone indicated that the surface density of these brushes was rather low. The dry film thicknesses were less than 40 {angstrom}, much lower than in the study of Kidoaki et al. On the basis of the molecular weights and dry film thicknesses, the surface density ({sigma}, chains/{angstrom}{sup 2}) ranged from 1 x 10{sup -4} to 2 x 10{sup -4} for those samples.
Resonant subwavelength gratings (RSGs) may be used as narrow-band wavelength and angular reflectors. Rigorous coupled wave analysis (RCWA) predicts 100% reflectivity at the resonant frequency of an incident plane wave from an RSG of infinite extent. For devices of finite extent or for devices illuminated with a finite beam, the peak reflectivity drops, coupled with a broadening of the peak. More complex numerical methods are required to model these finite effects. We have modeled finite devices and finite beams with a two-dimensional finite difference Helmholtz equation. The effect of finite grating aperture and finite beam size are investigated. Specific cases considered include Gaussian beam illumination of an infinite grating, Gaussian illumination of a finite grating, and plane wave illumination of an apertured grating. For a wide grating with a finite Gaussian beam, it is found that the reflectivity is an exponential function of the grating width. Likewise, for an apertured grating the reflectivity shows an exponential decay with narrowing aperture size. Results are compared to other methods, including plane wave decomposition of Gaussian beams using RCWA for the case of a finite input beam, and a semi-analytical techniques for the case of the apertured grating.
Changes in the cathodoluminescent (CL) brightness and in the surface chemistry of nanoparticulate SiO{sub 2}-coated and uncoated ZnS:Ag, Cl powder phosphor have been investigated using a PHI 545 scanning Auger electron spectrometer (AES), an Oriel optical spectrometer and a JEOL 6400 scanning electron microscope (SEM). The data were collected in a stainless steel UHV chamber with residual gas pressures between 1 x 10{sup -8} and 1 x 10{sup -6} Torr as measured by a Dycor LC residual gas analyzer (RGA). The primary electron current density was 272 {micro}A/cm{sup 2}, while the primary beam energy was varied bwteen 2 and 5 keV. In the presence of a 2keV primary electron beam in 1 x 10{sup -6} Torr of water for both the SiO{sub 2}-coated and the uncoated cases, the amounts of C and S on the surface decreased, that of O increased and the CL intensity decreased with electron dose. This surface chemistry change lead to the development of a surface dead layer and is explained by the electron beam stimulated surface chemical reaction model (ESSCR). The penetration range of the impinging low energy primary electrons is on the order of 10-100 nm creating a reaction region very close to the surface. The ESSCR takes this into account postulating that primary and secondary electrons dissociate physisorbed molecules to form reactive atomic species. These atomic species remove surface S as volatile SO{sub x} or H{sub 2}S. In the case of an oxidizing ambient (i.e. high partial pressure of water), a non-luminescent ZnO layer is formed. this oxide layer has been measured to be on the order of 3-30 nm. In the case where the vacuum of 1 x 10{sup -8} Torr was dominated by hydrogen and had a low water content, there was a small increase in the S signal, no rise in the O Auger signal, but the CL intensity still decreased. This is explained by the ESSCR whereby H removes S as H{sub 2}S leaving elemental Zn, which evaporates due to a high vapor pressure. In the case of ZnS:Ag,Cl coated with SiO{sub 2}, morphological changes were observed on the surface after extended electron beam exposure. Erosion of ZnS occurs more dramatically at an accelerating voltage of 5kV even at the same current density. Uncoated ZnS:Ag,Cl phosphors exhibited similar surface chemical changes to that of SiO{sub 2}-coated ZnS:Ag,Cl but did not degrade to the same extent. Also, no change in the surface morphology was observed. These SEM images as well as reaction rate data suggest that these nanometer sized SiO{sub 2} particles acted as a catalyst for decomposition of the ZnS especially in a reducing ambient (i.e. high hydrogen partial pressure). In order to reduce CL degradation of these and other phosphors, protective coatings were pulse laser deposited onto the phosphor surface. The effectiveness of these coatings was dependent upon both the thickness and the uniformity. Thicknesses of these coatings ranged from 1-5 nm and were uniform as determined using profilometry and TEM.
To address known shortcomings of classical metal plasticity for describing material behavior under shock loading, a model which incorporates a distribution in the deviatoric stress state is developed. This distribution will translate in stress space under loading, and growth of the distribution can be included in the model as well. This proposed model is capable of duplicating the key features of a set of reshock and release experiments on 6061-T6 aluminum, many of which are not captured by classical plasticity. The model is relatively simple, is only moderately more computationally intensive, and requires few additional material parameters.
Piezoelectric polymers based on PVDF are of interest for use in large aperture space-based telescopes similar to the James Web Space Telescope. Dimensional adjustments of polymer films depend on their piezoelectric properties with wireless (electron beam) shape control methods having been successfully demonstrated in the past. Such electron beam controls require a detailed understanding of the piezoelectric material responses. Similarly, space applications demand consistent, predictable, and reliable performance. While PVDF as a generic polymer type is a suitable piezoelectric material, it is also well known that fluorinated polymers are highly radiation-sensitive. Mechanical and other physical properties will suffer under various types of radiation (strong vacuum UV, {gamma}-, X-ray, e-beam, ion-beam) and atomic oxygen exposure. Likewise, extreme temperature fluctuations in space environments will result in annealing effects and cyclic stresses. While the radiative degradation chemistry of polymers is an established field there is little information available on the performance of piezoelectric features in PVDF with respect to their expected changes in these environments. Therefore, understanding such fundamental issues becomes mandatory for the design and deployment of satellite systems utilizing these materials/technology. We have investigated the degradation of PVDF and copolymers under a range of stress environments, and have studied the implications with regard to piezoelectrical properties necessary for reliable operation of thin films in space environments. Initial aging studies using {gamma}- and e-beam irradiation to explore material sensitivities for comparison with expected UV doses have shown complex material changes with lowered Curie temperatures, crystallinity, melting points and significant crosslinking, but little affect on piezoelectric d{sub 33} constants. Similar complexities of the aging processes have been observed in accelerated temperature environments. Overall, the results suggest that poling and polymer orientation are negatively affected by radiation effects and temperature. We have established fundamental correlations between chemical (structural) and physical (morphology) features of various PVDF copolymers and their piezoelectric properties. A frame work for material qualification issues and overall system survivability predictions in low earth orbit conditions has been developed. It will allow for improved material selection, feedback for manufacturing and processing technologies, avenues for material optimization/stabilization strategies and provide the necessary guidance on any alternative materials.
Thin polymer films have been identified as one of the major enabling technologies for future space-based systems. Potential devices include those based on piezoelectric bimorph polymers that deform when a charge is deposited, for example, from an electron gun. The thin-film and lightweight nature of the polymeric devices will allow them to be launched more readily and deployed to operating conditions once in orbit. Until now little work has been done aimed at investigating the performance of piezoelectric properties of PVDF and its copolymers and the prediction of their long-term stability in low Earth orbit (LEO) environmental conditions. In this paper, the piezoelectric properties of PVDF and the copolymers formed from polymerization of vinylidene fluoride and trifluoroethylene (TrFE) or hexafluoropropylene (HFP) have been studied over a broad temperature range simulating that expected in LEO. The temperatures experienced by unprotected polymers on low altitude spacecraft have previously been reported as ranging from approximately -100 C to +130 C as the polymer/spacecraft passes in and out of the Earth's shadow. To examine the effects of temperature on the piezoelectric properties of poled PVDF, P(VDF-TrFE) and P(VDF-HFP) the d{sub 33} piezoelectric coefficients and electric displacement-electric field (D-E) hysteresis loops were measured up to 160 C for the d{sub 33} measurements and from -80 to +110 C for the D-E loops. The room temperature d{sub 33} coefficient of PVDF homopolymer films, annealed for extended periods at 50, 80 and 125 C, dropped rapidly within a few days of heating, then remained unchanged for periods of up to 300 days. In contrast, the TrFE copolymer exhibited greater thermal stability than the homopolymer, with the d{sub 33} remaining almost unchanged from the pre-annealing value after heating at 50, 80 and 125 C. The HFP copolymer exhibited poor retention of d33 at temperatures above 80 C. For all three polymers short term annealing at 160 C reduced the d{sub 33} to zero. The decrease in d{sub 33} for the TrFE copolymer was correlated with the change in Curie temperature upon annealing of the copolymer, as observed by differential scanning calorimetry (DSC). Unlike radiation damage, which may occur from vacuum UV and atomic oxygen in LEO, the depoling of the polymers on exposure to elevated temperatures was attributed to a physical randomization of the morphology rather than a chemical degradation process. In situ D-E loop measurements over the temperature range -80 to +110 C showed that the remnant polarization of the TrFE copolymer was more stable than the PVDF homopolymer. These results suggest that the TrFE copolymer appears to have a better overall performance in thermal extremes compared with PVDF or an HFP copolymer.
This work demonstrates a polycrystalline silicon surface-micromachined inchworm actuator that exhibits high-performance characteristics such as large force ({+-}0.5 millinewtons), large velocity range (0 to {+-}4.4 mm/sec), large displacement range ({+-}100 microns), small step size ({+-}10, {+-}40 or {+-}100 nanometers), low power consumption (nanojoules per cycle), continuous bidirectional operation and relatively small area (600 x 200{micro}m{sup 2}). An in situ load spring calibrated on a logarithmic scale from micronewtons to millinewtons, optical microscopy and Michelson interferometry are used to characterize its performance. The actuator consists of a force-amplifying plate that spans two voltage-controlled clamps, and walking is achieved by appropriately sequencing signals to these three components. In the clamps, normal force is borne by equipotential rubbing counterfaces, enabling friction to be measured against load. Using different monolayer coatings, we show that the static coefficient of friction can be changed from 0.14 to 1.04, and that it is load-independent over a broad range. We further find that the static coefficient of friction does not accurately predict the force generated by the actuator and attribute this to nanometer-scale presliding tangential deflections.
This paper demonstrates a simple technique for building n-channel MOSFETs and complex micromechanical systems simultaneously instead of serially, allowing a more straightforward integration of complete systems. The fabrication sequence uses few additional process steps and only one additional masking layer compared to a MEMS-only technology. The process flow forms the MOSFET gate electrode using the first level of mechanical polycrystalline silicon, while the MOSFET source and drain regions are formed by dopant diffusions into the substrate from subsequent levels of heavily doped poly that is used for mechanical elements. The process yields devices with good, repeatable electrical characteristics suitable for a wide range of digital and analog applications.
Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is capable of generating huge volumes of data. TOF-SIMS spectrum-images, comprising complete mass spectra at each point in a spatial array, are easily acquired with modern instrumentation. With the addition of depth profiling, spectra can be collected from up to three spatial dimensions leading to data sets that are seemingly unlimited in size. Multivariate statistical techniques such as principal component analysis, multivariate curve resolution and other factor analysis methods are being used to meet the challenge of turning that mountain of data into analytically useful knowledge. These methods work by extracting the essential chemical information embedded in the high dimensional data into a limited number of factors that describe the spectrally active pure components present in the sample. A review of the recent literature shows that the mass spectral data are often scaled prior to multivariate analysis. Common preprocessing steps include normalization of the pixel intensities, and auto- or variance-scaling of the mass spectra. In this paper, we will demonstrate that these pretreatments can lead to less than satisfactory results and, in fact, can be counterproductive. By taking the Poisson nature of the data into consideration, however, a scaling method can be devised that is optimal in a maximum likelihood sense. Using a simple and intuitive example, we will demonstrate the superiority of the optimal scaling approach for estimating the number of pure components, for segregating the chemical information into as few components as possible, and for discriminating small features from noise.
The shock response of heterogeneous materials involves highly fluctuating states and localization effects that are produced by mesostructure. Prior studies have examined this shock behavior in randomized inert and reactive media. In this work, we investigate the shock behavior in a porous lattice consisting of hexagonally packed layers of 500 {micro}m tin spheres impacted at 0.5 km/s. This ordered geometry provides a well-defined configuration to validate mesoscale material modeling based on three-dimensional CTH calculations. Detailed wave fields are experimentally probed using a line-imaging interferometer and transmitted particle velocities are compared to numerical mesoscale calculations. Multiple shock fronts traverse the porous layers whereby particle-to-particle interactions cause stress bridging effects and the evolution of organized wave structures.
Findings are presented from the first year of a joint project between the U.S. Army Engineer Research and Development Center, the U.S. Army Research Laboratory, and the Sandia National Laboratories. The purpose of the project is to develop a finite-difference, time-domain (FDTD) capability for simulating the acoustic signals received by battlefield acoustic sensors. Many important effects, such as scattering from trees and buildings, interactions with dynamic atmospheric wind and temperature fields, and nonstationary target properties, can be accommodated by the simulation. Such a capability has much potential for mitigating the need for costly field data collection and furthering the development of robust identification and tracking algorithms. The FDTD code is based on a carefully derived set of first-order differential equations that is more general and accurate than most current sound propagation formulations. For application to three-dimensional problems of practical interest in battlefield acoustics, the code must be run on massively parallel computers. Some example computations involving sound propagation in a moving atmosphere and propagation in the presence of trees and barriers are presented.