We have investigated the liquid-phase self-assembly of 1-alkanethiols (HS(CH{sub 2}){sub n-1}CH{sub 3}, n = 8, 16, and 18) on hydrogenated Ge(111), using attenuated total reflection Fourier transform infrared spectroscopy as well as water contact angle measurements. The infrared absorbance of C-H stretching modes of alkanethiolates on Ge, in conjunction with water contact angle measurements, demonstrates that the final packing density is a function of alkanethiol concentration in 2-propanol and its chain length. High concentration and long alkyl chain increase the steady-state surface coverage of alkanethiolates. A critical chain length exists between n = 8 and 16, above which the adsorption kinetics is comparable for all long alkyl chain 1-alkanethiols. The steady-state coverage of hexadecanethiolates, representing long-chain alkanethiolates, reaches a maximum at approximately 5.9 x 10{sup 14} hexadecanethiolates/cm{sup 2} in 1 M solution. The characteristic time constant to reach a steady state also decreases with increasing chain length. This chain length dependence is attributed to the attractive chain-to-chain interaction in long-alkyl-chain self-assembled monolayers, which reduces the desorption-to-adsorption rate ratio (k{sub d}/k{sub a}). We also report the adsorption and desorption rate constants (k{sub a} and k{sub d}) of 1-hexadecanethiol on hydrogenated Ge(111) at room temperature. The alkanethiol adsorption is a two-step process following a first-order Langmuir isotherm: (1) fast adsorption with k{sub a} = 2.4 {+-} 0.2 cm{sup 3}/(mol s) and k{sub d} = (8.2 {+-} 0.5) x 10{sup -6} s{sup -1}; (2) slow adsorption with k{sub a} = 0.8 {+-} 0.5 cm{sup 3}/(mol s) and k{sub d} = (3 {+-} 2) x 10{sup -6} s{sup -1}.
The present study is a numerical investigation of the propagation of electromagnetic transients in dispersive media. It considers propagation in water using Debye and composite Rocard-Powles-Lorentz models for the complex permittivity. The study addresses this question: For practical transmitted spectra, does precursor propagation provide any features that can be used to advantage over conventional signal propagation in models of dispersive media of interest? A companion experimental study is currently in progress that will attempt to measure the effects studied here.
Time-of-flight secondary ion mass spectrometry (TOF-SIMS) by its parallel nature, generates complex and very large datasets quickly and easily. An example of such a large dataset is a spectral image where a complete spectrum is collected for each pixel. Unfortunately, the large size of the data matrix involved makes it difficult to extract the chemical information from the data using traditional techniques. Because time constraints prevent an analysis of every peak, prior knowledge is used to select the most probable and significant peaks for evaluation. However, this approach may lead to a misinterpretation of the system under analysis. Ideally, the complete spectral image would be used to provide a comprehensive, unbiased materials characterization based on full spectral signatures. Automated eXpert spectral image analysis (AXSIA) software developed at Sandia National Laboratories implements a multivariate curve resolution technique that was originally developed for energy dispersive X-ray spectroscopy (EDS) [Microsci. Microanal. 9 (2003) 1]. This paper will demonstrate the application of the method to TOF-SIMS. AXSIA distills complex and very large spectral image datasets into a limited number of physically realizable and easily interpretable chemical components, including both spectra and concentrations. The number of components derived during the analysis represents the minimum number of components needed to completely describe the chemical information in the original dataset. Since full spectral signatures are used to determine each component, an enhanced signal-to-noise is realized. The efficient statistical aggregation of chemical information enables small and unexpected features to be automatically found without user intervention.
The spreading of polymer droplets is studied using molecular dynamics simulations. To study the dynamics of both the precursor foot and the bulk droplet, large hemispherical drops of 200 000 monomers are simulated using a bead-spring model for polymers of chain length 10, 20, and 40 monomers per chain. We compare spreading on flat and atomistic surfaces, chain length effects, and different applications of the Langevin and dissipative particle dynamics thermostats. We find diffusive behavior for the precursor foot and good agreement with the molecular kinetic model of droplet spreading using both flat and atomistic surfaces. Despite the large system size and long simulation time relative to previous simulations, we find that even larger systems are required to observe hydrodynamic behavior in the hemispherical spreading droplet.
The Eulerian hydrocode, CTH, has been used to study the interaction of hypervelocity flyer plates with thin targets at velocities from 6 to 11 km/s. These penetrating impacts produce debris clouds that are subsequently allowed to stagnate against downstream witness plates. Velocity histories from this latter plate are used to infer the evolution and propagation of the debris cloud. This analysis, which is a companion to a parallel experimental effort, examined both numerical and physics-based issues. We conclude that numerical resolution and convergence are important in ways we had not anticipated. The calculated release from the extreme states generated by the initial impact shows discrepancies with related experimental observations, and indicates that even for well-known materials (e.g., aluminum), high-temperature failure criteria are not well understood, and that non-equilibrium or rate-dependent equations of state may be influencing the results.
Protein microtubules (MTs) 25 nm in diameter and tens of micrometers long have been used as templates for the biomimetic mineralization of FeOOH. Exposure of MTs to anaerobic aqueous solutions of Fe{sup 2+} buffered to neutral pH followed by aerial oxidation leads to the formation of iron oxide coated MTs. The iron oxide layer was found to grow via a two-step process: initially formed 10-30 nm thick coatings were found to be amorphous in structure and comprised of several iron-containing species. Further growth resulted in MTs coated with highly crystalline layers of lepidocrocite with a controllable thickness of up to 125 nm. On the micrometer size scale, these coated MTs were observed to form large, irregular bundles containing hundreds of individually coated MTs. Iron oxide grew selectively on the MT surface, a result of the highly charged MT surface that provided an interface favorable for iron oxide nucleation. This result illustrates that MTs can be used as scaffolds for the in-situ production of high-aspect-ratio inorganic nanowires.
The paper presents a theoretical study of synchronization between two coupled lasers. A theory valid for arbitrary coupling between lasers is used. Its key feature is that the laser field is decomposed in terms of the composite-cavity modes reflecting the spatial field dependence over the entire coupled-laser system. The ensuing multimode equations are reduced to class-B, and further to class-A equations which resemble competing species equations. Bifurcation analysis, supported by insight provided by analytical solutions, is used to investigate influences of pump, carrier decay rate, polarization decay rate, and coupling mirror losses on synchronization between lasers. Population pulsation is found to be an essential mode competition mechanism responsible for bistability in the synchronized solutions. Finally, we discovered that the mechanism leading to laser synchronization changes from strong composite-cavity mode competition in class-A regime to frequency locking of composite-cavity modes in class-B regime.
Dynamic compressive properties of an epoxy syntactic foam at various strain rates under lateral confinement have been investigated with a pulse-shaped split Hopkinson pressure bar (SHPB). The quasi-static responses were obtained with an MTS 810 materials test system. The quasi-static and dynamic stress-strain behavior of the foam under confinement exhibited an elastic-plastic-like response whereas an elastic-brittle behavior was observed under uniaxial stress loading conditions. The modulus of elasticity and yield strength, which had higher values than those in uniaxial stress case, were both sensitive to strain rates. However, the strain-hardening behavior under confinement was not strain-rate sensitive. A phenomenological elastic-plastic type of material model was employed to describe the strain-rate-dependent compressive properties of the syntactic foam under confinement, which agreed well with experimental results.
This research addresses effects of temperature, including adiabatic temperature rise in specimen during dynamic compression and environmental temperature, on the dynamic compressive properties of an epoxy syntactic foam. The adiabatic temperature rise in specimen during dynamic compression is found to be so small that its effects may be neglected. However, environmental temperature has significant effects on dynamic compressive behavior. With decreasing temperature, the foam initially hardens but then softens when below a transitional temperature, which are dominated by mechanisms of thermal-softening and damage-softening, respectively. A phenomenological material model accounting for both temperature and strain-rate effects has been developed, which well describes the compressive and failure behaviors at various strain rates and environmental temperatures.
We report for the first time a one-step, templateless method to directly prepare large arrays of oriented TiO{sub 2}-based nanotubes and continuous films. These titania nanostructures can also be easily prepared as conformal coatings on a substrate. The nanostructured films were formed on a Ti substrate seeded with TiO{sub 2} nanoparticles. SEM and TEM results suggested that a folding mechanism of sheetlike structures was involved in the formation of the nanotubes. The oriented arrays of TiO{sub 2} nanotubes, continuous films, and coatings are expected to have potentials for applications in catalysis, filtration, sensing, photovoltaic cells, and high surface area electrodes.
Currently, the Egyptian Atomic Energy Authority is designing a shallow-land disposal facility for low-level radioactive waste. To insure containment and prevent migration of radionuclides from the site, the use of a reactive backfill material is being considered. One material under consideration is hydroxyapatite, Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2}, which has a high affinity for the sorption of many radionuclides. Hydroxyapatite has many properties that make it an ideal material for use as a backfill including low water solubility (K{sub sp} > 10{sup -40}), high stability under reducing and oxidizing conditions over a wide temperature range, availability, and low cost. However, there is often considerable variation in the properties of apatites depending on source and method of preparation. In this work, we characterized and compared a synthetic hydroxyapatite with hydroxyapatites prepared from cattle bone calcined at 500 C, 700 C, 900 C and 1100 C. The analysis indicated the synthetic hydroxyapatite was similar in morphology to 500 C prepared cattle hydroxyapatite. With increasing calcination temperature the crystallinity and crystal size of the hydroxyapatites increased and the BET surface area and carbonate concentration decreased. Batch sorption experiments were performed to determine the effectiveness of each material to sorb uranium. Sorption of U was strong regardless of apatite type indicating all apatite materials evaluated. Sixty day desorption experiments indicated desorption of uranium for each hydroxyapatite was negligible.
High-power 18650 Li-ion cells have been developed for hybrid electric vehicle applications as part of the DOE Advanced Technology Development (ATD) program. The thermal abuse response of two advanced chemistries (Gen1 and Gen2) were measured and compared with commercial Sony 18650 cells. Gen1 cells consisted of an MCMB graphite based anode and a LiNi{sub 0.85}Co{sub 0.15}O{sub 2} cathode material while the Gen2 cells consisted of a MAG10 anode graphite and a LiNi{sub 0.80}Co{sub 0.15} Al{sub 0.05}O{sub 2} cathode. Accelerating rate calorimetry (ARC) and differential scanning calorimetry (DSC) were used to measure the thermal response and properties of the cells and cell materials up to 400 C. The MCMB graphite was found to result in increased thermal stability of the cells due to more effective solid electrolyte interface (SEI) formation. The Al stabilized cathodes were seen to have higher peak reaction temperatures that also gave improved cell thermal response. The effects of accelerated aging on cell properties were also determined. Aging resulted in improved cell thermal stability with the anodes showing a rapid reduction in exothermic reactions while the cathodes only showed reduced reactions after more extended aging.
{sup 90}Sr contamination is a major problem at several U.S. sites. At some sites, {sup 90}Sr has migrated deep underground making site remediation difficult. In this paper, we describe a novel method for precipitation of hydroxyapatite, a strong sorbent for {sup 90}Sr, in soil. The method is based on mixing a solution of calcium citrate and sodium phosphate in soil. As the indigenous soil microorganisms mineralize the citrate, the calcium is released and forms hydroxyapatite. Soil, taken from the Albuquerque desert, was treated with a sodium phosphate solution or a sodium phosphate/calcium citrate solution. TEM and EDS were used to identify hydroxyapatite with CO{sub 3}{sup 2-} substitutions, with a formula of (Ca{sub 4.8}Na{sub 0.2})[(PO{sub 4}){sub 2.8}(CO{sub 3}){sub 0.2}](OH), in the soil treated with the sodium phosphate/calcium citrate solution. Untreated and treated soils were used in batch sorption experiments for Sr uptake. Average Sr uptake was 19.5, 77.0 and 94.7% for the untreated soil, soil treated with sodium phosphate, and soil with apatite, respectively. In desorption experiments, the untreated soil, phosphate treated soil and apatite treated soil released an average of 34.2, 28.8 and 4.8% respectively. The results indicate the potential of forming apatite in soil using soluble reagents for retardation of radionuclide migration.
A fundamental challenge for engineering communication systems is the problem of transmitting information from the source to the receiver over a noisy channel. This same problem exists in a biological system. How can information required for the proper functioning of a cell, an organism, or a species be transmitted in an error introducing environment? Source codes (compression codes) and channel codes (error-correcting codes) address this problem in engineering communication systems. The ability to extend these information theory concepts to study information transmission in biological systems can contribute to the general understanding of biological communication mechanisms and extend the field of coding theory into the biological domain. In this work, we review and compare existing coding theoretic methods for modeling genetic systems. We introduce a new error-correcting code framework for understanding translation initiation, at the cellular level and present research results for Escherichia coli K-12. By studying translation initiation, we hope to gain insight into potential error-correcting aspects of genomic sequences and systems.
Visualization of scientific frontiers is a relatively new field, yet it has a long history and many predecessors. The application of science to science itself has been undertaken for decades with notable early contributions by Derek Price, Thomas Kuhn, Diana Crane, Eugene Garfield, and many others. What is new is the field of information visualization and application of its techniques to help us understand the process of science in the making. In his new book, Chaomei Chen takes us on a journey through this history, touching on predecessors, and then leading us firmly into the new world of Mapping Scientific Frontiers. Building on the foundation of his earlier book, Information Visualization and Virtual Environments, Chen's new offering is much less a tutorial in how to do information visualization, and much more a conceptual exploration of why and how the visualization of science can change the way we do science, amplified by real examples. Chen's stated intents for the book are: (1) to focus on principles of visual thinking that enable the identification of scientific frontiers; (2) to introduce a way to systematize the identification of scientific frontiers (or paradigms) through visualization techniques; and (3) to stimulate interdisciplinary research between information visualization and information science researchers. On all these counts, he succeeds. Chen's book can be broken into two parts which focus on the first two purposes stated above. The first, consisting of the initial four chapters, covers history and predecessors. Kuhn's theory of normal science punctuated by periods of revolution, now commonly known as paradigm shifts, motivates the work. Relevant predecessors outside the traditional field of information science such as cartography (both terrestrial and celestial), mapping the mind, and principles of visual association and communication, are given ample coverage. Chen also describes enabling techniques known to information scientists, such as multi-dimensional scaling, advanced dimensional reduction, social network analysis, Pathfinder network scaling, and landscape visualizations. No algorithms are given here; rather, these techniques are described from the point of view of enabling 'visual thinking'. The Generalized Similarity Analysis (GSA) technique used by Chen in his recent published papers is also introduced here. Information and computer science professionals would be wise not to skip through these early chapters. Although principles of gestalt psychology, cartography, thematic maps, and association techniques may be outside their technology comfort zone, or interest, these predecessors lay a groundwork for the 'visual thinking' that is required to create effective visualizations. Indeed, the great challenge in information visualization is to transform the abstract and intangible into something visible, concrete, and meaningful to the user. The second part of the book, covering the final three chapters, extends the mapping metaphor into the realm of scientific discovery through the structuring of literatures in a way that enables us to see scientific frontiers or paradigms. Case studies are used extensively to show the logical progression that has been made in recent years to get us to this point. Homage is paid to giants of the last 20 years including Michel Callon for co-word mapping, Henry Small for document co-citation analysis and specialty narratives (charting a path linking the different sciences), and Kate McCain for author co-citation analysis, whose work has led to the current state-of-the-art. The last two chapters finally answer the question - 'What does a scientific paradigm look like?' The visual answer given is specific to the GSA technique used by Chen, but does satisfy the intent of the book - to introduce a way to visually identify scientific frontiers. A variety of case studies, mostly from Chen's previously published work - supermassive black holes, cross-domain applications of Pathfinder networks, mass extinction debates, impact of Don Swanson's work, and mad cow disease and vCJD in humans - succeed in explaining how visualization can be used to show the development of, competition between, and eventual acceptance (or replacement) of scientific paradigms. Although not addressed specifically, Chen's work nonetheless makes the persuasive argument that visual maps alone are not sufficient to explain 'the making of science' to a non-expert in a particular field. Rather, expert knowledge is still required to interpret these maps and to explain the paradigms. This combination of visual maps and expert knowledge, used jointly to good effect in the book, becomes a potent means for explaining progress in science to the expert and non-expert alike. Work to extend the GSA technique to explore latent domain knowledge (important work that falls below the citation thresholds typically used in GSA) is also explored here.
The essential oil of white sage, Salvia apiana, was obtained by steam distillation and analysed by GC-MS. A total of 13 components were identified, accounting for >99.9% of the oil. The primary component was 1,8-cineole, accounting for 71.6% of the oil.