Naval Research Laboratory Chemistry Division

Molecular dynamics simulations and atomic force microscopy are used to investigate the atomistic mechanisms of adhesion, contact formation, nanoindentation, separation, and fracture that occur when a nickel tip interacts with a gold surface. The theoretically predicted and experimentally measured hysteresis in the force versus tip-to-sample distance relationship, found upon approach and subsequent separation of the tip from the sample, is related to inelastic deformation of the sample surface characterized by adhesion of gold atoms to the nickel tip and formation of a connective neck of atoms. At small tipsample distances, mechanical instability causes the tip and surface to jump-to-contact, which in turn leads to adhesion-induced wetting of the nickel tip by gold atoms. Subsequent indentation of the substrate results in the onset of plastic deformation of the gold surface. The atomic-scale mechanisms underlying the formation and elongation of a connective neck, which forms upon separation, consist of structural transformations involving elastic and yielding stages.

The design and fabrication of three-dimensional multifunctional architectures from the appropriate nanoscale building blocks, including the strategic use of void space and deliberate disorder as design components, permits a re-examination of devices that produce or store energy as discussed in this critical review. The appropriate electronic, ionic, and electrochemical requirements for such devices may now be assembled into nanoarchitectures on the bench-top through the synthesis of low density, ultraporous nanoarchitectures that meld high surface area for heterogeneous reactions with a continuous, porous network for rapid molecular flux. Such nanoarchitectures amplify the nature of electrified interfaces and challenge the standard ways in which electrochemically active materials are both understood and used for energy storage. An architectural viewpoint provides a powerful metaphor to guide chemists and materials scientists in the design of energy-storing nanoarchitectures that depart from the hegemony of periodicity and order with the promise--and demonstration--of even higher performance (265 references).

An intriguing problem in condensed matter physics is understanding the glass transition, in particular the dynamics in the equilibrium liquid close to vitrification. Recent advances have been made by using hydrostatic pressure as an experimental variable. These results are reviewed, with an emphasis in the insight provided into the mechanisms underlying the relaxation properties of glass-forming liquids and polymers.

An atomic force microscope (AFM) has been configured so that it measures the force between a tip mounted on a cantilever beam and a sample surface as a function of the tip–surface separation. This allows the AFM to study both the nanomechanical properties of the sample and the forces associated with the tip–surface interaction. More specifically, the AFM can measure the elastic and plastic behavior and hardness via nanoindentation, van der Waals forces, and the adhesion of thin-film and bulk materials with unprecedented force and spatial resolution. The force resolution is currently 1 nanonewton, and the depth resolution is 0.02 nm. Additionally, the instrument itself is compact and relatively inexpensive.

The self-limiting reaction of aqueous permanganate with carbon nanofoams produces conformal, nanoscopic deposits of birnessite ribbons and amorphous MnO2 throughout the ultraporous carbon structure. The MnO2 coating contributes additional capacitance to the carbon nanofoam while maintaining the favorable high-rate electrochemical performance inherent to the ultraporous carbon structure of the nanofoam. Such a three-dimensional design exploits the benefits of a nanoscopic MnO2-carbon interface to produce an exceptionally high area-normalized capacitance (1.5 F cm-2), as well as high volumetric capacitance (90 F cm-3).

Pt−Ru is the favored anode catalyst for the oxidation of methanol in direct methanol fuel cells (DMFCs). The nanoscale Pt−Ru blacks are accepted to be bimetallic alloys as based on their X-ray diffraction patterns. Our bulk and surface analyses show that although practical Pt−Ru blacks have diffraction patterns consistent with an alloy assignment, they are primarily a mix of Pt metal and Ru oxides plus some Pt oxides and only small amounts of Ru metal. Thermogravimetric analysis and X-ray photoelectron spectroscopy of as-received Pt−Ru electrocatalysts indicate that DMFC materials contain substantial amounts of hydrous ruthenium oxide (RuOxHy). A potential misidentification of nanoscale Pt−Ru blacks arises because RuOxHy is amorphous and cannot be discerned by X-ray diffraction. Hydrous ruthenium oxide is a mixed proton and electron conductor and innately expresses Ru−OH speciation. These properties are of key importance in the mechanism of methanol oxidation, in particular, Ru−OH is a critical component of the bifunctional mechanism proposed for direct methanol oxidation in that it is the oxygen-transfer species that oxidatively dissociates −C⋮O fragments from the Pt surface. The catalysts and membrane-electrode assemblies of DMFCs should not be processed at or exposed to temperatures >150 °C, as such conditions deleteriously lower the proton conductivity of hydrous ruthenium oxide and thus affect the ability of the Ru component of the electrocatalyst to dissociate water. With this analytical understanding of the true nature of practical nanoscale Pt−Ru electrocatalysts, we can now recommend that hydrous ruthenium oxide, rather than Ru metal or anhydrous RuO2, is the preferred Ru speciation in these catalysts.

The fracture behavior of a piperidine/bisphenol A diglycidyl ether (A) resin has been determined in bulk and as an adhesive using the linear elastic fracture methods developed by Mostovoy1. The effect of adding carboxy-terminated butadiene–acrylonitrile (CTBN) elastomer to resin A was investigated. The opening-mode fracture energy () of resin A was 120 to 150 J/m2, and largely attributable to plastic deformation. Fractographic evidence was obtained for plastic flow at the crack tip during crack initiation. Propagation was unstable due to the rate dependence of the plasticity. There were no significant differences in the bulk and adhesive fracture behavior. Addition of 5–15% CTBN to resin A produced minute elastomer particles which increased to ∼4000J/m2 (at 15%). Further CTBN addition resulted in an elastomer–epoxy blend and a decrease in fracture energy. Fractography again indicated that crack initiation involved plastic deformation but that the elastomer had greatly increased the volume in which the deformation occurred. The adhesive fracture of the elastomer–epoxy was found to be strongly dependent on the crack-tip deformation zone size (ryc) in that was a maximum when bond thickness was equal to 2 ryc. At bond thicknesses less than 2 ryc, there was a restraint on the development of the plastic zone resulting in lower values.

Zinc-based replacements for Li-ion batteries are now feasible by using 3D-interconnected Zn sponges that suppress dendrite formation when cycled.

The sharpness of tips used in scanning tunneling microscopy (STM) is one factor which affects the resolution of the STM image. In this paper, we report on a direct-current (dc) drop-off electrochemical etching procedure used to sharpen tips for STM. The shape of the tip is dependent on the meniscus which surrounds the wire at the air–electrolyte interface. The sharpness of the tip is related to the tensile strength of the wire and how quickly the electrochemical reaction can be stopped once the wire breaks. We have found that the cutoff time of the etch circuit has a significant effect on the radius of curvature and cone angle of the etched tip; i.e., the faster the cutoff time, the sharper the tip. We have constructed an etching circuit with a minimum cut-off time of 500 ns which uses two fast metal–oxide semiconductor field effect transistors (MOSFET) and a high-speed comparator. The radius of curvature of the tips can be varied from approximately 20 to greater than 300 nm by increasing the cutoff time of the circuit.

The creation of a sustainable energy generation, storage, and distribution infrastructure represents a global grand challenge that requires massive transnational investments in the research and development of energy technologies that will provide the amount of energy needed on a sufficient scale and timeframe with minimal impact on the environment and have limited economic and societal disruption during implementation. In this opinion paper, we focus on an important set of solar, thermal, and electrochemical energy conversion, storage, and conservation technologies specifically related to recent and prospective advances in nanoscale science and technology that offer high potential in addressing the energy challenge. We approach this task from a two-fold perspective: analyzing the fundamental physicochemical principles and engineering aspects of these energy technologies and identifying unique opportunities enabled by nanoscale design of materials, processes, and systems in order to improve performance and reduce costs. Our principal goal is to establish a roadmap for research and development activities in nanoscale science and technology that would significantly advance and accelerate the implementation of renewable energy technologies. In all cases we make specific recommendations for research needs in the near-term (2–5 years), mid-term (5–10 years) and long-term (>10 years), as well as projecting a timeline for maturation of each technological solution. We also identify a number of priority themes in basic energy science that cut across the entire spectrum of energy conversion, storage, and conservation technologies. We anticipate that the conclusions and recommendations herein will be of use not only to the technical community, but also to policy makers and the broader public, occasionally with an admitted emphasis on the US perspective.

Aerogels, which are nanoscale mesoporous materials of low density and high surface area, have been well studied as thermal insulators, heterogeneous catalysts, and novel particle or radiation detectors. Now, electrically conducting oxide aerogels are being explored as new materials in electrochemistry and for their innate ability to amplify the nature of the surfaces of technologically relevant conducting oxides in batteries, ultracapacitors, and fuel cells. Recent results are reviewed in which the mixed electron- and cation-conducting transition metal oxides of vanadium, molybdenum, ruthenium, and manganese have been prepared as low density, highly porous, and high surface area aerogels and then studied as charge-storage electrode materials. These materials challenge the standard ways in which electrochemically active oxides are conceived, studied, and used.

Contrary to the current understanding of Pt−Ru electrocatalyzed oxidation of methanol, the bimetallic alloy is not the most desired form of the catalyst. In the nanoscale Pt−Ru blacks used to electrooxidize methanol in direct methanol fuel cells, Pt0Ru0 has orders of magnitude less activity for methanol oxidation than does a mixed-phase electrocatalyst containing Pt metal and hydrous ruthenium oxides (RuOxHy). Bulk, rather than near-surface, quantities of electron−proton conducting RuOxHy are required to achieve high activity for methanol oxidation. The active catalyst forms a nanoscopic, phase-separated hydrons oxide-on-metal structure that retains the Pt metal−RuOxHy boundaries required to oxidize methanol fully to carbon dioxide and water.

Using an atomic force microscope (AFM), we have studied the attractive and adhesive forces between a cantilever tip and sample surfaces as a function of sample surface energy. The measured forces systematically increased with surface energy. The AFM is very sensitive; changes in the surface forces (i.e., attraction and adhesion) of monolayer covered samples could be clearly discerned when only the surface group of the monolayer film was changed from -${\mathrm{CH}}_{3}$ to -${\mathrm{CF}}_{3}$.

An electrochemical immunoassay protocol for the simultaneous measurements of proteins, based on the use of different inorganic nanocrystal tracers is described. The multiprotein electrical detection capability is coupled to the amplification feature of electrochemical stripping transduction (to yield fmol detection limits) and with an efficient magnetic separation (to minimize nonspecific adsorption effects). The multianalyte electrical sandwich immunoassay involves a dual binding event, based on antibodies linked to the nanocrystal tags and magnetic beads. Carbamate linkage is used for conjugating the hydroxyl-terminated nanocrystals with the secondary antibodies. Each biorecognition event yields a distinct voltammetric peak, whose position and size reflects the identity and level, respectively, of the corresponding antigen. The concept is demonstrated for a simultaneous immunoassay of beta(2)-microglobulin, IgG, bovine serum albumin, and C-reactive protein in connection with ZnS, CdS, PbS, and CuS colloidal crystals, respectively. These nanocrystal labels exhibit similar sensitivity. Such electrochemical coding could be readily multiplexed and scaled up in multiwell microtiter plates to allow simultaneous parallel detection of numerous proteins or samples and is expected to open new opportunities for protein diagnostics and biosecurity.

International audience

Abstract It has been found that by taking transforms of both Gaussian and Lorentzian line shapes into polynomial representations, it is possible in many instances to determine peak position, peak intensity and the full‐width at half‐maximum (FWHM) from wide‐scan XPS spectra that have a low number of data points per electron‐volt. This approach was tested with several samples, ranging from an insulator, Al 2 O 3 , to an excellent conductor, sputter‐cleaned gold. Several data sets were constructed from narrow‐scan spectra with points selected about 1 eV apart to simulate wide‐scan spectra. Then, comparisons were made between values calculated with a non‐linear least‐squares fit that used all of the data points from a given spectrum, and the polynomial procedure with the simulated wide‐scan data. It was found that the peak positions usually agreed to within 0.1 eV between the methods. The FWHM and intensities agreed to ∼20%. The area ratios usually were within ∼10%. Comparisons between actual and simulated wide‐scan data showed similar area ratio agreement. However, there appeared to be a systematic difference in the peak position of ∼0.5 eV, which was due to the spectrometer used in this study. Thus, in many cases, estimates of the relative atomic amounts can be made with those results from the polynomial procedure that would be comparable to those obtained from non‐linear least‐squares analysis of narrow‐scan data. The effects of such factors as baseline, overlapping peaks, computational techniques and line shape on the use of the polynomial method are discussed also.

Viscosities eta and their temperature T and volume V dependences are reported for seven molecular liquids and polymers. In combination with literature viscosity data for five other liquids, we show that the superpositioning of relaxation times for various glass-forming materials when expressed as a function of TV(gamma), where the exponent gamma is a material constant, can be extended to the viscosity. The latter is usually measured to higher temperatures than the corresponding relaxation times, demonstrating the validity of the thermodynamic scaling throughout the supercooled and higher T regimes. The value of gamma for a given liquid principally reflects the magnitude of the intermolecular forces (e.g., steepness of the repulsive potential); thus, we find decreasing gamma in going from van der Waals fluids to ionic liquids. For some strongly H-bonded materials, such as low molecular weight polypropylene glycol and water, the superpositioning fails, due to the nontrivial change of chemical structure (degree of H bonding) with thermodynamic conditions.

There has been substantial interest in the use of saliva as a diagnostic medium for drugs of abuse because it can be obtained noninvasively. Although drugs of abuse have been investigated in saliva for more than a decade, the role of saliva remains uncertain. A clear picture is difficult to obtain because of variations in (1) the analytical methods used; (2) the dose regimen of subjects, which was either unknown or differed between studies; and (3) the elapsed time between drug intake and sample collection. This communication summarizes the studies on the quantitative determination of different drugs of abuse in saliva to elucidate the current status in this area. Marijuana, cocaine, phencyclidine, opiates, barbiturates, amphetamines, and diazepines (or their metabolites) have all been detected in saliva by various analytical methods, including immunoassay, gas chromatography/mass spectrometry, and thin layer chromatography. Initial studies with cocaine and phencyclidine suggest a correlation between saliva and plasma concentrations of these drugs, indicating a dynamic equilibrium between saliva and blood. Tetrahydrocannabinol, the active component in marijuana, on the other hand, does not appear to be transferred from plasma to saliva. However, tetrahydrocannabinol is sequestered in the buccal cavity during smoking and can be detected in saliva. These findings point to the potential role of saliva in the analysis of many illicit drugs. To clearly identify the role of saliva as a diagnostic medium for drugs of abuse, research efforts should be directed towards (1) performing systematic studies on correlations between saliva, blood, and urine and (2) determining the concentrations of drugs and their metabolites in saliva as a function of dose and time after intake.

Dielectric spectra of the polyalcohols sorbitol and xylitol were measured under isobaric pressures up to 1.8 GPa. At elevated pressure, the separation between the alpha and beta relaxation peaks is larger than at ambient pressure, enabling the beta relaxation times to be unambiguously determined. Taking advantage of this, we show that the Arrhenius temperature dependence of the beta relaxation time does not persist for temperatures above T(g). This result, consistent with inferences drawn from dielectric relaxation measurements at ambient pressure, is obtained directly, without the usual problematic deconvolution the beta and alpha processes.

We describe a simple self-limiting electroless deposition process whereby conformal, nanoscale iron oxide (FeO(x)) coatings are generated at the interior and exterior surfaces of macroscopically thick ( approximately 90 microm) carbon nanofoam paper substrates via redox reaction with aqueous K(2)FeO(4). The resulting FeO(x)-carbon nanofoams are characterized as device-ready electrode structures for aqueous electrochemical capacitors and they demonstrate a 3-to-7 fold increase in charge-storage capacity relative to the native carbon nanofoam when cycled in a mild aqueous electrolyte (2.5 M Li(2)SO(4)), yielding mass-, volume-, and footprint-normalized capacitances of 84 F g(-1), 121 F cm(-3), and 0.85 F cm(-2), respectively, even at modest FeO(x) loadings (27 wt %). The additional charge-storage capacity arises from faradaic pseudocapacitance of the FeO(x) coating, delivering specific capacitance >300 F g(-1) normalized to the content of FeO(x) as FeOOH, as verified by electrochemical measurements and in situ X-ray absorption spectroscopy. The additional capacitance is electrochemically addressable within tens of seconds, a time scale of relevance for high-rate electrochemical charge storage. We also demonstrate that the addition of borate to buffer the Li(2)SO(4) electrolyte effectively suppresses the electrochemical dissolution of the FeO(x) coating, resulting in <20% capacitance fade over 1000 consecutive cycles.