Plasmonic dimer antennas for surface enhanced Raman scattering

Electron beam induced deposition (EBID) has recently been developed into a method to directly write optically active three-dimensional nanostructures. For this purpose a metal-organic precursor gas (here dimethyl-gold(III)-acetylacetonate) is introduced into the vacuum chamber of a scanning electron microscope where it is cracked by the focused electron beam. Upon cracking the aforementioned precursor gas, 3D deposits are realized, consisting of gold nanocrystals embedded in a carbonaceous matrix. The carbon content in the deposits hinders direct plasmonic applications. However, it is possible to activate the deposited nanostructures for plasmonics by coating the EBID structures with a continuous silver layer of a few nanometers thickness. Within this silver layer collective motions of the free electron gas can be excited. In this way, EBID structures with their intriguing precision at the nanoscale have been arranged in arrays of free-standing dimer antenna structures with nanometer sized gaps between the antennas that face each other with an angle of 90°. These dimer antenna ensembles can constitute a reproducibly manufacturable substrate for exploiting the surface enhanced Raman effect (SERS). The achieved SERS enhancement factors are of the order of 10? for the incident laser light polarized along the dimer axes. To prove the signal enhancement in a Raman experiment we used the dye methyl violet as a robust test molecule. In future applications the thickness of such a silver layer on the dimer antennas can easily be varied for tuning the plasmonic resonances of the SERS substrate to match the resonance structure of the analytes to be detected.     

Multiscale modeling reveals poisoning mechanisms of MgO-supported Au clusters in CO oxidation

Catalyst deactivation mechanisms on MgO-supported Au(6) clusters are studied for the CO oxidation reaction via first-principle kinetic Monte Carlo simulations and shown to depend on support vacancies. In defect-poor MgO or in the presence of a Mg vacancy, O(2) does not bind to the clusters and the catalyst is poisoned by CO. On Au clusters interacting with O vacancies of the support, O(2) can be chemisorbed and transient activity is observed. In this case, an unexpected catalyst "breathing" mechanism (restructuring) leads to carbonate formation and catalyst deactivation, rationalizing several experimental observations. Our study underscores the importance of the cluster's charge state and dynamics on catalytic activity.     

The Formation of Calcified Nanospherites during Micropetrosis Represents a Unique Mineralization Mechanism in Aged Human Bone

Osteocytes—the central regulators of bone remodeling—are enclosed in a network of microcavities (lacunae) and nanocanals (canaliculi) pervading the mineralized bone. In a hitherto obscure process related to aging and disease, local plugs in the lacuno‐canalicular network disrupt cellular communication and impede bone homeostasis. By utilizing a suite of high‐resolution imaging and physics‐based techniques, it is shown here that the local plugs develop by accumulation and fusion of calcified nanospherites in lacunae and canaliculi (micropetrosis). Two distinctive nanospherites phenotypes are found to originate from different osteocytic elements. A substantial deviation in the spherites' composition in comparison to mineralized bone further suggests a mineralization process unlike regular bone mineralization. Clearly, mineralization of osteocyte lacunae qualifies as a strong marker for degrading bone material quality in skeletal aging. The understanding of micropetrosis may guide future therapeutics toward preserving osteocyte viability to maintain mechanical competence and fracture resistance of bone in elderly individuals.     

Constitutive equations for the nonlinear elastic response of rubbers

Summary A constitutive model is derived for the elastic behavior of rubbers at three-dimensional deformations with finite strains. An elastomer is thought of as an incompressible network of flexible chains bridged by permanent junctions that move affinely with the bulk medium. The constraints imposed by surrounding macromolecules on configurations of an individual chain are introduced by combining the Flory–Erman and Erman–Monnerie approaches. To describe inter-chain interactions in a tractable way, the conventional picture of a tube where a chain is confined is replaced by geometrical restrictions on the positions of its ends and center of mass. The constraints on the chain ends are formulated within the traditional Flory concept, whereas those on the position of center of mass are described following the Ronca–Allegra scenario. Stress–strain relations for a network of constrained chains are derived by using the laws of thermodynamics. The constitutive equations involve four adjustable parameters with transparent physical meaning. The material constants are found by fitting experimental data on elastomers at uniaxial and equi-biaxial tensions and pure shear. It is demonstrated that (i) the model provides an acceptable prediction of stresses in a test with one deformation mode, when its parameters are found by matching observations in an experiment with another mode, and (ii) material constants are affected by chemical composition of elastomers in a physically plausible way.     

Whipple shield performance in the shatter regime

A series of hypervelocity impact tests have been performed on aluminum alloy Whipple shields to investigate failure mechanisms and performance limits in the shatter regime. Test results demonstrated a more rapid increase in performance than predicted by the latest iteration of the JSC Whipple shield ballistic limit equation (BLE) following the onset of projectile fragmentation. This increase in performance was found to level out between 4.0 and 5.0 km/s, with a subsequent decrease in performance for velocities up to 5.6 km/s. For a detached spall failure criterion, the failure limit was found to continually decrease up to a velocity of 7.0 km/s, substantially varying from the BLE, while for perforation-based failure an increase in performance was observed. An existing phenomenological ballistic limit curve was found to provide a more accurate reproduction of shield behavior that the BLE, prompting an investigation of appropriate models to replace linear interpolation in shatter regime. A largest fragment relationship was shown to provide accurate predictions up to 4.3 km/s, which was extended to the incipient melt limit (5.6 km/s) based on an assumption of no additional fragmentation. Alternate models, including a shock enhancement approach and debris cloud cratering model are discussed as feasible alternatives to the proposed curve in the shatter regime, due to conflicting assumptions and difficulties in extrapolating the current approach to oblique impact. These alternate models require further investigation.     

Toward local growth of individual nanowires on three-dimensional microstructures by using a minimally invasive catalyst templating method

We present a novel minimally invasive postprocessing method for catalyst templating based on focused charged particle beam structuring, which enables a localized vapor-liquid-solid (VLS) growth of individual nanowires on prefabricated three-dimensional micro- and nanostructures. Gas-assisted focused electron beam induced deposition (FEBID) was used to deposit a SiO(x) surface layer of about 10 × 10 μm(2) on top of a silicon atomic force microscopy cantilever. Gallium focused ion beam (FIB) milling was used to make a hole through the SiO(x) layer into the underlying silicon. The hole was locally filled with a gold catalyst via FEBID using either Me(2)Au(tfac) or Me(2)Au(acac) as precursor. Subsequent chemical vapor deposition (CVD)-induced VLS growth using a mixture of SiH(4) and Ar resulted in individual high quality crystalline nanowires. The process, its yield, and the resulting angular distribution/crystal orientation of the silicon nanowires are discussed. The presented combined FIB/FEBID/CVD-VLS process is currently the only proven method that enables the growth of individual monocrystalline Si nanowires on prestructured substrates and devices.     

The effect of annealing on the elastoplastic and viscoelastic responses of isotactic polypropylene

Observations are reported on isotactic polypropylene (i) in a series of tensile tests with a constant strain rate on specimens annealed for 24 h at various temperatures in the range from 110 to 150 °C, (ii) in two series of creep tests in the subyield region of deformations on samples not subjected to thermal treatment and on specimens annealed at 140 °C, and (iii) in a series of tensile relaxation tests on non-annealed specimens. Constitutive equations are derived for the elastoplastic and non-linear viscoelastic responses of semicrystalline polymers. A polymer is treated as an equivalent transient network of macro-molecules bridged by junctions (physical cross-links, entanglements and lamellar blocks). The network is assumed to be highly heterogeneous, and it is thought of as an ensemble of meso-regions with different activation energies for separation of strands from temporary nodes. The elastoplastic behavior is modelled as sliding of junctions in meso-domains with respect to their reference positions driven by macro-deformation. The viscoelastic response is attributed to detachment of active strands from temporary junctions and attachment of dangling chains to the network. Constitutive equations for isothermal deformations with small strains are derived by using the laws of thermodynamics. Adjustable parameters in the stress–strain relations are found by fitting the experimental data.