Switchable Explosives: Performance Tuning of Fluid-Activated High Explosive Architectures.

We present our discovery of switchable high explosives (HEs) as a new class of energetic material that cannot detonate unless filled with a fluid. The performance of fluid-filled additive-manufactured HE lattices is herein evaluated by analysis of detonation velocity and Gurney energy. The Gurney energy of the unfilled lattice was 98% lower than that of the equivalent water-filled lattice and changing the fluid mechanical properties allowed tuning of the Gurney energy and detonation velocity by 8.5% and 13.4%, respectively. These results provide, for the first time since the development of HEs, a method to completely remove the hazard of unplanned detonations during storage and transport.

Lanthanide Complexes of Bis(tetrazolato)amine: A Route to Lanthanide Nitride Foams.

Metal nitrides are strong refractory ceramic materials known for applications in the coatings, catalysis, and semiconductor industries. Lanthanide nitrides are difficult to prepare in high purity and often require high temperatures and sophisticated equipment. In this work, we present an approach to the synthesis of high-purity f-element nitrides through the use of simple lanthanide salts and the nitrogen-rich ligand 5,5'-bis(1H-tetrazolyl)amine (H2BTA) to form lanthanide complexes of 5,5'-bis(tetrazolato)amine (BTA2-). We have demonstrated that, when dehydrated, these types of complexes undergo a self-sustained combustion reaction under an inert atmosphere to yield nanostructured f-element nitride foams for lanthanum and cerium. The synthesis, characterization, and single-crystal X-ray crystallography of the BTA2- complexes of lanthanum, cerium, praseodymium, neodymium, and europium are also discussed.

Kläui ligand thin films for rapid plutonium analysis by alpha spectrometry.

As part of a nuclear forensics capability, rapid and effective methods to analyze for plutonium and other actinide metals are needed. A key requirement of these methods is that they afford a high chemical yield while still providing isotopic information necessary for forensic evaluation. Toward this objective, a new method for binding plutonium for analysis by alpha spectrometry has been developed. Thin films of Kläui-type tripodal oxygen donor ligands were prepared by spin-casting solutions onto glass substrates. Three different ligands were evaluated for plutonium binding, and the best results were obtained using the ethyl-substituted complex Na[Cp*Co(P(O)(OEt)2)3], which bound 80-88% of the dissolved Pu under equilibrium conditions. The thin films are simple and inexpensive to prepare and exhibit excellent alpha spectral resolution, having line widths of ~33 keV. The method has been successfully applied to analyze for plutonium in both an archived nuclear debris sample and a certified environmental soil sample. The results obtained from the soil analysis are in good agreement with the certified values, demonstrating the effectiveness of the method for rapid plutonium analysis.

Imaging high jitter, very fast phenomena: A remedy for shutter lag.

Dielectric breakdown is an example of a natural phenomenon that occurs on very short time scales, making it incredibly difficult to capture optical images of the process. Event initiation jitter is one of the primary challenges, as even a microsecond of jitter time can cause the imaging attempt to fail. Initial attempts to capture images of dielectric breakdown using a gigahertz frame rate camera and an exploding bridge wire initiation were stymied by high initiation jitter. Subsequently, a novel optical delay line apparatus was developed in order to effectively circumvent the jitter and reliably image dielectric breakdown. The design and performance of the optical delay line apparatus are presented. The optical delay line increased the image capture success rate from 25% to 94% while also permitting enhanced temporal resolution and has application in imaging other high-jitter, extremely fast phenomena.

Monolithic Nanoporous Gold Foams with Catalytic Activity for Chemical Vapor Deposition Growth of Carbon Nanostructures.

While bulk gold is generally considered to be a catalytically inactive material, nanostructured forms of gold can in fact be highly catalytically active. However, few methods exist for preparing high-purity macroscopic forms of catalytically active gold. In this work, we describe the synthesis of catalytically active macroscopic nanoporous gold foams via combustion synthesis of gold bis(tetrazolato)amine complexes. The resulting metallically pure porous gold nanoarchitectures exhibit bulk densities of <0.1 g/cm3 and Brunauer-Emmett-Teller (BET) surface areas as high as 10.9 m2/g, making them among the lowest-density and highest-surface-area monolithic forms of gold produced to date. Thanks to the presence of a highly nanostructured gold surface, such gold nanofoams have also been found to be highly catalytically active toward thermal chemical vapor deposition (CVD) growth of carbon nanotubes, providing a novel method for direct synthesis of carbon nanostructures on macroscopic gold substrates. In contrast, analogous copper nanofoams were found to be catalytically inactive toward the growth of graphitic nanostructures under the same synthesis conditions, highlighting the unusually high catalytic propensity of this form factor of gold. The combustion synthesis process described herein represents a never-wet approach for directly synthesizing macroscopic catalytically active gold. Unlike sol-gel and dealloying approaches, combustion synthesis eliminates the time-consuming diffusion-mediated steps associated with previous methods and offers multiple degrees of freedom for tuning morphology, electrical conductivity, and mechanical properties.

Multicolor light-emitting diodes based on semiconductor nanocrystals encapsulated in GaN charge injection layers.

Numerous technologies including solid-state lighting, displays, and traffic signals can benefit from efficient, color-selectable light sources that are driven electrically. Semiconductor nanocrystals are attractive types of chromophores that combine size-controlled emission colors and high emission efficiencies with excellent photostability and chemical flexibility. Applications of nanocrystals in light-emitting technologies, however, have been significantly hindered by difficulties in achieving direct electrical injection of carriers. Here we report the first successful demonstration of electroluminescence from an all-inorganic, nanocrystal-based architecture in which semiconductor nanocrystals are incorporated into a p-n junction formed from GaN injection layers. The critical step in the fabrication of these nanocrystal/GaN hybrid structures is the use of a novel deposition technique, energetic neutral atom beam lithography/epitaxy, that allows for the encapsulation of nanocrystals within a GaN matrix without adversely affecting either the nanocrystal integrity or its luminescence properties. We demonstrate electroluminescence (injection efficiencies of at least 1%) in both single- and two-color regimes using structures comprising either a single monolayer or a bilayer of nanocrystals.

A mechanistic investigation of the carbon-carbon bond cleavage of aryl and alkyl cyanides using a cationic RhIII silyl complex.

Cationic Rh(III) complex [Cp(PMe(3))Rh(SiPh(3))(CH(2)Cl(2))]BAr(4)' (1) activates the carbon-carbon bond of aryl and alkyl cyanides (R-CN, where R = Ph, (4-(CF(3))C(6)H(4)), (4-(OMe)C(6)H(4)), Me, (i)Pr, (t)Bu) to produce complexes of the general formula [Cp*(PMe(3))Rh(R)(CNSiPh(3))]BAr(4)'. With the exception of the (t)BuCN case, every reaction proceeds at room temperature (t(1/2) < 1 h for aryl cyanides, t(1/2) < 14 h for alkyl cyanides). A general mechanism is presented on the basis of (1) an X-ray crystal structure determination of an intermediate isolated from the reaction involving 4-methoxybenzonitrile and (2) kinetic studies performed on the C-C bond cleavage of para-substituted aryl cyanides. Initial formation of an eta(1)-nitrile species is observed, followed by conversion to an eta(2)-iminoacyl intermediate, which was observed to undergo migration of R (aryl or alkyl) to rhodium to form the product [Cp*(PMe(3))Rh(R)(CNSiPh(3))]BAr(4)'.