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Analytical electron microscopy was used to examine the grain boundary chemistry in boron carbide containing Al-O-rich phases at triple junctions. In this study, SiO2, Al2O3, and B2O3 additives were used to synthesize an aluminoborosilicate glass on the grain boundaries with the long-term goal to enhance fracture resistance. Nanolayer films were not observed using high-angle annular dark field imaging; however, energy-dispersive spectroscopy quantification revealed grain boundaries with varying excess of Si and Al. Overall, it was concluded variations in grain boundary chemistry depend upon the intrinsic grain boundary character and spatial heterogeneity of the oxide additives.

Accurate quantification of light elements which produce only soft X-ray lines via X-ray energy dispersive spectrometry (XEDS) has been traditionally difficult due to poor X-ray emission and detector efficiencies at low energies and significant X-ray absorption effects. The ζ-factor microanalysis method enables one to correct for these shortcomings; however, ζ-factor microanalysis has not yet been thoroughly applied to inorganic materials which are entirely or mostly composed of light elements such as boron carbide, boron nitride, or boron suboxide. This work successfully extended ζ-factor microanalysis to boron-rich ceramics and accurately determined stoichiometries of multiple boron carbides and measured grain boundary compositions of a boron carbide mixed with additives consisting of rare-earth ions. Various strategies were employed to experimentally determine a full range of ζ-factors and measurements were validated using materials of known composition including silicon hexaboride and silicon carbide. Overall, this work has shown that XEDS is a viable technique for light element quantification in (scanning) transmission electron microscopy, in terms of both the accuracy and precision, which is comparable or superior to the complementary electron energy loss spectrometry.

Boron-based ceramics are appealing for lightweight applications in both vehicle and personnel protection, stemming from their combination of high hardness, high elastic modulus, and low density as compared to other ceramics and metal alloys. However, the performance of these ceramics and ceramic composites is lacking because of their inherent low fracture toughness and reduced strength under high-velocity threats. The objective of the present article is to briefly discuss both the challenges and the state of the art in experimental and computational approaches for engineering grain boundaries in boron-based armor ceramics, focusing mainly on boron carbide (B4C) and boron suboxide (B6O). The experimental challenges involve processing these ceramics at full density while trying to promote microstructure features such as intergranular films to improve toughness during shock. Many of the computational challenges for boron-based ceramics stem from their complex crystal structure which has hitherto complicated the exploration of grain boundaries and interfaces. However, bridging the gaps between experimental and computational studies at multiple scales to engineer grain boundaries in these boron-based ceramics may hold the key to maturing these material systems for lightweight defense applications.

The well-documented formation of amorphous bands in boron carbide (B4C) under contact loading has been identified in the literature as one of the possible mechanisms for its catastrophic failure. To mitigate amorphization, Si-doping was suggested by an earlier computational work, which was further substantiated by an experimental study. However, there have been discrepancies between theoretical and experimental studies, about Si replacing atom/s in B12 icosahedra or the C-B-C chain. Dense single phase Si-doped boron carbide was produced through a conventional scalable route. A powder mixture of SiB6, B4C, and amorphous boron was reactively sintered, yielding a dense single phase Si-doped boron carbide material. A combined analysis of Rietveld refinement on XRD pattern coupled with electron density difference Fourier maps and DFT simulations were performed in order to investigate the location of Si atoms in the boron carbide lattice. Si atoms occupy an interstitial position, between the icosahedra and the chain. These Si atoms are bonded to the chain end C atoms, which result in a kinked chain. Additionally, these Si atoms are also bonded to the neighboring equatorial B atom of the icosahedra, which is already bonded to the C atom of the chain, forming a bridge like structure. Owing to this bonding, Si is anticipated to stabilize the icosahedra through electron donation, which is expected to help in mitigating stress-induced amorphization. Possible supercell structures are suggested along with the most plausible structure for Si-doped boron carbide.

We describe a novel approach for coupling pristine graphene with superparamagnetic iron oxide nanoparticles to create dispersed, magnetically responsive hybrids. The magnetic iron oxide (Fe3O4) nanoparticles are synthesized by a co-precipitation method using ferric (Fe3+) and ferrous (Fe2+) salts and then grafted with polyvinylpyrrolidone (PVP). These PVP-grafted Fe3O4 nanoparticles are then used to stabilize colloidal graphene in water. The PVP branches non-covalently attach to the surface of the pristine graphene sheets without functionalization or defect creation. These Fe3O4–graphene hybrids are stable against aggregation and are highly responsive to external magnetic fields. These hybrids can be freeze-dried to a powder or magnetically separated from solution and still easily redisperse while retaining magnetic functionality. At all stages of synthesis, the Fe3O4–graphene hybrids display no coercivity after being brought to magnetic saturation, confirming superparamagnetic properties. Microscopy and light scattering data confirm the presence of pristine graphene sheets decorated with Fe3O4 nanoparticles. These materials show promise for multifunctional polymer composites as well as biomedical applications and environmental remediation.

Solid-state shock-wave propagation is strongly nonequilibrium in nature and hence rate dependent. Using high-power pulsed-laser-driven shock compression, unprecedented high strain rates can be achieved; here we report the directional amorphization in boron carbide polycrystals. At a shock pressure of 45∼50 GPa, multiple planar faults, slightly deviated from maximum shear direction, occur a few hundred nanometers below the shock surface. High-resolution transmission electron microscopy reveals that these planar faults are precursors of directional amorphization. It is proposed that the shear stresses cause the amorphization and that pressure assists the process by ensuring the integrity of the specimen. Thermal energy conversion calculations including heat transfer suggest that amorphization is a solid-state process. Such a phenomenon has significant effect on the ballistic performance of B4C.

While nanocrystalline diamond is quickly becoming one of the most widely studied nanomaterials, achieving a large fraction of diamond nanoparticles in a polymer coating has been an unresolved problem. In this work, polymer nano- and microfibers containing high loadings of 5 nm diamond particles (up to 80 wt % in polyacrylonitrile and 40% in polyamide 11) have been demonstrated using electrospun nanofibers as a delivery vehicle. The electrospun nanofibers with a high load of nanodiamond in the polymers were fused into thin transparent films, which had high mechanical properties; an improvement of 4 times for the Young's modulus and 2 times for the hardness was observed already at 20% nanodiamond in polyamide 11. These films can provide UV protection and scratch resistance to a variety of surfaces, especially in applications where a combination of mechanical, thermal, and dielectric properties is required.

Multifunctional structural batteries and supercapacitors have the potential to improve performance and efficiency in advanced lightweight systems. A critical requirement is a structural electrolyte with superior multifunctional performance. We present here structural electrolytes prepared by the integration of liquid electrolytes with structural epoxy networks. Two distinct approaches were investigated: direct blending of an epoxy resin with a poly(ethylene-glycol) (PEG)- or propylene carbonate (PC)-based liquid electrolyte followed by in-situ cure of the resin; and formation of a porous neat epoxy sample followed by backfill with a PC-based electrolyte. The results show that in situ cure of the electrolytes within the epoxy network does not lead to good multifunctional performance due to a combination of plasticization of the structural network and limited percolation of the liquid network. In contrast, addition of a liquid electrolyte to a porous monolith results in both good stiffness and high ionic conductivity that approach multifunctional goals. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42681.