Publications

A micromechanical model is developed for grain bridging in monolithic ceramics. Specifically, bridge formation of a single, non-equiaxed grain spanning adjacent grains is addressed. A cohesive zone framework enables crack initiation and propagation along grain boundaries. The evolution of the bridge is investigated through a variance in both grain angle and aspect ratio. We propose that the bridging process can be partitioned into five distinct regimes of resistance: propagate, kink, arrest, stall, and bridge. Although crack propagation and kinking are well understood, crack arrest and subsequent “stall” have been largely overlooked. Resistance during the stall regime exposes large volumes of microstructure to stresses well in excess of the grain boundary strength. Bridging can occur through continued propagation or reinitiation ahead of the stalled crack tip. The driving force required to reinitiate is substantially greater than the driving force required to kink. In addition, the critical driving force to reinitiate is sensitive to grain aspect ratio but relatively insensitive to grain angle. The marked increase in crack resistance occurs prior to bridge formation and provides an interpretation for the rapidly rising resistance curves which govern the strength of many brittle materials at realistically small flaw sizes.

Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Au x Pd1−x (x = 0, 0.25, 0.5, 0.75, 1) nanoparticle (NP) catalysts (8–11 nm) were synthesized by a one-pot reaction strategy using colloidal chemistry. XPS depth profiles with variable X-ray energies and scanning transmission electron microscopy (STEM) analyses show that the as-synthesized Au x Pd1−x (x = 0.25 and 0.5) bimetallic NPs have gradient alloy structures with Au-rich cores and Pd-rich shells. The evolution of composition and structure in the surface region corresponding to a mean free path of 0.6–0.8 nm (i.e., 2–3 layers to the bulk from the particle surface) was studied with ambient pressure X-ray photoelectron spectroscopy (AP-XPS) under CO/O2 reaction in the Torr pressure regime. Under the reaction conditions of 80 mTorr CO and 200 mTorr O2 at 200 °C, the surface region of Au0.75Pd0.25 NP is Au-rich (~70% by Au). All Au x Pd1−x (x = 0.25, 0.5, 0.75) NP catalysts have higher turnover rates for the model CO/O2 reaction than pure Pd and pure Au NPs. The Pd-rich Au0.25Pd0.75 NPs show the highest turnover rates and the Pd-rich Au0.5Pd0.5 NPs the lowest turnover rates at 200 °C. Interestingly, the Au-rich Au0.75Pd0.25 NPs exhibit steady-state turnover rates which are intermediate to those of the Pd-rich bimetallic nanoparticles.

CaFe₂O₄-type sodium postspinels (Na-CFs), with Na⁺ occupying tunnel sites, are of interest as prospective battery electrodes. While many compounds of this structure type require high-pressure synthesis, several compounds are known to form at ambient pressure. Here we report a large expansion of the known Na-CF phase space at ambient pressure, having successfully synthesized NaCrTiO₄, NaRhTiO₄, NaCrSnO₄, NaInSnO₄, NaMg_0.5Ti_1.5O₄, NaFe_0.5Ti_1.5O₄, NaMg_0.5Sn_1.5O₄, NaMn_0.5Sn_1.5O₄, NaFe_0.5Sn_1.5O₄, NaCo_0.5Sn_1.5O₄, NaNi_0.5Sn_1.5O₄, NaCu_0.5Sn_1.5O₄, NaZn_0.5Sn_1.5O₄, NaCd_0.5Sn_1.5O₄, NaSc_1.5Sb_0.5O₄, Na_1.16In_1.18Sb_0.66O₄, and several solid solutions. In contrast to earlier reports, even cations that are strongly Jahn-Teller active (e.g., Mn³⁺ and Cu²⁺) can form Na-CFs at ambient pressure when combined with Sn⁴⁺ rather than with the smaller Ti⁴⁺. Order and disorder are probed at the average and local length-scales with synchrotron powder X-ray diffraction and solid-state NMR spectroscopy. Strong ordering of framework cations between the two framework sites is not observed, except in the case of Na_1.16In_1.18Sb_0.66O₄. This compound is the first example of an Na-CF that contains Na⁺ in both the tunnel and framework sites, reminiscent of Li-rich spinels. Trends in the thermodynamic stability of the new compounds are explained on the basis of crystal-chemistry and density functional theory (DFT). Further DFT calculations examine the relative stability of the CF versus spinel structures at various degrees of sodium extraction in the context of electrochemical battery reactions.

We report three design principles for obtaining extra-large pore openings and cages in the metal-organic analogues of inorganic zeolites, zeolitic imidazolate frameworks (ZIFs). Accordingly, we prepared a series of 15 ZIFs, members of which have the largest pore opening (22.5 Å) and the largest cage size (45.8 Å) known for all porous tetrahedral structures. The key parameter allowing us to access these exceptional ZIFs is what we define as the steric index (δ), which is related to the size and shape of the imidazolate linkers employed in the synthesis. The three principles are based on using multiple linkers with specific range and ratios of δ to control the size of rings and cages from small to large, and therefore are universally applicable to all existing ZIFs. The ZIF with the largest cage size (ZIF-412) shows the best selectivity of porous materials tested toward removal of octane and p-xylene from humid air.

We synthesized two isoreticular furan-based metal–organic frameworks (MOFs), MOF-LA2-1(furan) and MOF-LA2-2(furan) with rod-like secondary building units (SBUs) featuring 1D channels, as sorbents for atmospheric water harvesting (LA = long arm). These aluminum-based MOFs demonstrated a combination of high water uptake and stability, exhibiting working capacities of 0.41 and 0.48 g of water per g of MOF (under isobaric conditions of 1.70 kPa), respectively. Remarkably, both MOFs showed negligible loss in water uptake after 165 adsorption-desorption cycles. These working capacities rival those of MOF-LA2-1(pyrazole), which has a working capacity of 0.55 g of water per g of MOF. The current MOFs stand out for their high water stability as evidenced by 165 cycles of water uptake and release. MOF-LA2-2(furan) is the first aluminum MOF to employ a double 'long arm' extension strategy, confirmed through single-crystal X-ray diffraction (SCXRD). The MOFs were synthesized using a straightforward synthesis route. This study offers valuable insights into designing durable, water-stable MOFs and underscores their potential for efficient water harvesting.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

We consider the problem of separating consistency-related safety properties from availability and durability in distributed data stores via the application of a "bolt-on" shim layer that upgrades the safety of an underlying general-purpose data store. This shim provides the same consistency guarantees atop a wide range of widely deployed but often inflexible stores. As causal consistency is one of the strongest consistency models that remain available during system partitions, we develop a shim layer that upgrades eventually consistent stores to provide convergent causal consistency. Accordingly, we leverage widely deployed eventually consistent infrastructure as a common substrate for providing causal guarantees. We describe algorithms and shim implementations that are suitable for a large class of application-level causality relationships and evaluate our techniques using an existing, production-ready data store and with real-world explicit causality relationships.