The authors describe the first enantioselective α-arylation of ketones with aryl triflates to provide access to enantioenriched quaternary stereocenters through use of chiral biarylphosphine-palladium and -nickel complexes. The combination of electron-rich aryl triflates and a palladium catalyst, and that of electron-poor aryl triflates and a nickel catalyst led to a series of α-arylations that occur with much higher enantioselectivity than the previously reported reactions of aryl bromides with other catalysts.
Metallic lithium (Li) is a promising anode candidate for high-energy-density rechargeable batteries because of its low redox potential and high theoretical capacity. However, its practical application is not imminent because of issues related to the dendritic growth of Li metal with repeated battery operation, which presents a serious safety concern. Herein, various aspects of the electrochemical deposition and stripping of Li metal are investigated with consideration of the reaction rate/current density, electrode morphology, and solid electrolyte interphase (SEI) layer properties to understand the conditions inducing abnormal Li growth. It is demonstrated that the irregular ( i.e., filamentary or dendritic) growth of Li metal mostly originates from local perturbation of the surface current density, which stems from surface irregularities arising from the morphology, defective nature of the SEI, and relative asymmetry in the deposition/stripping rates. Importantly, we find that the use of a stripping rate of Li metal that is slower than the deposition rate seriously aggravates the formation of disconnected Li debris from the irregularly grown Li metal. This finding challenges the conventional belief that high-rate stripping/plating of Li in an electrochemical cell generally results in more rapid cell failure because of the faster growth of Li metal dendrites. Figure 1
Describes the re‐establishment of a department of librarianship and information science at Bucharest University, Romania. Discusses some of the problems and dilemmas encountered and gives details of the curriculum and courses taught. Ends by assessing what has been achieved and outlining aims for the future.
Gamma-TiAl based alloys have recently received attention for potential elevated temperature applications in gas-turbine engines. However, although expected critical crack sizes for some targeted applications (e.g. gas-turbine engine blades) may be less than ∼500 μm, most fatigue-crack growth studies to date have focused on the behavior of large (on the order of a few millimeters) through-thickness cracks. Since successful implementation of damage-tolerant life-prediction methodologies requires that the fatigue properties be understood for crack sizes representative of those seen in service conditions, the present work is focused on characterizing the initiation and growth behavior of small (a∼25–300 μm) fatigue cracks in a γ-TiAl based alloy, of composition Ti–47Al–2Nb–2Cr–0.2B (at.%), with both duplex (average grain size of ∼17 μm) and refined lamellar (average colony size of ∼145 μm) microstructures. Results are compared to the behavior of large (a>5mm), through-thickness cracks from a previous study. Superior crack initiation resistance is observed in the duplex microstructure, with no cracks nucleating after up to 500 000 cycles at maximum stress levels (R=0.1) in excess of the monotonic yield stress, σ y. Comparatively, in the lamellar microstructure cracks nucleated readily at applied maximum stresses below the yield stress (85% σ y) after as few as 500 cycles. In terms of crack growth, measurements for small fatigue cracks in the duplex and lamellar microstructures showed that both microstructures have comparable intrinsic fatigue-crack growth resistance in the presence of small flaws. This observation contrasts previous comparisons of large-crack data, where the lamellar structure showed far superior fatigue-crack growth resistance than the duplex structure. Such “small-crack effects” are examined both in terms of similitude (i.e. crack tip shielding) and continuum (i.e. biased microstructural sampling) limitations of traditional linear elastic fracture mechanics.
