Compressive deformation and failure of trabecular structures in a turtle shell.

Turtle shells comprising of cortical and trabecular bones exhibit intriguing mechanical properties. In this work, compression tests were performed using specimens made from the carapace of Kinixys erosa turtle. A combination of imaging techniques and mechanical testing were employed to examine the responses of hierarchical microstructures of turtle shell under compression. Finite element models produced from microCT-scanned microstructures and analytical foam structure models were then used to elucidate local responses of trabecular bones deformed under compression. The results reveal the contributions from micro-strut bending and stress concentrations to the fractural mechanisms of trabecular bone structures. The porous structures of turtle shells could be an excellent prototype for the bioinspired design of deformation-resistant structures. STATEMENT OF SIGNIFICANCE: In this study, a combination of analytical, computational models and experiments is used to study the underlying mechanisms that contribute to the compressive deformation of a Kinixys erosa turtle shell between the nano-, micro- and macro-scales. The proposed work shows that the turtle shell structures can be analyzed as sandwich structures that have the capacity to concentrate deformation and stresses within the trabecular bones, which enables significant energy absorption during compressive deformation. Then, the trends in the deformation characteristics and the strengths of the trabecular bone segments are well predicted by the four-strut model, which captures the effects of variations in strut length, thickness and orientation that are related to microstructural uncertainties of the turtle shells. The above results also suggest that the model may be used to guide the bioinspired design of sandwich porous structures that mimic the properties of the cortical and trabecular bone segments of turtle shells under a range of loading conditions.

Synthesis and Characterization of Alkylamine-Functionalized Si(111) for Perovskite Adhesion With Minimal Interfacial Oxidation or Electronic Defects.

We investigated synthetic strategies for the functionalization of Si(111) surfaces with organic species containing amine moieties. We employed the functionalized surfaces to chemically "glue" perovskites to silicon with efficient electron transfer and minimal oxidation leading to deleterious recombination at the silicon substrate. A two-step halogenation-alkylation reaction produced a mixed allyl-methyl monolayer on Si(111). Subsequent reactions utilized multiple methods of brominating the allyl double bond including reaction with HBr in acetic acid, HBr in THF, and molecular bromine in dichloromethane. Reaction with ammonia in methanol effected conversion of the bromide to the amine. X-ray photoelectron spectroscopy (XPS) quantified chemical states and coverages, transient-microwave photoconductivity ascertained photogenerated carrier lifetimes, atomic force microscopy (AFM) quantified perovskite-silicon adhesion, and nonaqueous photoelectrochemistry explored solar-energy-conversion performance. The HBr bromination followed by the amination yielded a surface with ∼10% amine sites on the Si(111) with minimal oxide and surface recombination velocity values below 120 cm s-1, following extended exposures to air. Importantly, conversion of amine sites to ammonium and deposition of methylammonium lead halide via spin coating and annealing did not degrade carrier lifetimes. AFM experiments quantified adhesion between perovskite films and alkylammonium-functionalized or native-oxide silicon surfaces. Adhesion forces/interactions between the perovskite and the alkylammonium-functionalized films were comparable to the interaction between the perovskite and native-oxide silicon surface. Photoelectrochemistry of perovskite thin films on alkylammonium-functionalized n+-Si showed significantly higher Voc than n+-Si with a native oxide when in contact with a nonaqueous ferrocene+/0 redox couple. We discuss the present results in the context of utilizing molecular organic recognition to attach perovskites to silicon utilizing organic linkers so as to inexpensively modify silicon for future tandem-junction photovoltaics.