In Situ Bottom-up Synthesis of Porphyrin-Based Covalent Organic Frameworks.

Synthesis and processing of two- or three-dimensional covalent organic frameworks (COFs) have been limited by solvent intractability and sluggish condensation kinetics. Here, we report on the electrochemical deposition of poly(5,10,15,20-tetrakis(4-aminophenyl)porphyrin)-covalent organic frameworks (POR-COFs) via formation of phenazine linkages. By adjusting the synthetic parameters, we demonstrate the rapid and bottom-up synthesis of COF dendrites. Both experiment and density functional theory underline the prominent role of pyridine, not only as a polymerization promoter but as a stabilizing sublattice, cocrystallizing with the framework. The crucial role of pyridine in dictating the structural properties of such a cocrystal (Py-POR-COF) is discussed. Also, a structure-to-function relationship for this class of materials, governing their electrocatalytic activity for the oxygen reduction reaction in alkaline media, is reported.

Fatigue-resistant high-performance elastocaloric materials made by additive manufacturing.

Elastocaloric cooling, a solid-state cooling technology, exploits the latent heat released and absorbed by stress-induced phase transformations. Hysteresis associated with transformation, however, is detrimental to efficient energy conversion and functional durability. We have created thermodynamically efficient, low-hysteresis elastocaloric cooling materials by means of additive manufacturing of nickel-titanium. The use of a localized molten environment and near-eutectic mixing of elemental powders has led to the formation of nanocomposite microstructures composed of a nickel-rich intermetallic compound interspersed among a binary alloy matrix. The microstructure allowed extremely small hysteresis in quasi-linear stress-strain behaviors-enhancing the materials efficiency by a factor of four to seven-and repeatable elastocaloric performance over 1 million cycles. Implementing additive manufacturing to elastocaloric cooling materials enables distinct microstructure control of high-performance metallic refrigerants with long fatigue life.

Tough and strong porous bioactive glass-PLA composites for structural bone repair.

Bioactive glass scaffolds have been used to heal small contained bone defects but their application to repairing structural bone is limited by concerns about their mechanical reliability. In the present study, the addition of an adherent polymer layer to the external surface of strong porous bioactive glass (13-93) scaffolds was investigated to improve their toughness. Finite element modeling (FEM) of the flexural mechanical response of beams composed of a porous glass and an adherent polymer layer predicted a reduction in the tensile stress in the glass with increasing thickness and elastic modulus of the polymer layer. Mechanical testing of composites with structures similar to the models, formed from 13-93 glass and polylactic acid (PLA), showed trends predicted by the FEM simulations but the observed effects were considerably more dramatic. A PLA layer of thickness -400 µm, equal to -12.5% of the scaffold thickness, increased the load-bearing capacity of the scaffold in four-point bending by ~50%. The work of fracture increased by more than 10,000%, resulting in a non-brittle mechanical response. These bioactive glass-PLA composites, combining bioactivity, high strength, high work of fracture and an internal architecture shown to be conducive to bone infiltration, could provide optimal implants for healing structural bone defects.

Creation of bioactive glass (13-93) scaffolds for structural bone repair using a combined finite element modeling and rapid prototyping approach.

There is a clinical need for synthetic bioactive materials that can reliably repair intercalary skeletal tissue loss in load-bearing bones. Bioactive glasses have been investigated as one such material but their mechanical response has been a concern. Previously, we created bioactive silicate glass (13-93) scaffolds with a uniform grid-like microstructure which showed a compressive strength comparable to human cortical bone but a much lower flexural strength. In the present study, finite element modeling (FEM) was used to re-design the scaffold microstructure to improve its flexural strength without significantly lowering its compressive strength and ability to support bone infiltration in vivo. Then scaffolds with the requisite microstructures were created by a robotic deposition method and tested in four-point bending and compression to validate the FEM simulations. In general, the data validated the predictions of the FEM simulations. Scaffolds with a porosity gradient, composed of a less porous outer region and a more porous inner region, showed a flexural strength (34±5MPa) that was more than twice the value for the uniform grid-like microstructure (15±5MPa) and a higher compressive strength (88±20MPa) than the grid-like microstructure (72±10MPa). Upon implantation of the scaffolds for 12weeks in rat calvarial defects in vivo, the amount of new bone that infiltrated the pore space of the scaffolds with the porosity gradient (37±16%) was similar to that for the grid-like scaffolds (35±6%). These scaffolds with a porosity gradient that better mimics the microstructure of human long bone could provide more reliable implants for structural bone repair.

Effect of vacancy defects on generalized stacking fault energy of fcc metals.

Molecular dynamics (MD) and density functional theory (DFT) studies were performed to investigate the influence of vacancy defects on generalized stacking fault (GSF) energy of fcc metals. MEAM and EAM potentials were used for MD simulations, and DFT calculations were performed to test the accuracy of different common parameter sets for MEAM and EAM potentials in predicting GSF with different fractions of vacancy defects. Vacancy defects were placed at the stacking fault plane or at nearby atomic layers. The effect of vacancy defects at the stacking fault plane and the plane directly underneath of it was dominant compared to the effect of vacancies at other adjacent planes. The effects of vacancy fraction, the distance between vacancies, and lateral relaxation of atoms on the GSF curves with vacancy defects were investigated. A very similar variation of normalized SFEs with respect to vacancy fractions were observed for Ni and Cu. MEAM potentials qualitatively captured the effect of vacancies on GSF.