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A major challenge in synthesizing strong and tough protein fibers based on spider silk motifs is understanding the coupling between protein sequence and the postspin drawing process. We clarify how drawing-induced elongational force affects ordering, chain extension, interchain contacts, and molecular mobility through mesoscale simulations of silk-based fibers. We show that these emergent features can be used to predict mechanical property enhancements arising from postspin drawing. Simulations recapitulate a purely process-dependent mechanical property envelope in which order enhances fiber strength while preserving toughness. The relationship between chain extension and crystalline domain alignment observed in simulations is validated by Raman spectroscopy of wet-spun fibers. Property enhancements attributed to the progression of anisotropic extension are verified by mechanical tests of drawn silk fibers and justified by theory. These findings elucidate how drawing enhances properties of protein-based fibers and shed light on how to incorporate this effect into predictive models. 

Abstract Boiling heat transfer serves as an efficient mechanism to dissipate large amounts of thermal energy due to the latent heat of phase change. In academic studies, typically ultra-pure deionized (DI) water is used to avoid contamination. However, in industrial and commercial settings, the working fluid might be contaminated with sediments, dust, salts, or organic matter. Long-term boiling processes in non-DI water cause substantial build-up of a stable layer of deposit that dramatically reduces the heat transfer coefficient. Therefore, heating applications in a contaminated medium demand strategies to prevent such fouling. Here, we studied the use of lubricant infused surfaces (LIS) and their ability to possibly minimize the deposition of calcium sulfate. Aluminum samples were infused with Krytox 102 oil and the heat transfer coefficient was investigated at a vertical and horizontal surface orientation. Fouling effects were introduced by pool boiling for 7.5 hours in a 6.97 mM calcium sulfate solution at constant heat flux. Heat flux curves for both plain aluminum and LIS were calibrated before contamination. Initially, the LIS was unable to support a nucleate phase and transitioned directly from liquid convection to film boiling heat transfer. Upon partial degradation of the lubricant layer during long-run experiments, nucleate boiling ensued. Over 7.5 hours, the heat transfer coefficient of each sample (Al and LIS) degraded between 5.4% and 7.9% with no significant correlation with either lubricant treatment or surface orientation. Post boiling profilometry was conducted on each sample to characterize the thickness and distribution of the calcium sulfate layer. In these experiments, the plain aluminum surface outperformed the LIS at both orientations in minimizing calcium layer thickness. The LIS oriented vertically outperformed the LIS oriented horizontally. 

Quadrupole-bound anions are negative ions in which their excess electrons are loosely bound by long-range electron-quadrupole attractions. Experimental evidence for quadrupole-bound anions has been scarce; until now, only trans -succinonitrile had been experimentally confirmed to form a quadrupole-bound anion. In this study, we present experimental evidence for a new quadrupole-bound anion. Our combined Rydberg electron transfer/anion photoelectron spectroscopy study demonstrates that the ee conformer of 1,4-dicyanocyclohexane (DCCH) supports a quadrupole-bound anion state, and that the cis -DCCH conformer forms a dipole-bound anion state. The electron binding energies of the quadrupole- and dipole-bound anions are measured as 18 and 115 meV, respectively, both of which are in excellent agreement with theoretical calculations by Sommerfeld. 

Helium atom scattering and density-functional theory (DFT) are used to characterize the phonon band structure of the (3 × 1)-O surface reconstruction of Nb(100). Innovative DFT calculations comparing surface phonons of bare Nb(100) to those of the oxide surface show increased resonances for the oxide, especially at higher energies. Calculated dispersion curves align well with experimental results and yield atomic displacements to characterize polarizations. Inelastic helium time-of-flight measurements show phonons with mixed longitudinal and shear-vertical displacements along both the ⟨[Formula: see text]⟩, [Formula: see text] and ⟨[Formula: see text]⟩, [Formula: see text] symmetry axes over the entire first surface Brillouin zone. Force constants calculated for bulk Nb, Nb(100), and the (3 × 1)-O Nb(100) reconstruction indicate much stronger responses from the oxide surface, particularly for the top few layers of niobium and oxygen atoms. Many of the strengthened bonds at the surface create the characteristic ladder structure, which passivates and stabilizes the surface. These results represent, to our knowledge, the first phonon dispersion data for the oxide surface and the first ab initio calculation of the oxide’s surface phonons. This study supplies critical information for the further development of advanced materials for superconducting radiofrequency cavities.