Fluid-Mediated Fabrication of Complex Assemblies.

This Perspective accounts for recent progress in the directed control of interfacial fluid flows harnessed to assemble architected soft materials. We are focusing on the paradigmatic problem of free-surface flows in curable elastomers. These elastomers are initially liquid and cure into elastic solids whose shape is imparted by concomitant and competing phenomena: flow-induced deformations and curing. Particular attention is given to the role of capillary forces in these systems. Originating from the cohesive nature of liquids and thus favoring smooth interfaces, capillary forces can also promote the destabilization of interfaces, e.g., into droplets. In turn, such mechanical instabilities tend to grow into regular patterns, e.g., forming hexagonal lattices. We discuss how the universality, robustness, and ultimate regularity of these out-of-equilibrium processes could serve as a basis for new fabrication paradigms, where instabilities are directed to generate target architected solids obtained without each element laid in place by direct mechanized intervention.

Dynamics of Liquid Transfer from Nanoporous Stamps in High-Resolution Flexographic Printing.

Printing of ultrathin layers of polymeric and colloidal inks is critical for the manufacturing of electronics on nonconventional substrates such as paper and polymer films. Recently, we found that nanoporous stamps overcome key limitations of traditional polymer stamps in flexographic printing, namely, enabling the printing of ultrathin nanoparticle films with micron-scale lateral precision. Here, we study the dynamics of liquid transfer between nanoporous stamps and solid substrates. The stamps comprise forests of polymer-coated carbon nanotubes, and the surface mechanics and wettability of the stamps are engineered to imbibe colloidal inks and transfer the ink upon contact with the target substrate. By high-speed imaging during printing, we observe the dynamics of liquid spreading, which is mediated by progressing contact between the nanostructured stamp surface and by the substrate and imbibition within the stamp-substrate gap. From the final contact area, the volume of ink transfer is mediated by rupture of a capillary bridge; and, after rupture, liquid spreads to fill the area defined by a precursor film matching the stamp geometry with high precision. Via modeling of the liquid dynamics, and comparison with data, we elucidate the scale- and rate-limiting aspects of the process. Specifically, we find that the printed ink volume and resulting layer thickness are independent of contact pressure; and that printed layer thickness decreases with retraction speed. Under these conditions, nanoparticle films with controlled thickness in the <100 nm regime can be printed using nanoporous stamp flexography, at speeds commensurate with industrial printing equipment.

An introduction to the mechanics of the lasso.

Trick roping evolved from humble origins as a cattle-catching tool into a sport that delights audiences all over the world with its complex patterns or 'tricks'. Its fundamental tool is the lasso, formed by passing one end of a rope through a small loop (the honda) at the other end. Here, we study the mechanics of the simplest rope trick, the Flat Loop, in which the rope is driven by the steady circular motion of the roper's hand in a horizontal plane. We first consider the case of a fixed (non-sliding) honda. Noting that the rope's shape is steady in the reference frame rotating with the hand, we analyse a string model in which line tension is balanced by the centrifugal force and the rope's weight. We use numerical continuation to classify the steadily rotating solutions in a bifurcation diagram and analyse their stability. In addition to Flat Loops, we find planar 'coat-hanger' solutions, and whirling modes in which the loop collapses onto itself. Next, we treat the more general case of a honda that can slide due to a finite coefficient of friction of the rope on itself. Using matched asymptotic expansions, we resolve the shape of the rope in the boundary layer near the honda where the rope's bending stiffness cannot be neglected. We use this solution to derive a macroscopic criterion for the sliding of the honda in terms of the microscopic Coulomb static friction criterion. Our predictions agree well with rapid-camera observations of a professional trick roper and with laboratory experiments using a 'robo-cowboy'.

Subcomponent self-assembly of rare-earth single-molecule magnets.

A family of lanthanide complexes has been synthesized by the subcomponent self-assembly methodology. Molecular architectures, which were stable in solution and under ambient conditions, were designed by the in situ formation of ligands around lanthanide ion templates. Magnetic studies indicated that, despite the low C2 symmetry, 1 and 2 display single molecule magnet (SMM) behavior, with 1 exhibiting an effective energy barrier of the relaxation of the magnetization U(eff)/k(B) = 50 K and the pre-exponential factor τ(o) = 6.80 × 10(-7) s. Step-like features in the hysteresis loops indicate the presence of quantum tunneling of the magnetization (QTM).