Embedded three-dimensional (EMB3D) printing is an emerging technique that enables free-form fabrication of complex architectures. In this approach, a nozzle is translated omnidirectionally within a soft matrix that surrounds and supports the patterned material. To optimize print fidelity, we have investigated the effects of matrix viscoplasticity on the EMB3D printing process. Specifically, we determine how matrix composition, print path and speed, and nozzle diameter affect the yielded region within the matrix. By characterizing the velocity and strain fields and analyzing the dimensions of the yielded regions, we determine that scaling relationships based on the Oldroyd number, Od, exist between these dimensions and the rheological properties of the matrix materials and printing parameters. Finally, we use EMB3D printing to create complex architectures within an elastomeric silicone matrix. Our methods and findings will both facilitate future characterization of viscoplastic matrices and motivate the development of new materials for EMB3D printing.

No abstract

In the published communication, the author lists of several of the references were presented incorrectly, with the first name of some of the authors given as the family name.These references are corrected here:[3] M. G. Mazza,

No abstract

The flow behavior of fiber suspensions has been studied extensively, especially in the limit of dilute concentrations and rigid fibers; at the other extreme, however, where the suspensions are concentrated and the fibers are highly flexible, much less is understood about the flow properties. We use a microfluidic method to produce uniform concentrated suspensions of high aspect ratio, flexible microfibers, and we demonstrate the shear thickening and gelling behavior of such microfiber suspensions, which, to the best of our knowledge, has not been reported previously. By rheological means, we show that flowing the suspension triggers the irreversible formation of topological entanglements of the fibers resulting in an entangled water-filled network. This phenomenon suggests that flexible fiber suspensions can be exploited to produce a new family of flow-induced gelled materials, such as porous hydrogels. A significant consequence of these flow properties is that the microfiber suspension is injectable through a needle, from which it can be extruded directly as a hydrogel without any chemical reactions or further treatments. Additionally, we show that this fiber hydrogel is a soft, viscoelastic, yield-stress material.

Stable oil/water emulsions are usually obtained by using mixtures of different surfactants. Such systems display synergistic interface stabilizing effects, which have not been fully elucidated yet. Moreover, in many applications surfactants are added at concentrations well above their critical micellar concentration (CMC), and this regime has not been thoroughly explored in the literature as well. Here, we investigate oil/water emulsions through oil/water interfacial tension using two common non-ionic surfactants, Tween 80 and Span 20, in the concentration range C (0.3–1 wt%) well above their respective CMCs. Mesoscale molecular simulations coupled interfacial tensiometry experiments to characterise these interfaces at a molecular level. Interfacial tension g was measured by a pendant drop technique. Coarse-grained calculations provided a microscopic view of the interface at the molecular level (i.e.surfactant arrangement, interface thickness), and were employed to extend the study to those surfactant concentrations where experiments could hardly provide reliable data, if any. We found a significant synergistic effect between Tween 80 and Span 20, with low molecular weight Span molecules occupying free spaces between the much larger, bulky Tween compounds. The surfactant intermolecular interactions could be associated to a striking decrease of interfacial tension in going from pure surfactants to a mixture at the same total weight concentration. Furthermore, the interface was found to exhibit a spatial inhomogeneity with a “patch-like” organisation, reminiscent of microphase separation. Our results show that the proposed, combined experimental/in silico approach provides relevant insights for several industrial applications, such as emulsion stability and oil spill remediation

Understanding jet formation from non-Newtonian fluids is important for improving the quality of various printing and dispensing techniques. Here, we use a laser-based nozzleless method to investigate impulsively formed jets of non-Newtonian fluids. Experiments with a time-resolved imaging setup demonstrate multiple regimes during jet formation that can result in zero, single, or multiple drops per laser pulse. These regimes depend on the ink thickness, ink rheology, and laser energy. For optimized printing, it is desirable to select parameters that result in a single-drop breakup; however, the strain-rate dependent rheology of these inks makes it challenging to determine these conditions a priori. Rather, we present a methodology for characterizing these regimes using dimensionless parameters evaluated from the process parameters and measured ink rheology that are obtained prior to printing and, so, offer a criterion for a single-drop breakup.

A continuous Buchwald−Hartwig reaction using the bulky N-heterocyclic carbene (NHC) precatalyst [Pd(IPr*)(cin)Cl] 4 has been developed for the synthesis of a key pharmaceutical intermediate 2. Using microreactor technology, the reaction could be optimized under dilute conditions with low material burden and the kinetic parameters investigated. For larger lab-scale operation (gram scale), process-relevant concentrations could be employed and the conditions developed for continuous workup effectively demonstrated (batch methodology published concurrently). The stability of the NHC catalyst allowed for a continuous acidic extraction of the product and on-stream recycling of the catalyst in the organic phase. At this scale, sonication is employed to prevent clogging in the reactor unit. Finally, a bespoke continuous flow reactor has been developed for carrying out the reaction beyond lab scale. This novel reactor concept for running heterogeneous reactions in flow combines the flexibility of continuously stirred tank reactors (CSTRs) with the smooth operation, low residence time distribution and excellent heat transfer capability of a conventional flow reactor. A LCA (life cycle analysis) study has been carried out on the resulting process in comparison with the existing batch protocol, revealing it to be favorable under the majority of environmental factors considered.