Preparation of monodisperse cerium oxide particle suspensions from a tetravalent precursor.

Cerium oxide particles are a unique material that enables studying the intersection of metal oxides, f-elements, and nanomaterials. Distinct from diverse applications in catalysis, energy, and medicine, cerium possesses additional influence as a non-radioactive actinide surrogate. Herein, we present a synthesis for sub-micron cerium particles using hexamethylenetetramine and ammonium hydroxide as precipitating agents with a CeIV precursor. The combinatorial homogeneous precipitation approach yields monodisperse and moderately-stable CeO2 particle suspensions in ethanol, as determined by powder X-ray diffraction, scanning electron microscopy, dynamic light scattering, and zeta potential measurements. Various additives may be used to moderate and manipulate the surface charge of the particles. Proof-of-concept electrophoretic deposition of the particles produces a uniform layer of CeO2 on graphite. The synthesis and suspension properties are developed as a methodology towards future controlled actinide hydrolysis and film deposition.

A Bioinspired Artificial Injury Response System Based on a Robust Polymer Memristor to Mimic a Sense of Pain, Sign of Injury, and Healing.

Flexible electronic skin with features that include sensing, processing, and responding to stimuli have transformed human-robot interactions. However, more advanced capabilities, such as human-like self-protection modalities with a sense of pain, sign of injury, and healing, are more challenging. Herein, a novel, flexible, and robust diffusive memristor based on a copolymer of chlorotrifluoroethylene and vinylidene fluoride (FK-800) as an artificial nociceptor (pain sensor) is reported. Devices composed of Ag/FK-800/Pt have outstanding switching endurance >106  cycles, orders of magnitude higher than any other two-terminal polymer/organic memristors in literature (typically 102 -103 cycles). In situ conductive atomic force microscopy is employed to dynamically switch individual filaments, which demonstrates that conductive filaments correlate with polymer grain boundaries and FK-800 has superior morphological stability under repeated switching cycles. It is hypothesized that the high thermal stability and high elasticity of FK-800 contribute to the stability under local Joule heating associated with electrical switching. To mimic biological nociceptors, four signature nociceptive characteristics are demonstrated: threshold triggering, no adaptation, relaxation, and sensitization. Lastly, by integrating a triboelectric generator (artificial mechanoreceptor), memristor (artificial nociceptor), and light emitting diode (artificial bruise), the first bioinspired injury response system capable of sensing pain, showing signs of injury, and healing, is demonstrated.

In-situ monitoring for liquid metal jetting using a millimeter-wave impedance diagnostic.

This article presents a millimeter-wave diagnostic for the in-situ monitoring of liquid metal jetting additive manufacturing systems. The diagnostic leverages a T-junction waveguide device to monitor impedance changes due to jetted metal droplets in real time. An analytical formulation for the time-domain T-junction operation is presented and supported with a quasi-static full-wave electromagnetic simulation model. The approach is evaluated experimentally with metallic spheres of known diameters ranging from 0.79 to 3.18 mm. It is then demonstrated in a custom drop-on-demand liquid metal jetting system where effective droplet diameters ranging from 0.8 to 1.6 mm are detected. Experimental results demonstrate that this approach can provide information about droplet size, timing, and motion by monitoring a single parameter, the reflection coefficient amplitude at the input port. These results show the promise of the impedance diagnostic as a reliable in-situ characterization method for metal droplets in an advanced manufacturing system.

Additive manufacturing of platinum group element (PGE) reference materials with a silica matrix.

RATIONALE: The microanalytical community has an outstanding need for platinum group element (PGE) reference materials, particularly for trace element analysis by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). National Institute of Standards and Technology (NIST) glasses contain Rh, Pd, and Pt, but lack Ru, Os, and Ir. Synthesis of silicate PGE standards has proven difficult due the tendency of PGEs to form metallic nuggets. METHODS: Additive manufacturing methods were used to produce PGE standards with a silica matrix. Monodispersed submicron PGE-doped Stöber particles were used as feedstock materials for electrophoretic deposition (EPD). Two-cm-sized samples produced by EPD were subsequently densified by thermal processing. The homogeneity of PGEs was tested using LA-ICPMS and concentrations were measured by laser ablation and solution ICPMS. RESULTS: The PGE concentrations ranged from 0.5 to 3 µg/g. The inhomogeneity was at the 3% RSD level for Ru, Rh, Ir, and Os throughout and 5% for Pt and Pd in the interior of the samples. Based on LA-ICPMS analyses, the interiors of the two samples have near identical concentrations in PGEs. CONCLUSIONS: The samples fabricated in this study represent the most complete and homogeneous PGE standards produced with a silicate matrix. The ability to produce multiple samples with the same composition provides opportunities for validating methods, monitoring long-term reproducibility, and facilitating interlaboratory comparisons.

Colloidal Materials for 3D Printing.

In recent years, 3D printing has led to a disruptive manufacturing revolution that allows complex architected materials and structures to be created by directly joining sequential layers into designed 3D components. However, customized feedstocks for specific 3D printing techniques and applications are limited or nonexistent, which greatly impedes the production of desired structural or functional materials. Colloids, with their stable biphasic nature, have tremendous potential to satisfy the requirements of various 3D printing methods owing to their tunable electrical, optical, mechanical, and rheological properties. This enables materials delivery and assembly across the multiple length scales required for multifunctionality. Here, a state-of-the-art review on advanced colloidal processing strategies for 3D printing of organic, ceramic, metallic, and carbonaceous materials is provided. It is believed that the concomitant innovations in colloid design and 3D printing will provide numerous possibilities for the fabrication of new constructs unobtainable using traditional methods, which will significantly broaden their applications.

Additively manufacturable micro-mechanical logic gates.

Early examples of computers were almost exclusively based on mechanical devices. Although electronic computers became dominant in the past 60 years, recent advancements in three-dimensional micro-additive manufacturing technology provide new fabrication techniques for complex microstructures which have rekindled research interest in mechanical computations. Here we propose a new digital mechanical computation approach based on additively-manufacturable micro-mechanical logic gates. The proposed mechanical logic gates (i.e., NOT, AND, OR, NAND, and NOR gates) utilize multi-stable micro-flexures that buckle to perform Boolean computations based purely on mechanical forces and displacements with no electronic components. A key benefit of the proposed approach is that such systems can be additively fabricated as embedded parts of microarchitected metamaterials that are capable of interacting mechanically with their surrounding environment while processing and storing digital data internally without requiring electric power.

Field responsive mechanical metamaterials.

Typically, mechanical metamaterial properties are programmed and set when the architecture is designed and constructed, and do not change in response to shifting environmental conditions or application requirements. We present a new class of architected materials called field responsive mechanical metamaterials (FRMMs) that exhibit dynamic control and on-the-fly tunability enabled by careful design and selection of both material composition and architecture. To demonstrate the FRMM concept, we print complex structures composed of polymeric tubes infilled with magnetorheological fluid suspensions. Modulating remotely applied magnetic fields results in rapid, reversible, and sizable changes of the effective stiffness of our metamaterial motifs.

Mesoscale Particle-Based Model of Electrophoretic Deposition.

We present and evaluate a semiempirical particle-based model of electrophoretic deposition using extensive mesoscale simulations. We analyze particle configurations in order to observe how colloids accumulate at the electrode and arrange into deposits. In agreement with existing continuum models, the thickness of the deposit increases linearly in time during deposition. Resulting colloidal deposits exhibit a transition between highly ordered and bulk disordered regions that can give rise to an appreciable density gradient under certain simulated conditions. The overall volume fraction increases and falls within a narrow range as the driving force due to the electric field increases and repulsive intercolloidal interactions decrease. We postulate ordering and stacking within the initial layer(s) dramatically impacts the microstructure of the deposits. We find a combination of parameters, i.e., electric field and suspension properties, whose interplay enhances colloidal ordering beyond the commonly known approach of only reducing the driving force.

On-demand and location selective particle assembly via electrophoretic deposition for fabricating structures with particle-to-particle precision.

Programmable positioning of 2 µm polystyrene (PS) beads with single particle precision and location selective, "on-demand", particle deposition was demonstrated by utilizing patterned electrodes and electrophoretic deposition (EPD). An electrode with differently sized hole patterns, from 0.5 to 5 µm, was used to illustrate the discriminatory particle deposition events based on the voltage and particle-to-hole size ratio. With decreasing patterned hole size, a larger electric field was required for a particle deposition event to occur in that hole. For the 5 µm hole, particle deposition began to occur at 10 V/cm where as an electric field of 15 V/cm was required for particles to begin depositing in the 2 µm holes. The likelihood of particle depositions continued to increase for smaller sized holes as the electric field increased. Eventually, a monolayer of particles began to form at approximately 20 V/cm. In essence, a voltage threshold was found for each hole pattern of different sizes, allowing fine adjustments in pattern hole size and voltage to control when a particle deposition event took place, even with the patterns on the same electrode. This phenomenon opens a route toward controlled, multimaterial deposition and assembly onto substrates without repatterning of the electrode or complicated surface modification of the particles. An analytical approach using the theories for electrophoresis and dielectrophoresis found the former to be the dominating force for depositing a particle into a patterned hole. Ebeam lithography was used to pattern spherical holes in precise configurations onto electrode surfaces, where each hole accompanied a polystyrene (PS) particle placement and attachment during EPD. The versatility of e-beam lithography was utilized to create arbitrary pattern configurations to fabricate particle assemblies of limitless configurations, enabling fabrication of unique materials assemblies and interfaces.

Induced charge electroosmosis micropumps using arrays of Janus micropillars.

We report on a microfluidic AC-driven electrokinetic pump that uses Induced Charge Electro-Osmosis (ICEO) to generate on-chip pressures. ICEO flows occur when a bulk electric field polarizes a metal object to induce double layer formation, then drives electroosmotic flow. A microfabricated array of metal-dielectric Janus micropillars breaks the symmetry of ICEO flow, so that an AC electric field applied across the array drives ICEO flow along the length of the pump. When pumping against an external load, a pressure gradient forms along the pump length. The design was analyzed theoretically with the reciprocal theorem. The analysis reveals a maximum pressure and flow rate that depend on the ICEO slip velocity and micropillar geometry. We then fabricate and test the pump, validating our design concept by demonstrating non-local pressure driven flow using local ICEO slip flows. We varied the voltage, frequency, and electrolyte composition, measuring pump pressures of 15-150 Pa. We use the pump to drive flows through a high-resistance microfluidic channel. We conclude by discussing optimization routes suggested by our theoretical analysis to enhance the pump pressure.

Morphology of electrophoretically deposited films on electrode strips.

Studies of the kinetics of electrophoretic deposition (EPD) processes have generally focused on electrode geometries that yield analytical solutions, such as infinite parallel planes and concentric cylinders. In this article, we construct a finite element model for EPD of material onto a planar strip electrode, which shows excellent qualitative agreement to experimental results in a similar system. Notably, we demonstrate that the presence of the edges of the electrode lead to a singularity in the electric field that significantly affects the morphology of the deposit at short times or for thin deposits.

An automated, high-throughput experimental system for induced charge electrokinetics.

Recent experiments in induced charge electrokinetics (ICEK) have shown that the standard theory generally overpredicts experimentally observed velocities. Such discrepancies reduce the efficacy of practical ICEK devices, and highlight our incomplete understanding of electrokinetic phenomena. Here, we present an automated experimental system that allows for the rapid collection of ICEK data under a variety of conditions ( approximately 1000 per day) to help develop and constrain new theories. We demonstrate this system by studying the ICEK slip flows over electrodes that have been controllably "contaminated" with a dielectric layer, either SiO(2) or an alkanethiol self-assembled monolayer, of known thickness. We also develop a theory that accounts for the effects of the dielectric coatings surface chemistry that yields quantitative agreement with experiments over nearly a thousand distinct conditions in the SiO(2) system and present an additional three thousand experiments of flows over alkanethiol monolayers. Our experimental system allows the direct interrogation of the physico-chemical effects that influence ICEK flows and for the optimization of these flows in lab-on-a-chip systems.

Induced charge electro-osmosis over controllably contaminated electrodes.

Recent studies in nonlinear electrokinetics reveal the standard theory to generally overpredict measured velocities, sometimes dramatically. Contamination of the driving surface provides a natural mechanism for electrokinetic suppression. We measure induced charge electro-osmosis over gold electrodes "contaminated" with silica layers of controlled thickness for nearly a thousand distinct conditions, in a system that enables direct comparisons between theoretical predictions and experimental measurements. Both the magnitude and frequency dependence of the measured slip velocity are captured quantitatively over the entire range of experiments by accounting for the physical capacitance and surface chemistry of the dielectric layer. More generally, the quantitative characterization enabled by our apparatus will prove invaluable for the rational design and prediction of electrokinetic systems.

Acid-base bifunctional and dielectric outer-sphere effects in heterogeneous catalysis: a comparative investigation of model primary amine catalysts.

Dielectric and acid-base bifunctional effects are elucidated in heterogeneous aminocatalysis using a synthetic strategy based on bulk silica imprinting. Acid-base cooperativity between silanols and amines yields a bifunctional catalyst for the Henry reaction that forms alpha,beta-unsaturated product via quasi-equilibrated iminium intermediate. Solid-state UV/vis spectroscopy of catalyst materials treated with salicylaldehyde demonstrates zwitterionic iminium ion to be the thermodynamically preferred product in the bifunctional catalyst. This product is observed to a much lesser extent relative to its neutral imine tautomer in primary amine catalysts having outer-sphere silanols partially replaced by aprotic functional groups. One of these primary amine catalysts, consisting of a polar outer-sphere environment derived from cyano-terminated capping groups, has activity comparable to that of the bifunctional catalyst in the Henry reaction, but instead forms the beta-nitro alcohol product in high selectivity (approximately 99%). This appears to be the first observation of selective alcohol formation in primary amine catalysis of the Henry reaction. A primary amine catalyst with a methyl-terminated outer-sphere also produces alcohol, albeit at a rate that is 50-fold slower than the cyano-terminated catalyst, demonstrating that outer-sphere dielectric constant affects catalyst activity. We further investigate the importance of organizational effects in enabling acid-base cooperativity within the context of bifunctional catalysis, and the unique role of the solid surface as a macroscopic ligand to impose this cooperativity. Our results unequivocally demonstrate that reaction mechanism and product selectivity in heterogeneous aminocatalysis are critically dependent on the outer-sphere environment.