Sorption-based low-pressure green ammonia synthesis using supported metal halide salts enables efficient interconversion between hydrogen and ammonia, allowing the high hydrogen density and well-established transportation network of ammonia to be used for green energy storage. Magnesium chloride supported on silica gel (MgCl2/SiO2) sorbent has been the subject of much investigation owing to its high capacity, selectivity, and reversibility at temperatures close to reactor conditions; however, MgCl2/SiO2 suffers from low thermal conductivity, which complicates absorber design at larger scales and prolongs absorption-desorption cycle times. We present a scalable, solventless method for supporting MgCl2 on thermally conductive aluminum fibers (MgCl2/Al) - a thermally conductive ammonia sorbent with a high working capacity of 220 mgNH3/gabsorbent. Although the solventless synthesis causes variance in initial-cycle pressure drop and capacity, we show that this stabilizes after cycling. The high thermal conductivity of MgCl2/Al allows for rapid absorption-desorption cycles, enabling easier scale-up. MgCl2/Al also maintains its cyclic capacity up to 50 cycles without any signs of degradation.

Atmosphere- and/or moisture-sensitive materials can be challenging to characterize using electron microscopy techniques due to sample preparation workflows that generally require exposure to ambient conditions. Here, we describe a novel preparation method that uses aluminum foil in combination with a commercial cryo-EM transfer system to circumvent undesired exposure to the atmosphere. First, hygroscopic MgCl 2 was used as a model material, and prepared samples (both protected and unprotected) were placed in a controlled-humidity environment (> 80% relative humidity) for various exposure lengths (circa seconds to hours). Following this, the effectiveness of the sample preparation method was determined by comparing qualitative photos and quantitative X-ray diffraction patterns between the two sample subsets. The combined results of these experiments suggest that the outlined preparation method effectively protects MgCl 2 from atmospheric contamination compared to MgCl 2 samples that had no protective measures taken. Finally, the preparation method was utilized to protect a highly hygroscopic crystalline BaO thin film for characterization via scanning electron microscopy, thereby demonstrating a functional application of the outlined preparation technique and an additional use for the commercial cryo-EM transfer system beyond its intended application.

Metal halides such as MgCl2 have a high capacity for ammonia absorption and can be used in place of a condenser to efficiently separate ammonia from the reactor effluent in the Haber-Bosch process. Although these salts are effective at capturing and storing ammonia, they show reduced working capacity in their pure form with repeated cycling due to slowed uptake and release with particle agglomeration and heat transfer limitations. To stabilize the ammonia uptake performance, MgCl2 salt crystals were supported on aluminum fibers. Incorporating aluminum fibers into pure MgCl2 was found to reduce the sample charging during electron microscopy and increase the bed thermal conductivity. By using a 40 wt % MgCl2-Al absorbent mixture, cyclic ammonia working capacity was increased by a third over our previously reported absorbent (40 wt % MgCl2-SiO2) and the bed thermal conductivity increased by an order of magnitude. Higher performance stability using aluminum was attributed to two possible factors: the aluminum fibers guide recrystallization so as to maintain a crust of small crystals that adhered to the metal surface and the high thermal conductivity of the aluminum fibers can help suppress temperature overshoot or undershoot during ammonia uptake or release, respectively.

Synthesized ammonia exiting a reactor with hydrogen and nitrogen can be selectively absorbed by MgCl2 for renewable absorbent-based Haber Bosch for dispersed ammonia manufacturing. Such separation can be more efficient even at elevated temperatures compared to the condensation method used in conventional Haber Bosch process. To determine the optimal conditions to capture and release the most ammonia per thermal cycle of sorbent salt, the sorbent capacity was measured with varying regeneration temperature, regeneration time, and sweep rate under steady-state cycling conditions. In all cases, uptake was limited to bed breakthrough, and cyclic steady state was achieved. By using lower temperature for MgCl2 regeneration (200 °C), the working capacities were maintained comparable to those at higher desorption temperatures (~ 400 ⁰C), even without the use of inert sweep gas. Using a sufficiently high regeneration temperature (~200 ⁰C) allowed for sufficiently low sweep gas that the product ammonia can exceed 72 mol% purity in a mixture of N2 and H2. These results were achieved with a short regeneration time of 20 minutes or less, which is an improvement from hour-long regeneration time previously reported. These measurements identified new operating parameters for more efficient absorber design to produce economical renewable ammonia at small scale.

Metal halides such as MgCl2 have a high capacity for ammonia absorption and can be used in place of a condenser to efficiently separate ammonia from reactor effluent in the Haber-Bosch process. Although these salts are effective at capturing and storing ammonia, they show reduced working capacity in their pure form with repeated cycling due to slowed uptake and release with particle agglomeration and heat transfer limitations. To stabilize ammonia uptake performance, MgCl2 salt crystals were supported on aluminum fibers. Incorporating aluminum fibers into pure MgCl2 was found to reduce sample charging during electron microscopy and increase bed thermal conductivity. By using a 40 wt.% MgCl2-Al absorbent mixture, ammonia storage capacity was increased 33%, and the absorbent bed thermal conductivity increased by two orders of magnitude over our previously reported absorbent (40 wt.% MgCl2-SiO2). Higher stability of the aluminum-supported MgCl2 was attributed to sorbent surface area stabilized by the aluminum fibers, which guided recrystallization events to maintain small crystals that adhered to the metal surface; thermal conductivity of the metal fibers also suppressed temperature overshoot or undershoot during ammonia uptake or release, respectively.

We analyze dynamic adsorption of surfactant from a micellar solution to a rapidly created surface that acts as an absorbing boundary for surfactant monomers (single molecules), along which the monomer concentration vanishes, with no direct micelle adsorption. This somewhat idealized situation is analyzed as a prototype for situations in which strong suppression of monomer concentration accelerates micelle dissociation, and will be used as a starting point for analysis of more realistic boundary conditions in sub-sequent work. We present scaling arguments and approximate models for particular time and parameter regimes and compare the resulting predictions to numerical simulations of the reaction-diffusion equa-tions for a polydisperse system containing surfactant monomers and clusters of arbitrary aggregation number. The model considered here exhibits an initial period of rapid shrinkage and ultimate dissociation of micelles within a narrow region near the interface. This opens a micelle-free region near the interface after some time tie, the width of which increases as t1=2 at times t >> tie. In systems that exhibit disparate fast and slow bulk relaxation times ti1 and ti2 in response to small perturbations, tie is usually comparable to or greater than ti1 but much less than ti2. Such systems exhibit a wide intermediate time regime tie < t < ti2 in which the remaining micellar region reaches a state of partial local equilibrium, followed by a final stage t >> ti2 in which full local equilibrium is established.(c) 2023 Elsevier Inc. All rights reserved.

Sulfate-rich wastewater poses ecological hazards to freshwater ecosystems, and sulfate is highly regulated in many Minnesota lakes. Biological sulfate reduction results in the reduction of sulfate to sulfide, and this process is used to remediate acid mine drainage. Theoretically, the aqueous sulfide can be immobilized into a solid-phase material and removed from the aqueous system. This study focuses on sulfide immobilization using iron-bearing waste minerals. Specifically, the extent of reaction of siderite (FeCO3), an abundant ferrous mineral in some mining wastes, with sulfide was studied. Mildly acidic batch reactors containing powdered siderite were consecutively injected with a sodium sulfide solution. Solid reaction products were identified and characterized using powder X-ray diffraction, scanning and transmission electron microscopy, and energy-dispersive X-ray spectroscopy. Mackinawite (FeS) appeared to be the most abundant product, with greigite (Fe3S4) also detected. Results reveal that the immobilization capacity of sulfide by siderite is limited by the concentration of the Fe2+(aq) presented in the system immediately before the initial sulfide exposure as the Fe2+(aq) levels are not replenished after sulfidation. These results improve our understanding of the sulfidation of siderite and provide insight to improve the viability of using siderite-containing mining waste rock in a sulfate remediation technology.

The phospholipid lecithin (L) and the nonionic surfactant Tween 80 (T) are used together in various contexts, including in drug delivery and oil spill remediation. There is hence a need to elucidate the nanostructures in LT mixtures, which is the focus of this paper. We study these mixtures using cryogenic transmission electron microscopy (cryo-TEM), coupled with dynamic light scattering and small-angle neutron scattering. As the concentration of Tween 80 is increased, the vesicles formed by lecithin are transformed into spherical micelles. We identify bicelles (i.e., disc-like micelles) as well as cylindrical micelles as the key stable nanostructures formed at intermediate L/T ratios. The bicelles have diameters ∼13-26 nm, and the bicelle size decreases as the Tween 80 content increases. We propose that the lecithin lipids form the body of the discs, while the Tween 80 surfactants occupy the rims. This hypothesis is consistent with geometric arguments because lecithin is double-tailed and favors minimal curvature, whereas the single-tailed Tween 80 molecules prefer curved interfaces. In the case of cylindrical micelles, cryo-TEM reveals that the micelles are short (length < 22 nm) and flexible. We are able to directly visualize the microstructure of the aggregates formed by lecithin-Tween 80 mixtures, thereby enhancing the understanding of morphological changes in the lecithin-Tween 80 system.

This is the first of a pair of articles that present the theory of kinetic and transport phenomena in micelle-forming surfactant solutions in a form that facilitates discussion of large deviations from equilibrium. Our goal is to construct approximate but robust reduced models for both homogeneous and inhomogeneous systems as differential equations for unimer concentration c_{1}, micelle number concentration c_{m}, average micelle aggregation number q and (optionally) aggregation number variance σ_{m}^{2}. This first article discusses kinetics in homogeneous solutions. We focus particularly on developing models that can describe both weakly perturbed states and states in which c_{1} is suppressed significantly below the critical micelle concentration, which leads to rapid shrinkage and dissociation of any remaining micelles. This focus is motivated by the strong local suppression of c_{1} that is predicted to occur near interfaces during some adsorption processes that are considered in the second article. Toward this end, we develop a general nonlinear theory of fast stepwise processes for systems that may be subjected to large changes in q and c_{1}. This is combined with the existing nonlinear theory of slow association and dissociation processes to construct a general model for systems governed by stepwise reaction kinetics. We also consider situations in which the slow process of micelle creation and destruction instead occurs primarily by micelle fission and fusion, and analyze the dependencies of micelle lifetime and the slow relaxation time upon surfactant concentration in systems controlled by either association-dissociation or fission-fusion mechanisms.

We discuss diffusion in micellar surfactant solutions in a form appropriate for analyzing experiments that involve large deviations from equilibrium. A general nonlinear dynamical model for inhomogeneous systems is developed that describes the effects of diffusion and micelle kinetics as a set of coupled partial differential equations for unimer concentration, micelle number concentration, average micelle aggregation number, and, optionally, the variance of the micelle aggregation number. More specialized models are developed to describe slow dynamics in situations in which the system stays in a state of partial local equilibrium or full local equilibrium. As an illustrative example of a nonlinear transport phenomenon, we discuss a simple model of diffusion from an initially homogeneous micellar solution to a rapidly created absorbing interface with fast unimer adsorption.

Ammonia absorber columns offer an alternative separation unit to replace condensation in the Haber-Bosch synthesis loop. Metal halide salts can selectively separate ammonia from the reactor outlet gas mixture and incorporate it into their crystal lattice with remarkably high thermodynamic capacity. While the salts’ working capacity can be limited and unstable when they are in their pure form, the capacity is stable and can be high when using a porous ceramic support. In this project, we found optimal conditions for sorbent fabrication, we demonstrated benchmark levels of uptake and release of ammonia, and we fabricated and demonstrated a prototype at a scale of 1 kg/day ammonia. This task allowed us to assess improvement in the techno-economic prospects for this new separation approach, making viable more distributed production of green ammonia from geographically dispersed renewable energy sources.

Dense nanolipid fluid (DNLF) dispersions are highly concentrated aqueous dispersions of lipid nanocarriers (LNCs) with more than 1015 lipid particles per cubic centimeter. Descriptions of dense nanolipid fluid dispersions in the scientific literature are rare, and they have not been used to encapsulate drugs. In this paper we describe the synthesis of DNLF dispersions comprising ibuprofen using a recently described twin-screw extrusion process. We report that such dispersions are stable, bind ibuprofen tightly and yet provide high transdermal drug permeation. Ibuprofen DNLF dispersions prepared according to the present study provide up to five times greater flux of the pharmacologically active S-ibuprofen isomer through human skin than a commercially available racemic ibuprofen emulsion product. We demonstrate scaling up the twin-screw extrusion method to pilot production for a stable, highly permeating ibuprofen DNLF composition based on excipients approved by the US FDA for use in topical products as a key step towards development of a commercially viable, FDA approvable topical ibuprofen medicine to treat osteoarthritis, which has never before been accomplished.

Marine oil dispersants typically contain blends of surfactants dissolved in solvents. When introduced to the crude oil-seawater interface, dispersants facilitate the breakup of crude oil into droplets that can disperse in the water column. Recently, questions about the environmental persistence and toxicity of commercial dispersants have led to the development of "greener" dispersants consisting solely of food-grade surfactants such as l-α-phosphatidylcholine (lecithin, L) and polyoxyethylenated sorbitan monooleate (Tween 80, T). Individually, neither L nor T is effective at dispersing crude oil, but mixtures of the two (LT blends) work synergistically to ensure effective dispersion. The reasons for this synergy remain unexplained. More broadly, an unresolved challenge is to be able to predict whether a given surfactant (or a blend) can serve as an effective dispersant. Herein, we investigate whether the LT dispersant effectiveness can be correlated with thermodynamic phase behavior in model systems. Specifically, we study ternary "DOW" systems comprising LT dispersant (D) + a model oil (hexadecane, O) + synthetic seawater (W), with the D formulation being systematically varied (across 0:100, 20:80, 40:60, 60:40, 80:20, and 100:0 L:T weight ratios). We find that the most effective LT dispersants (60:40 and 80:20 L:T) induce broad Winsor III microemulsion regions in the DOW phase diagrams (Winsor III implies that the microemulsion coexists with aqueous and oil phases). This correlation is generally consistent with expectations from hydrophilic-lipophilic deviation (HLD) calculations, but specific exceptions are seen. This study then outlines a protocol that allows the phase behavior to be observed on short time scales (ca. hours) and provides a set of guidelines to interpret the results. The complementary use of HLD calculations and the outlined fast protocol are expected to be used as a predictive model for effective dispersant blends, providing a tool to guide the efficient formulation of future marine oil dispersants.

In this study, fast and continuous fabrication of microscale structures by roll-to-roll UV imprinting or micromolding is demonstrated on a 121 mm wide web. This process is enabled by a UV curable thiol-ene-acrylate resin system, following the work of Stadlober and coworkers. A series of formulations were prepared with fast curing speeds at ambient conditions, low viscosities, and tunable mechanical properties. The rate and extent of curing as a function of the formulation composition were investigated with Fourier transform infrared spectroscopy. Consistent with the past work, we show that the thiol-ene-acrylate formulations reached high double bond conversions (> 80%) with the maximum conversion increasing with the relative thiol content and decreasing with the viscous urethane acrylate oligomer content. The double bond conversion of the patterned coatings (in contact with the mold) is shown to be ~ 80% for a range of UV lamp powers and web speeds up to 2.7 cm/s. Areas of the coating not covered by the mold required higher UV lamp power and/or lower web speeds to cure to a tack-free state. Microscale channels and arrays of recessed wells with various dimensions and pattern densities were continuously fabricated. Our findings show the successful use of a tetrafunctional thiol in the thiol-ene-acrylate resin system. We also discuss guidelines for the selection of processing conditions for the manufacturing of structured plastic substrates using roll-to-roll imprinting processes, opening up potential new applications.

Ammonia made with hydrogen from sustainable wind energy can be separated from unreacted hydrogen and nitrogen by absorption in magnesium chloride. The absorption is rapid, but desorption can be slower. This work shows that the mechanism of desorption involves two steps: (i) decomposition of ammines to make ammonia and (ii) solid-state diffusion of the produced NH3 . With current absorbents, the diffusion step is usually controlling. These experiments suggest the best operating conditions for a pilot scale, wind-powered ammonia separation and provide a strategy for improving the metal-chloride absorbent.

Monte Carlo simulations are used to study adsorption of highly asymmetric diblock copolymers to a polymer-polymer interface, and the results compared to self-consistent field theory (SCFT) predictions. The simulation model used here is a bead-spring model that has been used previously to study equilibrium and kinetic properties of spherical micelles [J. A. Mysona et al., Phys. Rev. E 100, 012602 (2019)2470-004510.1103/PhysRevE.100.012602; Phys. Rev. E 100, 012603 (2019)10.1103/PhysRevE.100.012603; Phys. Rev. Lett. 123, 038003 (2019)10.1103/PhysRevLett.123.038003]. Interfacial copolymer concentration Γ and interfacial tension γ are measured as functions of bulk copolymer concentration at concentrations up to the critical micelle concentration over a range of values of the Flory-Huggins χ parameter. The dependence of interfacial pressure Π = γ_{0}-γ on Γ (where γ_{0} is the interfacial tension in the absence of copolymer) is found to be almost independent of χ and to be accurately predicted by SCFT. The bare interfacial tension γ_{0} and total interfacial tension γ(Γ) can also be accurately predicted by SCFT using an estimate of χ obtained from independent analysis of properties of symmetric diblock copolymer melts. SCFT predictions obtained with this estimate of χ do not, however, adequately describe the thermodynamics of the coexisting bulk copolymer solution, as a result of contraction of the strongly interacting core block of dissolved copolymers. Accurate predictions of the relationship between bulk and interfacial properties can thus only be obtained for this system by combining SCFT predictions of the interfacial equation of state with a fit to the measured equation of state for the bulk solution.

Metal halide salts such as magnesium chloride have been demonstrated to be promising candidates for ammonia storage materials for energy storage and agriculture applications due to their ability to incorporate several moles of ammonia per mole of salt. Ammonia exiting a synthesis reactor can be separated from nitrogen and hydrogen by absorption into magnesium chloride. Such an absorption can be more complete and hotter than separation via ammonia condensation, the current standard in the Haber-Bosch process. Here, we discuss the optimal conditions for the cyclic uptake and release of ammonia from the supported magnesium chloride absorbents. An automated system was designed for measuring the nonequilibrium working capacity of the absorbent, as well as the impact of important operating conditions such as absorption and desorption temperature, pressure, and desorption time. Measurements of absorption and desorption kinetics provide insight into the mechanisms involved. The temperatures and pressures during absorption and desorption were designed to use minimal energy input to maximize the uptake and release of ammonia within a reasonable amount of time. In a laboratory-scale bed, absorption has a small unused bed length, so it is largely independent of mass transfer; it is dominated by how fast ammonia is fed to the bed. On the other hand, desorption is restricted both by the speed of heating the bed and by diffusion out of the absorbent. These measurements provide guidelines for ammonia separations and cycling sorbent materials on a larger scale.

In micellar surfactant solutions, changes in the total number of micelles are rare events that can occur by either of two mechanisms-by stepwise association and dissociation via insertion and expulsion of individual molecules or by fission and fusion of entire micelles. Molecular dynamics simulations are used here to estimate rates of these competing mechanisms in a simple model of block copolymer micelles in homopolymer solvent. This model exhibits a crossover with increasing degree of repulsion between solvent and micelle core components, from a regime dominated by association and dissociation to a regime dominated by fission and fusion.