Publications

2021
van der Hoeven J, Krämer S, Dussi S, Shirman T, Park K, Rycroft C, Bell D, Friend C, Aizenberg J. On the Origin of Sinter‐Resistance and Catalyst Accessibility in Raspberry‐Colloid‐Templated Catalyst Design. Advanced Functional Materials. 2021 :2106876. Publisher's VersionAbstract

Nanoparticle (NP) sintering is a major cause of the deactivation of supported catalysts. Raspberry-Colloid-Templated (RCT) catalysts are an emerging class of materials that show an unprecedented level of sinter-resistance and exhibit high catalytic activity. Here a comprehensive study of the origin of NP stability and accessibility in RCT catalysts using theoretical modeling, 3D electron microscopy, and epitaxial overgrowth is reported. The approach is showcased for silica-based RCT catalysts containing dilute Pd-in-Au NPs previously used in hydrogenation and oxidation catalysis. Modeling of the contact line of the silica precursor infiltrating into the assembled raspberry colloids suggests that a large part of the particles must be embedded into silica, which is confirmed by quantitative visualization of >200 individual NPs by dual-axis electron tomography. The RCT catalysts have a unique structure in which all NPs reside at the pore wall but have >50% of their surface embedded in the matrix, giving rise to the strongly enhanced thermal and mechanical stability. Importantly, epitaxial overgrowth of Ag on the supported NPs reveals that not only the NP surface exposed to the pore but the embedded interface as well remained chemically accessible. This mechanistic understanding provides valuable guidance in the design of stable catalytic materials.

Li S, Librandi G, Yao Y, Richard A, Yamamura AS, Aizenberg J, Bertoldi K. Controlling Liquid Crystal Orientations for Programmable Anisotropic Transformations in Cellular Microstructures. Advanced Materials. 2021 :2105024.Abstract

Geometric reconfigurations in cellular structures have recently been exploited to realize adaptive materials with applications in mechanics, optics, and electronics. However, the achievable symmetry breakings and corresponding types of deformation and related functionalities have remained rather limited, mostly due to the fact that the macroscopic geometry of the structures is generally co-aligned with the molecular anisotropy of the constituent material. To address this limitation, cellular microstructures are fabricated out of liquid crystalline elastomers (LCEs) with an arbitrary, user-defined liquid crystal (LC) mesogen orientation encrypted by a weak magnetic field. This platform enables anisotropy to be programmed independently at the molecular and structural levels and the realization of unprecedented director-determined symmetry breakings in cellular materials, which are demonstrated by both finite element analyses and experiments. It is illustrated that the resulting mechanical reconfigurations can be harnessed to program microcellular materials with switchable and direction-dependent frictional properties and further exploit ”area-specific” deformation patterns to locally modulate transmitted light and precisely guide object movement. As such, the work provides a clear route to decouple anisotropy at the materials level from the directionality of the macroscopic cellular structure, which may lead to a new generation of smart and adaptive materials and devices.

Li L, Goodrich C, Yang H, Phillips KR, Jia Z, Chen H, Wang L, Zhang J, Liu A, Lu J, et al. Microscopic origins of the crystallographically preferred growth in evaporation-induced colloidal crystals. Proceedings of the National Academy of Sciences. 2021;118 (32) :e2107588118. Publisher's VersionAbstract

Self-assembly is one of the central themes in biologically controlled synthesis, and it also plays a pivotal role in fabricating a variety of advanced engineering materials. In particular, evaporation-induced self-assembly of colloidal particles enables versatile fabrication of highly ordered two- or three-dimensional nanostructures for optical, sensing, catalytic, and other applications. While it is well known that this process results in the formation of the face-centered cubic (fcc) lattice with the close-packed {111} plane parallel to the substrate, the crystallographic texture development of colloidal crystals is less understood. In this study, we show that the preferred <110> growth in the fcc colloidal crystals synthesized through evaporation-induced assembly is achieved through a gradual crystallographic rotation facilitated by mechanical stress-induced geometrically necessary dislocations.

Jia Z, Fernandes MC, Deng Z, Yang T, Zhang Q, Lethbridge A, Yin J, Lee J-H, Han L, Weaver J, et al. Microstructural design for mechanical–optical multifunctionality in the exoskeleton of the flower beetle Torynorrhina flammea. Proceedings of the National Academy of Sciences. 2021;118 (25) :e2101017118. Publisher's VersionAbstract

In the design of multifunctional materials, harnessing structural and compositional synergies while avoiding unnecessary trade-offs is critical in achieving high performance of all required functions. Biological material systems like the cuticles of many arthropods often fulfill multifunctionality through the intricate design of material structures, simultaneously achieving mechanical, optical, sensory, and other vital functionalities. A better understanding of the structural basis for multifunctionality and the functional synergies and trade-offs in biological materials could thus provide important insights for the design of bioinspired multifunctional materials. In this study, we demonstrate a concerted experimental, theoretical, and computational approach that uncovers the structure–mechanics–optics relationship of the beetle’s cuticle, opening avenues to investigate biological materials and design photonic materials with robust mechanical performance.

Filie A, Shirman T, Foucher AC, Stach EA, Aizenberg M, Aizenberg J, Friend CM, Madix RJ. Dilute Pd-in-Au alloy RCT-SiO2 catalysts for enhanced oxidative methanol coupling. Journal of Catalysis. 2021. Publisher's VersionAbstract

Dilute alloy catalysts have the potential to enhance selectivity and activity for large-scale reactions. Highly dilute Pd-in-Au nanoparticle alloys partially embedded in porous silica (“raspberry colloid templated” (RCT)-SiO2) prove to be robust and selective catalysts for oxidative coupling of methanol. Palladium concentrations in the bimetallic nanoparticles as low as ~3.4 at.% catalyze the production of methyl formate with a selectivity of ~95% at conversions of ~55%, whereas conversions are low (<10%) for ~1.7 at.% Pd-in-Au nanoparticle and pure Au nanoparticle catalysts. Fractional reaction orders for both CH3OH and O2measured for ~3.4 at.% Pd-in-Au nanoparticles supported on RCT-SiO2 indicated a complex mechanism in which the sites for O2 dissociation are not saturated. Optimal methyl formate production was found for an equimolar mixture. There is no conversion of methanol in the absence of O2 between 360 and 450 K. All observations are consistent with a mechanism derived from model studies, requiring that clusters of Pd be available on the catalyst for O2 dissociation.

van der Hoeven JES, Ngan HT, Taylor A, Eagan NM, Aizenberg J, Sautet P, Madix RJ, Friend CM. Entropic Control of HD Exchange Rates over Dilute Pd-in-Au Alloy Nanoparticle Catalysts. ACS Catalysis. 2021;11 :6971-6981. Publisher's VersionAbstract

Dilute Pd-in-Au alloy catalysts are promising materials for selective hydrogenation catalysis. Extensive surface science studies have contributed mechanistic insight on the energetic aspect of hydrogen dissociation, migration, and recombination on dilute alloy systems. Yet, translating these fundamental concepts to the kinetics and free energy of hydrogen dissociation on nanoparticle catalysts operating at ambient pressures and temperatures remains challenging. Here, the effect of the Pd concentration and Pd ensemble size on the catalytic activity, apparent activation energy, and rate-limiting process is addressed by combining experiment and theory. Experiments in a flow reactor show that a compositional change from 4 to 8 atm% Pd of the Pd-in-Au alloy catalyst leads to a strong increase in activity, even exceeding the activity per Pd atom of monometallic Pd under the same conditions, albeit with an increase in apparent activation energy. First-principles calculations show that the rate and apparent activation enthalpy for HD exchange increase when increasing the Pd ensemble size from single Pd atoms to Pd trimers in a Au surface, suggesting that the ensemble size distribution shifts from mainly single Pd atoms on the 4 atm% Pd alloy to larger Pd ensembles of at least three atoms for the 8 atm% Pd/Au catalyst. The DFT studies also indicated that the rate-controlling process is different: H2 (D2) dissociation determines the rate for single atoms, whereas recombination of adsorbed H and D determines the rate on Pd trimers, similar to bulk Pd. Both experiment and theory suggest that the increased reaction rate with increasing Pd content and ensemble size stems from an entropic driving force. Finally, our results support hydrogen migration between Pd sites via Au and indicate that the dilute alloy design prevents the formation of subsurface hydrogen, which is crucial in achieving high selectivity in hydrogenation catalysis.

Adera S, Naworski L, Davitt A, Mandsberg N, Shneidman AV, Alvarenga J, Aizenberg J. Enhanced condensation heat transfer using porous silica inverse opal coatings on copper tubes. Scientific Reports. 2021;11 (1) :1-11. Publisher's VersionAbstract

Phase-change condensation is commonplace in nature and industry. Since the 1930s, it is well understood that vapor condenses in filmwise mode on clean metallic surfaces whereas it condenses by forming discrete droplets on surfaces coated with a promoter material. In both filmwise and dropwise modes, the condensate is removed when gravity overcomes pinning forces. In this work, we show rapid condensate transport through cracks that formed due to material shrinkage when a copper tube is coated with silica inverse opal structures. Importantly, the high hydraulic conductivity of the cracks promote axial condensate transport that is beneficial for condensation heat transfer. In our experiments, the cracks improved the heat transfer coefficient from ≈ 12 kW/m2 K for laminar filmwise condensation on smooth clean copper tubes to ≈ 80 kW/m2 K for inverse opal coated copper tubes; nearly a sevenfold increase from filmwise condensation and identical enhancement with state-of-the-art dropwise condensation. Furthermore, our results show that impregnating the porous structure with oil further improves the heat transfer coefficient by an additional 30% to ≈ 103 kW/m2 K. Importantly, compared to the fast-degrading dropwise condensation, the inverse opal coated copper tubes maintained high heat transfer rates when the experiments were repeated > 20 times; each experiment lasting 3–4 h. In addition to the new coating approach, the insights gained from this work present a strategy to minimize oil depletion during condensation from lubricated surfaces.

Zhu P, Chen R, Zhou C, Aizenberg M, Aizenberg J, Wang L. Bioinspired Soft Microactuators. Advanced Materials Interfaces. 2021;33 (21) :2008558. Publisher's VersionAbstract
Soft actuators have the potential of revolutionizing the field of robotics. However, it has been a long-standing challenge to achieve simultaneously: i) miniaturization of soft actuators, ii) high contrast between materials properties at their “on” and “off” states, iii) significant actuation for high-payload mechanical work, and iv) ability to perform diverse shape transformations. This challenge is addressed by synergistically utilizing structural concepts found in the dermis of sea cucumbers and the tendrils of climbing plants, together with microfluidic fabrication to create diatomite-laden hygroscopically responsive fibers with a discontinuous ribbon of stiff, asymmetrically shaped, and hygroscopically inactive microparticles embedded inside. The microactuators can undergo various deformations and have very high property contrast ratios (20–850 for various mechanical characteristics of interest) between hydrated and dehydrated states. The resulting energy density, actuation strain, and actuation stress are shown to exceed those of natural muscle by ≈4, >2, and >30 times, respectively, and their weight-lifting ratio is 2–3 orders of magnitude higher than the value of recent hygroscopic actuators. This work offers a new and general way to design and fabricate next-generation soft microactuators, and thus advances the field of soft robotics by tailoring the structure and properties of deformable elements to suit a desired application.
Frost IM, Mendoza A, Chiou T-T, Wattanatorn N, Zhao C, Yang Q, Kim P, Aizenberg J, De Oliveira S, Weiss PS, et al. Slippery Liquid-Infused Porous Surfaces (SLIPS) for Cell Deformation Enabling Intracellular Cargo Delivery. MOLECULAR THERAPY. 2021;29 (4) :233.
Li S, Deng B, Grinthal A, Schneider-Yamamura A, Kang J, Martens RS, Zhang CT, Li J, Yu S, Bertoldi K, et al. Liquid-induced topological transformations of cellular microstructures. Nature . 2021;592 (7854) :386-391. Publisher's VersionAbstract

The fundamental topology of cellular structures—the location, number and connectivity of nodes and compartments—can profoundly affect their acoustic, electrical, chemical, mechanical, and optical properties, as well as heat, fluid and particle transport. Approaches that harness swelling, electromagnetic actuation and mechanical instabilities in cellular materials have enabled a variety of interesting wall deformations and compartment shape alterations, but the resulting structures generally preserve the defining connectivity features of the initial topology. Achieving topological transformation presents a distinct challenge for existing strategies: it requires complex reorganization, repacking, and coordinated bending, stretching and folding, particularly around each node, where elastic resistance is highest owing to connectivity. Here we introduce a two-tiered dynamic strategy that achieves systematic reversible transformations of the fundamental topology of cellular microstructures, which can be applied to a wide range of materials and geometries. Our approach requires only exposing the structure to a selected liquid that is able to first infiltrate and plasticize the material at the molecular scale, and then, upon evaporation, form a network of localized capillary forces at the architectural scale that ‘zip’ the edges of the softened lattice into a new topological structure, which subsequently restiffens and remains kinetically trapped. Reversibility is induced by applying a mixture of liquids that act separately at the molecular and architectural scales (thus offering modular temporal control over the softening–evaporation–stiffening sequence) to restore the original topology or provide access to intermediate modes. Guided by a generalized theoretical model that connects cellular geometries, material stiffness and capillary forces, we demonstrate programmed reversible topological transformations of various lattice geometries and responsive materials that undergo fast global or localized deformations. We then harness dynamic topologies to develop active surfaces with information encryption, selective particle trapping and bubble release, as well as tunable mechanical, chemical and acoustic properties.

Zhang C, Adera S, Aizenberg J, Chen Z. Why Are Water Droplets Highly Mobile on Nanostructured Oil-Impregnated Surfaces?. ACS Applied Materials & Interfaces. 2021;13 (13) :15901-15909. Publisher's VersionAbstract

Porous lubricated surfaces (aka slippery liquid-infused porous surfaces, SLIPS) have been demonstrated to repel various liquids. The origin of this repellency, however, is not fully understood. By using surface-sensitive sum frequency generation vibrational spectroscopy, we characterized the water/oil interface of a water droplet residing on (a) an oil-impregnated nanostructured surface (SLIPS) and (b) the same oil layer without the underlying nanostructures. Different from water molecules in contact with bulk oil without nanostructures, droplets on SLIPS adopt a molecular orientation that is predominantly parallel to the water/oil interface, leading to weaker hydrogen bonding interactions between water droplets and the lubrication film, giving SLIPS their water repellency. Our results demonstrate that the molecular interactions between two contacting liquids can be manipulated by the implementation of nanostructured substrates. The results also offer the molecular principles for controlling nanostructure to reduce oil depletion—one of the limitations and major concerns of SLIPS.

Nicolas N, Duffy MA, Hansen A, Aizenberg J. Inverse Opal Films for Medical Sensing: Application in Diagnosis of Neonatal Jaundice. Advanced Healthcare Materials. 2021;10 (4) :2001326. Publisher's VersionAbstract

A non-invasive, at-home test for neonatal jaundice can facilitate early jaundice detection in infants, improving clinical outcomes for neonates with severe jaundice and helping to prevent the development of kernicterus, a type of brain damage whose symptoms include hearing loss, impairment of cognitive capacity, and death. Here a photonic sensor that utilizes color changes induced by analyte infiltration into a chemically functionalized inverse opal structure is developed. The sensor is calibrated to detect differences in urinary surface tension due to increased bile salt concentration in urine, which is symptomatic of abnormal liver function and linked to jaundice. The correlation between neonatal urinary surface tension and excess serum bilirubin, the physiologic cause of neonatal jaundice, is explored. It is shown that these non-invasive sensors can improve the preliminary diagnosis of neonatal jaundice, reducing the number of invasive blood tests and hospital visits necessary for healthy infants while ensuring that jaundiced infants are treated in a timely manner. The use of inverse opal sensors to measure bulk property changes in bodily fluids can be extended to the detection of several other conditions, making this technology a versatile platform for convenient point-of-care diagnosis.

Fernandes M, Aizenberg J, Weaver J, Bertoldi K. Mechanically robust lattices inspired by deep-sea glass sponges. Nature Materials. 2021;20 (2) :237-241. Publisher's VersionAbstract

The predominantly deep-sea hexactinellid sponges are known for their ability to construct remarkably complex skeletons from amorphous hydrated silica. The skeletal system of one such species of sponge, Euplectella aspergillum, consists of a square-grid-like architecture overlaid with a double set of diagonal bracings, creating a chequerboard-like pattern of open and closed cells. Here, using a combination of finite element simulations and mechanical tests on 3D-printed specimens of different lattice geometries, we show that the sponge’s diagonal reinforcement strategy achieves the highest buckling resistance for a given amount of material. Furthermore, using an evolutionary optimization algorithm, we show that our sponge-inspired lattice geometry approaches the optimum material distribution for the design space considered. Our results demonstrate that lessons learned from the study of sponge skeletal systems can be exploited for the realization of square lattice geometries that are geometrically optimized to avoid global structural buckling, with implications for improved material use in modern infrastructural applications.

Hwang V, Stephenson A, Barkley S, Brandt S, Xiao M, Aizenberg J, Manoharan VN. Designing angle-independent structural colors using Monte Carlo simulations of multiple scattering. Proceedings of the National Academy of Sciences. 2021;118 (4) :e2015551118. Publisher's VersionAbstract

Disordered nanostructures with correlations on the scale of visible wavelengths can show angle-independent structural colors. These materials could replace dyes in some applications because the color is tunable and resists photobleaching. However, designing nanostructures with a prescribed color is difficult, especially when the application—cosmetics or displays, for example—requires specific component materials. A general approach to solving this constrained design problem is modeling and optimization: Using a model that predicts the color of a given system, one optimizes the model parameters under constraints to achieve a target color. For this approach to work, the model must make accurate predictions, which is challenging because disordered nanostructures have multiple scattering. To address this challenge, we develop a Monte Carlo model that simulates multiple scattering of light in disordered arrangements of spherical particles or voids. The model produces quantitative agreement with measurements when we account for roughness on the surface of the film, particle polydispersity, and wavelength-dependent absorption in the components. Unlike discrete numerical simulations, our model is parameterized in terms of experimental variables, simplifying the connection between simulation and fabrication. To demonstrate this approach, we reproduce the color of the male mountain bluebird (Sialia currucoides) in an experimental system, using prescribed components and a microstructure that is easy to fabricate. Finally, we use the model to find the limits of angle-independent structural colors for a given system. These results enable an engineering design approach to structural color for many different applications.

Shirman T, Toops TJ, Shirman E, Shneidman AV, Liu S, Gurkin K, Alvarenga J, Lewandowski M, Aizenberg M, Aizenberg J. Raspberry colloid-templated approach for the synthesis of palladium-based oxidation catalysts with enhanced hydrothermal stability and low-temperature activity. Catalysis Today. 2021;360 :241-251. Publisher's VersionAbstract

It is becoming increasingly urgent to develop and utilize novel, more efficient and stable materials for mobile and stationary emission control applications as the deleterious consequences of anthropogenic air pollution are becoming more evident and pressing. Tightening regulations, particularly related to automotive exhaust treatment, together with continued improvements in engine design, that result in lowering the engine operating temperatures and inadvertently lead to the release of an overwhelming proportion of pollutants during the cold start, present new challenges for materials design, specifically for oxidation catalysts. In particular, improvements in the low-temperature activity while maintaining catalyst stability at high temperatures are required from the next-generation catalyst. Typical catalysts for removal of pollutants from automotive exhaust streams incorporate platinum group metals (PGMs). They tend to be inefficient at low temperatures (below 250 °C), thus accounting for the cold start problem, yet sinter and lose their activity at high temperatures that are frequently encountered during catalyst operation. High PGM loadings are often employed to compensate for catalyst inefficiencies and fast degradation, ultimately resulting in high-cost catalytic converters. We have developed a new approach for the design and formation of catalytic materials that allows for both significantly more efficient PGM incorporation and improved overall catalyst performance at reduced PGM loadings. The method provides control over the composition and geometry of the support through self-assembly of sacrificial composite template — “raspberry” polymeric colloids decorated with catalytic particles — accompanied by infiltration with metal-oxide precursor and subsequent removal of the colloids. This method simultaneously structures the porous network and organizes the catalytic particles within it. Uniquely, the resulting catalytic particles are partially embedded in the support matrix and partially exposed to the pore interior, producing catalytic sites that are both stable and accessible. Herein, the feasibility of this novel and versatile approach for automotive catalytic conversion is demonstrated: the studies include testing alumina-based raspberry-colloid-templated (RCT) catalysts containing Pd nanoparticles (RCT Pd/Al2O3) for oxidation of propane and carbon monoxide under simulated diesel exhaust conditions and hydrothermal aging at 800 °C for 50 h in the simulated stream. The RCT Pd/Al2O3 catalysts exhibit exceptional activity toward CO oxidation, reduced reaction onset temperature, and high stability to elevated temperatures (demonstrated through prolonged exposure to temperatures up to 950 °C) and reactive gas streams, without migration, sintering or loss of the precious metal NPs. Notably, the novel catalyst shows the same or slightly better performance than the commercial catalysts even when the PGM load is reduced by ∼80 % compared to the commercial counterparts. These results provide confidence for the utilization of the RCT approach for the fabrication of robust nanostructured catalysts for next-generation, energy-efficient catalytic converters with improved performance at low and high temperatures and reduced costs. The RCT methodology is, in addition, highly generalizable, and can thus be applied for the design of a wide range of catalytic systems in the automotive sector and beyond.

Chatterjee R, Biswas S, Yashin VV, Aizenberg M, Aizenberg J, Balazs AC. Controllable growth of interpenetrating or random copolymer networks . Soft Matter. 2021;17 (30) :7177-7187. Publisher's VersionAbstract

Interpenetrating and random copolymer networks are vital in a number of industrial applications, including the fabrication of automotive parts, damping materials, and tissue engineering scaffolds. We develop a theoretical model for a process that enables the controlled growth of interpenetrating network (IPNs), or a random copolymer network (RCN) of specified size and mechanical properties. In this process, a primary gel “seed” is immersed into a solution containing the secondary monomer and crosslinkers. After the latter species are absorbed into the primary network, the absorbed monomers are polymerized to form the secondary polymer chains, which then can undergo further crosslinking to form an IPN, or undergo inter-chain exchange with the existing network to form a RCN. The swelling and elastic properties of the IPN and RCN networks can be tailored by modifying the monomer and crosslinker concentrations in the surrounding solution, or by tuning the enthalpic interactions between the primary polymer, secondary monomer and solvent through a proper choice of chemistry. This process can be used repeatedly to fabricate gels with a range of mechanical properties from stiff, rigid materials to soft, flexible networks, allowing the method to meet the materials requirements of a variety of applications.

Filie A, Shirman T, Aizenberg M, Aizenberg J, Friend CM, Madix RJ. The dynamic behavior of dilute metallic alloy Pd x Au 1− x/SiO 2 raspberry colloid templated catalysts under CO oxidation. Catalysis Science & Technology. 2021;(11) :4072-4082. Publisher's VersionAbstract

Dilute palladium-in-gold alloys have potential as efficient oxidation catalysts; controlling the Pd surface distribution is critical. Here, the activity for CO oxidation catalyzed by robust dilute Pd-in-Au nanoparticles supported on raspberry-colloid-templated (RCT) silica depends on the pretreatment and gas environment. The activities of oxygen-pretreated catalysts are different in light-off studies versus after long-term use. Transient increases in activity are also induced by flowing CO/He at 553 K. Altogether, these results indicate changes in Pd distribution at the surface induced by reactive gases and that light-off studies alone are not adequate for evaluation of alloy catalyst performance. Kinetic studies show evidence of both isolated and multiple Pd atoms. A dual-site mechanism is operative over Pd0.02Au0.98 RCT-SiO2, whereas a single-site mechanism governs reaction over Pd0.10Au0.90 RCT-SiO2. The distinct mechanisms suggest that tuning the ratio of isolated to clustered Pd sites is possible, underscoring the importance of characterization under reaction conditions.

Vena A, Kolle S, Stafslien S, Aizenberg J, Kim P. Self‐Stratifying Porous Silicones with Enhanced Liquid Infusion and Protective Skin Layer for Biofouling Prevention. Advanced Materials Interfaces. 2021;8 (22) :2000359. Publisher's VersionAbstract

Liquid-infused silicones are a promising solution for common surface adhesion problems, such as ice accumulation and biofilm formation, yet they generally lack the tunability, mechanical durability and/or longevity essential for industrial applications. Self-stratifying porous silicones (SPS) infused with compatible silicone oil are developed as a passive strategy to address these shortcomings. Through emulsion templating, porosity is formed in the bulk polymer, providing increased free volume for oil infusion, while a non-porous skin layer is formed at the surface. The bulk porosity and pore size distribution of SPS are independently controlled by varying water and surfactant concentration respectively, leading to a higher volume of oil infusion and improved oil retention relative to an unmodified silicone. Despite a higher oil loading and bulk porosity, the skin layer provides liquid-infused SPS with a comparable surface elasticity to liquid-infused silicones. The potential of liquid-infused SPS as a nontoxic fouling release coating for marine applications is demonstrated using laboratory assays against a variety of soft and hard fouling organisms.

2020
Tomholt L, Geletina O, Alvarenga J, Shneidman AV, Weaver JC, Fernandes MC, Mota SA, Bechthold M, Aizenberg J. Tunable infrared transmission for energy-efficient pneumatic building façades. Energy and Buildings. 2020;(226) :110377. Publisher's VersionAbstract

Thermal regulation of buildings in climates with daily and seasonal weather changes can prove challenging and result in high building energy consumption. While adaptable façades with tunable infrared transmitting properties could modulate solar transmittance through the building envelope and, as such, increase energy efficiency, available technologies to meet these needs are often expensive, relatively complicated, and challenging to implement in a lightweight form factor.

Motivated by these limitations, this report presents a novel tunable light-modulating technology for energy-efficient pneumatic façades in the form of polydimethylsiloxane (PDMS) film with a thin gold surface coating. Sequential stretching and relaxing of this film results in strain-induced microscale surface cracks that can significantly modulate both visible and near infrared light transmission, and consequently, the material’s solar heat gain coefficient (SHGC).

The material’s tunability has shown a significant potential to reduce building energy use, as assessed with building simulation software. The technology offers additional advantages for light modulation in pneumatic façades including real-time operation, ease of implementation and control, and predictable performance. Façade design guidelines for the integration of the infrared-regulating film into ethylene tetrafluoroethylene (ETFE) building envelopes and climate suitability are described, and a critical evaluation of material durability, optical clarity, and material costs are provided.

Adera S, Alvarenga J, Shneidman AV, Zhang CT, Davitt A, Aizenberg J. Depletion of Lubricant from Nanostructured Oil-Infused Surfaces by Pendant Condensate Droplets. ACS Nano. 2020;14 (7) :8024–8035. Publisher's VersionAbstract

Due to recent advances in nanofabrication, phase-change condensation heat transfer has seen a renaissance. Compared to conventional heat transfer surfaces, nanostructured surfaces impregnated with chemically matched lubrication films (hereinafter referred to as “nanostructured lubricated surfaces”) have been demonstrated to improve vapor-side phase-change condensation heat transfer by facilitating droplet nucleation, growth, and departure. While the presence of nanoscale roughness improves performance longevity by stabilizing the lubrication film via capillary forces, such enhancement is short-lived due to the eventual loss of lubrication oil by the departing droplets. The objective of this study is to characterize oil depletion caused by pendant droplets during condensation. For our study, we nanostructured, chemically functionalized, and lubricated horizontal copper tubes that are widely used in shell-and-tube heat exchangers in power plants and process industries. Using high-speed fluorescence imaging and thermogravimetric analysis, we show that shedding droplets exert a shear force on the oil in the wetting ridge at the water–oil interface. The viscous shear draws the lubrication film from the nanostructured surface onto the upper portion of the droplet and forms a ring-like oil skirt. Through detailed theoretical analysis, we show that the thickness of this oil skirt scales with the classical Landau–Levich–Derjaguin (LLD) theory for dip-coating. Our results reveal that droplets falling from horizontal tubes break unequally and leave behind small satellite droplets that retain the bulk of the oil in the wetting ridge. This observation is in stark contrast with the earlier description of droplets shedding from tilted flat plates where the entire oil-filled wetting ridge is demonstrated to leave the surface upon droplet departure. By selecting lubrication oils of varying viscosity and spreading coefficient, we provide evidence that the contribution of the wrapping layer to the rate of oil depletion is insignificant. Furthermore, we show that due to the nanoscale features on the tubes, nearly half of the lubrication film remains on the surface after 10 h of continuous steam condensation at ambient pressure, 23 °C, and 60% relative humidity, a 2–3-fold improvement over previous results.The insights gained from this work will provide guidelines for the rational design of long-lasting nanostructured lubricated surfaces for phase-change condensation.

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