Corrosion and surface fouling of structural materials, such as concrete, are persistent problems accelerating undesirable material degradation for many industries and infrastructures. To counteract these detrimental effects, protective coatings are frequently applied, but these solid-based coatings can degrade or become mechanically damaged over time. Such irreversible and irreparable damage on solid-based protective coatings expose underlying surfaces and bulk materials to adverse environmental stresses leading to subsequent fouling and degradation. We introduce a new concept of a hybrid liquid-in-solid protective barrier (LIB) to overcome the limitations of traditional protective coatings with broad applicability to structural materials. Through optimization of capillary forces and reduction of the interfacial energy between an upper mobile liquid and a lower immobile solid phase, a stable liquid-based protective layer is created. This provides a persistent self-repairing barrier against the infiltration of moisture and salt, in addition to omniphobic surface properties. As a model experimental test bed, we applied this concept to cementitious materials, which are commonly used as binders in concrete, and investigated how the mobile liquid phase embedded within a porous solid support contributes to the material’s barrier protection and antifouling properties. Using industry standard test methods for acid resistance, chloride-ion penetrability, freeze–thaw cyclability, and mechanical durability, we demonstrate that LIBs exhibit significantly reduced water absorption and ion penetrability, improved repellency against various nonaqueous liquids, and resistance to corrosion while maintaining their required mechanical performance as structural materials.Corrosion and surface fouling of structural materials, such as concrete, are persistent problems accelerating undesirable material degradation for many industries and infrastructures. To counteract these detrimental effects, protective coatings are frequently applied, but these solid-based coatings can degrade or become mechanically damaged over time. Such irreversible and irreparable damage on solid-based protective coatings expose underlying surfaces and bulk materials to adverse environmental stresses leading to subsequent fouling and degradation. We introduce a new concept of a hybrid liquid-in-solid protective barrier (LIB) to overcome the limitations of traditional protective coatings with broad applicability to structural materials. Through optimization of capillary forces and reduction of the interfacial energy between an upper mobile liquid and a lower immobile solid phase, a stable liquid-based protective layer is created. This provides a persistent self-repairing barrier against the infiltration of moisture and salt, in addition to omniphobic surface properties. As a model experimental test bed, we applied this concept to cementitious materials, which are commonly used as binders in concrete, and investigated how the mobile liquid phase embedded within a porous solid support contributes to the material’s barrier protection and antifouling properties. Using industry standard test methods for acid resistance, chloride-ion penetrability, freeze–thaw cyclability, and mechanical durability, we demonstrate that LIBs exhibit significantly reduced water absorption and ion penetrability, improved repellency against various nonaqueous liquids, and resistance to corrosion while maintaining their required mechanical performance as structural materials.
This research introduces a novel approach to control light transmittance based on flexible polydimethylsiloxane (PDMS) films that have been plasma-treated such that micro-scale surface features have a visual effect as the film responds to applied strain. The effect is continuously tunable from optically clear (71.5% Transmittance over a 400–900 nm wavelength) to completely diffuse (18.1% T). Changes in the film's optical properties are triggered by bi-axial strains applied using a pneumatic system to form pressurized envelopes. This paper reports on a series of experimental studies and provides system integration research using prototypes, simulations and geometric models to correlate measured optical properties, strain, and global surface curvatures. In conclusion, a design is proposed to integrate PDMS light control within existing building envelopes.
Two alternatives are investigated and compared: System A uses positive pressure featuring an exterior grid to restrain and shape the inflated film during expansion; System B uses negative pressure where the films are shaped according to the geometry of an interstitial grid that serves as a spacer between two film surfaces. Both systems can provide effective control of opacity levels using pneumatic pressure and may be suitable for use with existing glazing systems or ethylene tetrafluoroethylene (ETFE) pneumatic envelopes.
Mechanical forces in the cell’s natural environment have a crucial impact on growth, differentiation and behaviour. Few areas of biology can be understood without taking into account how both individual cells and cell networks sense and transduce physical stresses. However, the field is currently held back by the limitations of the available methods to apply physiologically relevant stress profiles on cells, particularly with sub-cellular resolution, in controlled in vitro experiments. Here we report a new type of active cell culture material that allows highly localized, directional and reversible deformation of the cell growth substrate, with control at scales ranging from the entire surface to the subcellular, and response times on the order of seconds. These capabilities are not matched by any other method, and this versatile material has the potential to bridge the performance gap between the existing single cell micro-manipulation and 2D cell sheet mechanical stimulation techniques.
We describe the behavior of a temperature-responsive hydrogel actuated integrated responsive structure (HAIRS). The structure is constructed by embedding a rigid high-aspect-ratio post in a layer of poly(Nisopropylacrylamide) (PNIPAM) hydrogel which is bonded to a rigid substrate. As the hydrogel contracts, the post abruptly tilts. The HAIRS has demonstrated its broad applications in generating reversible micropattern formation, active optics, tunable wettability, and artificial homeostasis. To quantitatively describe and predict the system behavior, we construct an analytical model combining the structural instability, i.e. buckling of the post, and the material instability, i.e. the volume phase transition of PNIPAM hydrogel. The two instabilities of the system result in a large hysteresis in response to heating and cooling processes. Experimental results validate the predicted phenomenon of the abrupt tilting as temperature and large hysteresis in a heating-and-cooling cycle in the PNIPAM actuated HAIRS. Based on this model, we further discuss the influence of the material properties on the actuation of the structure.
Controlling dropwise condensation is fundamental to water-harvesting systems, desalination, thermal power generation, air conditioning, distillation towers, and numerous other applications. For any of these, it is essential to design surfaces that enable droplets to grow rapidly and to be shed as quickly as possible. However, approaches based on microscale, nanoscale or molecular-scale textures suffer from intrinsic trade-offs that make it difficult to optimize both growth and transport at once. Here we present a conceptually different design approach—based on principles derived from Namib desert beetles, cacti, and pitcher plants—that synergistically combines these aspects of condensation and substantially outperforms other synthetic surfaces. Inspired by an unconventional interpretation of the role of the beetle’s bumpy surface geometry in promoting condensation, and using theoretical modelling, we show how to maximize vapour diffusion flux at the apex of convex millimetric bumps by optimizing the radius of curvature and cross-sectional shape. Integrating this apex geometry with a widening slope, analogous to cactus spines, directly couples facilitated droplet growth with fast directional transport, by creating a free-energy profile that drives the droplet down the slope before its growth rate can decrease. This coupling is further enhanced by a slippery, pitcher-plant-inspired nanocoating that facilitates feedback between coalescence-driven growth and capillary-driven motion on the way down. Bumps that are rationally designed to integrate these mechanisms are able to grow and transport large droplets even against gravity and overcome the effect of an unfavourable temperature gradient. We further observe an unprecedented sixfold-higher exponent of growth rate, faster onset, higher steady-state turnover rate, and a greater volume of water collected compared to other surfaces. We envision that this fundamental understanding and rational design strategy can be applied to a wide range of water-harvesting and phase-change heat-transfer applications.
Passive anti-icing surfaces, or icephobic surfaces, are an area of great interest because of their significant economic, energy and safety implications in the prevention and easy removal of ice in many facets of society. The complex nature of icephobicity, which requires performance in a broad range of icing scenarios, creates many challenges when designing ice-repellent surfaces. Although superhydrophobic surfaces incorporating micro- or nanoscale roughness have been shown to prevent ice accumulation under certain conditions, the same roughness can be detrimental in other environments. Surfaces that present a smooth liquid interface can eliminate some of the drawbacks of textured superhydrophobic surfaces, but additional study is needed to fully realize their potential. As attention begins to shift towards alternative anti-icing strategies, it is important to consider and to understand the nature of ice repellency in all environments to identify the limitations of current solutions and to design new materials with robust icephobicity.
There is a dire need for infection prevention strategies that do not require the use of antibiotics, which exacerbate the rise of multi- and pan-drug resistant infectious organisms. An important target in this area is the bacterial attachment and subsequent biofilm formation on medical devices (e.g., catheters). Here we describe nonfouling, lubricant-infused slippery polymers as proof-of-concept medical materials that are based on oil-infused polydimethylsiloxane (iPDMS). Planar and tubular geometry silicone substrates can be infused with nontoxic silicone oil to create a stable, extremely slippery interface that exhibits exceptionally low bacterial adhesion and prevents biofilm formation. Analysis of a flow culture of Pseudomonas aeruginosa through untreated PDMS and iPDMS tubing shows at least an order of magnitude reduction of biofilm formation on iPDMS, and almost complete absence of biofilm on iPDMS after a gentle water rinse. The iPDMS materials can be applied as a coating on other polymers or prepared by simply immersing silicone tubing in silicone oil, and are compatible with traditional sterilization methods. As a demonstration, we show the preparation of silicone-coated polyurethane catheters and significant reduction of Escherichia coli and Staphylococcus epidermidis biofilm formation on the catheter surface. This work represents an important first step toward a simple and effective means of preventing bacterial adhesion on a wide range of materials used for medical devices.
The stability and longevity of surface-stabilized lubricant layers is a critical question in their application as low- and nonfouling slippery surface treatments in both industry and medicine. Here, we investigate lubricant loss from surfaces under flow in water using both quantitative analysis and visualization, testing the effects of underlying surface type (nanostructured versus flat), as well as flow rate in the physiologically relevant range, lubricant type, and time. We find lubricant losses on the order of only ng/cm2 in a closed system, indicating that these interfaces are relatively stable under the flow conditions tested. No notable differences emerged between surface type, flow rate, lubricant type, or time. However, exposure of the lubricant layers to an air/water interface did significantly increase the amount of lubricant removed from the surface, leading to disruption of the layer. These results may help in the development and design of materials using surface-immobilized lubricant interfaces for repellency under flow conditions.
Formation of unwanted deposits on steels during their interaction with liquids is an inherent problem that often leads to corrosion, biofouling and results in reduction in durability and function. Here we report a new route to form anti-fouling steel surfaces by electrodeposition of nanoporous tungsten oxide (TO) films. TO-modified steels are as mechanically durable as bare steel and highly tolerant to compressive and tensile stresses due to chemical bonding to the substrate and island-like morphology. When inherently superhydrophilic TO coatings are converted to superhydrophobic, they remain non-wetting even after impingement with yttria-stabilized-zirconia particles, or exposure to ultraviolet light and extreme temperatures. Upon lubrication, these surfaces display omniphobicity against highly contaminating media retaining hitherto unseen mechanical durability. To illustrate the applicability of such a durable coating in biofouling conditions, we modified naval construction steels and surgical instruments and demonstrated significantly reduced marine algal film adhesion, Escherichia coli attachment and blood staining.
Recently, diffraction elements that reverse the color sequence normally observed in planar diffraction gratings have been found in the wing scales of the butterfly Pierella luna. Here, we describe the creation of an artificial photonic material mimicking this re- verse color-order diffraction effect. The bioinspired system con- sists of ordered arrays of vertically oriented microdiffraction gratings. We present a detailed analysis and modeling of the cou- pling of diffraction resulting from individual structural compo- nents and demonstrate its strong dependence on the orientation of the individual miniature gratings. This photonic material could provide a basis for novel developments in biosensing, anticoun- terfeiting, and efficient light management in photovoltaic systems and light-emitting diodes.
Thrombosis and biofouling of extracorporeal circuits and indwelling medical devices cause significant morbidity and mortality worldwide. We apply a bioinspired, omniphobic coating to tubing and catheters and show that it completely repels blood and suppresses biofilm formation. The coating is a covalently tethered, flexible molecular layer of perfluorocarbon, which holds a thin liquid film of medical-grade perfluorocarbon on the surface. This coating prevents fibrin attachment, reduces platelet adhesion and activation, suppresses biofilm formation and is stable under blood flow in vitro. Surface-coated medical-grade tubing and catheters, assembled into arteriovenous shunts and implanted in pigs, remain patent for at least 8 h without anticoagulation. This surface-coating technology could reduce the use of anticoagulants in patients and help to prevent thrombotic occlusion and biofouling of medical devices.
The deep building layouts typical in the U.S. have led to a nearly complete reliance on artificial lighting in standard office buildings. The development of daylight control systems that maximize the penetration and optimize the distribution of natural daylight in buildings has the potential for saving a significant portion of the energy consumed by artificial lighting, but existing systems are either static, costly, or obstruct views towards the outside. We report the Dynamic Daylight Control System (DDCS) that in- tegrates a thin cast transparent polydimethylsiloxane (PDMS)-based deformable array of louvers and waveguides within a millimeter-scale fluidic channel system. This system can be dynamically tuned to the different climates and sun positions to control daylight quality and distribution in the interior space. The series of qualitative and quantitative tests confirmed that DDCS exceeds conventional double glazing system in terms of reducing glare near the window and distributing light to the rear of the space. The system can also be converted to a visually transparent or a translucent glazing by filling the channels with an appropriate fluid. DDCS can be integrated or retrofitted to conventional glazing systems and allow for diffusivity and transmittance control.
The development of a stain-resistant and pressure-stable textile is desirable for consumer and industrial applications alike, yet it remains a challenge that current technologies have been unable to fully address. Traditional superhydrophobic surfaces, inspired by the lotus plant, are characterized by two main components: hydrophobic chemical functionalization and surface roughness. While this approach produces water-resistant surfaces, these materials have critical weaknesses that hinder their practical utility, in particular as robust stain-free fabrics. For example, traditional superhydrophobic surfaces fail (i.e., become stained) when exposed to low-surface-tension liquids, under pressure when impacted by a high-velocity stream of water (e.g., rain), and when exposed to physical forces such as abrasion and twisting. We have recently introduced slippery lubricant-infused porous surfaces (SLIPS), a self-healing, pressure-tolerant and omniphobic surface, to address these issues. Herein we present the rational design and optimization of nanostructured lubricant-infused fabrics and demonstrate markedly improved performance over traditional superhydrophobic textile treatments: SLIPS-functionalized cotton and polyester fabrics exhibit decreased contact angle hysteresis and sliding angles, omni-repellent properties against various fluids including polar and nonpolar liquids, pressure tolerance and mechanical robustness, all of which are not readily achievable with the state-of-the-art superhydrophobic coatings.
Omniphobic fluorogel elastomers were prepared by photocuring perfluorinated acrylates and a perfluoropolyether crosslinker. By tuning either the chemical composition or the temperature that control the crystallinity of the resulting polymer chains, a broad range of optical and mechanical properties of the fluorogel can be achieved. After infusing with fluorinated lubricants, the fluorogels showed excellent resist- ance to wetting by various liquids and anti-biofouling behavior, while maintaining cytocompatiblity.
Biofilms, surface-bound communities of microbes, are economically and medically important due to their pathogenic and obstructive properties. Among the numerous strategies to prevent bacterial adhesion and subsequent biofilm formation, surface topography was recently proposed as a highly nonspecific method that does not rely on small-molecule antibacterial compounds, which promote resistance. Here, we provide a detailed investigation of how the introduction of submicrometer crevices to a surface affects attachment of Escherichia coli. These crevices reduce substrate surface area available to the cell body but increase overall surface area. We have found that, during the first 2 h, adhesion to topographic surfaces is significantly reduced compared with flat controls, but this behavior abruptly reverses to significantly increased adhesion at longer exposures. We show that this reversal coincides with bacterially induced wetting transitions and that flagellar filaments aid in adhesion to these wetted topographic surfaces. We demonstrate that flagella are able to reach into crevices, access additional surface area, and produce a dense, fibrous network. Mutants lacking flagella show comparatively reduced adhesion. By varying substrate crevice sizes, we determine the conditions under which having flagella is most advantageous for adhesion. These findings strongly indicate that, in addition to their role in swimming motility, flagella are involved in attachment and can furthermore act as structural elements, enabling bacteria to overcome unfavorable surface topographies. This work contributes insights for the future design of antifouling surfaces and for improved understanding of bacterial behavior in native, structured environments.
Most bacteria live in multicellular communities known as biofilms that are adherent to surfaces in our environment, from sea beds to plumbing systems. Biofilms are often associated with clinical infections, nosocomial deaths and industrial damage such as bio-corrosion and clogging of pipes. As mature biofilms are extremely challenging to eradicate once formed, prevention is advantageous over treatment. However, conventional surface chemistry strategies are either generally transient, due to chemical masking, or toxic, as in the case of leaching marine antifouling paints. Inspired by the nonfouling skins of echinoderms and other marine organisms, which possess highly dynamic surface structures that mechanically frustrate bio-attachment, we have developed and tested a synthetic platform based on both uniaxial mechanical strain and buckling-induced elastomer microtopography. Bacterial biofilm attachment to the dynamic substrates was studied under an array of parameters, including strain amplitude and timescale (1–100 mm s−1), surface wrinkle length scale, bacterial species and cell geometry, and growth time. The optimal conditions for achieving up to ~ 80% Pseudomonas aeruginosa biofilm reduction after 24 h growth and ~ 60% reduction after 48 h were combinatorially elucidated to occur at 20% strain amplitude, a timescale of less than ~ 5 min between strain cycles and a topography length scale corresponding to the cell dimension of ~ 1 μm. Divergent effects on the attachment of P. aeruginosa, Staphylococcus aureus and Escherichia coli biofilms showed that the dynamic substrate also provides a new means of species-specific biofilm inhibition, or inversely, selection for a desired type of bacteria, without reliance on any toxic or transient surface chemical treatments.
Lubricant-infused textured solid substrates are gaining remarkable interest as a new class of omni-repellent nonfouling materials and surface coatings. We investigated the effect of the length scale and hierarchy of the surface topography of the underlying substrates on their ability to retain the lubricant under high shear conditions, which is important for maintaining nonwetting properties under application-relevant conditions. By comparing the lubricant loss, contact angle hysteresis, and sliding angles for water and ethanol droplets on flat, microscale, nanoscale, and hierarchically textured surfaces subjected to various spinning rates (from 100 to 10 000 rpm), we show that lubricant-infused textured surfaces with uniform nanofeatures provide the most shear-tolerant liquid-repellent behavior, unlike lotus leaf-inspired superhydrophobic surfaces, which generally favor hierarchical structures for improved pressure stability and low contact angle hysteresis. On the basis of these findings, we present generalized, low-cost, and scalable methods to manufacture uniform or regionally patterned nanotextured coatings on arbitrary materials and complex shapes. After functionalization and lubrication, these coatings show robust, shear-tolerant omniphobic behavior, transparency, and nonfouling properties against highly contaminating media.
Ice repellent coatings have been studied and keenly sought after for many years, where any advances in the durability of such coatings will result in huge energy savings across many fields. Progress in creating anti-ice and anti-frost surfaces has been particularly rapid since the discovery and development of slippery, liquid infused porous surfaces (SLIPS). Here we use SLIPS-coated differential scanning calorimeter (DSC) pans to investigate the effects of the surface modification on the nucleation of supercooled water. This investigation is inherently different from previous studies which looked at the adhesion of ice to SLIPS surfaces, or the formation of ice under high humidity conditions. Given the stochastic nature of nucleation of ice from supercooled water, multiple runs on the same sample are needed to determine if a given surface coating has a real and statistically significant effect on the nucleation temperature. We have cycled supercooling to freezing and then thawing of deionized water in hydrophilic (untreated aluminum), hydrophobic, superhydrophobic, and SLIPS-treated DSC pans multiple times to determine the effects of surface treatment on the nucleation and subsequent growth of ice. We find that SLIPS coatings lower the nucleation temperature of supercooled water in contact with statistical significance and show no deterioration or change in the coating performance even after 150 freeze–thaw cycles.
Rational design strategies for mechano‐responsive optical material systems are created by introducing a simple experimental system that can continuously vary the state of bi‐axial stress to induce various wrinkling patterns, including stripes, labyrinths, herringbones, and rarely observed checkerboards, that can dynamically tune the optical properties. In particular, a switching of two orthogonally oriented stripe wrinkle patterns from oxidized polydimethylsiloxane around the critical strain value is reported, as well as the coexistence of these wrinkles forming elusive checkerboard patterns, which are predicted only in previous simulations. These strain‐induced wrinkle patterns give rise to dynamic changes in optical transmittance and diffraction patterns. A theoretical description of the observed pattern formation is presented which accounts for the residual stress in the membrane and allows for the fine‐tuning of the window of switching of the orthogonal wrinkles. Applications of wrinkle‐induced changes in optical properties are demonstrated, including a mechanically responsive instantaneous privacy screen and a transparent sheet that reversibly reveals a message or graphic and dynamically switches the transmittance when stretched and released.