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Reconfigurable metamaterials require constituent nanostructures to demonstrate switching of shapes with external stimuli. Yet, a longstanding challenge is in overcoming stiction caused by van der Waals forces in the deformed configuration, which impedes shape recovery. Here, we introduce stiff shape memory polymers. This designer material has a storage modulus of ∼5.2 GPa at room temperature and ∼90 MPa in the rubbery state at 150 °C, 1 order of magnitude higher than those in previous reports. Nanopillars with diameters of ∼400 nm and an aspect ratio as high as ∼10 were printed by two-photon lithography. Experimentally, we observe shape recovery as collapsed and touching structures overcome stiction to stand back up. We develop a theoretical model to explain the recoverability of these sub-micrometer structures. Reconfigurable structural color prints with a resolution of 21150 dots per inch and holograms are demonstrated, indicating potential applications of the stiff shape memory polymers in high-resolution reconfigurable nanophotonics.

Four-dimensional (4D) printing of shape memory polymer (SMP) imparts time responsive properties to 3D structures. Here, we explore 4D printing of a SMP in the submicron length scale, extending its applications to nanophononics. We report a new SMP photoresist based on Vero Clear achieving print features at a resolution of ~300 nm half pitch using two-photon polymerization lithography (TPL). Prints consisting of grids with size-tunable multi-colours enabled the study of shape memory effects to achieve large visual shifts through nanoscale structure deformation. As the nanostructures are flattened, the colours and printed information become invisible. Remarkably, the shape memory effect recovers the original surface morphology of the nanostructures along with its structural colour within seconds of heating above its glass transition temperature. The high-resolution printing and excellent reversibility in both microtopography and optical properties promises a platform for temperature-sensitive labels, information hiding for anti-counterfeiting, and tunable photonic devices., Four-dimensional (4D) printing of shape memory polymer (SMP) imparts time responsive properties to 3D structures. Here, the authors explore 4D printing of a SMP in the submicron length scale, extending its applications to nanophononics.

Temperature triggered switchable cellulose acetate-poly(N-isopropylacrylamide) (CA-PNIPAM) core-shell and blend nanofibers are fabricated for controlled moisture harvesting applications. Core-shell fibers are fabricated using a co-axial electrospinning setup whereas the conventional electrospinning setup is employed for fabricating the blend fibers. Investigation of their wettability behaviour demonstrated that the blend fibers are superhydrophilic whereas the core-shell fibers are hydrophilic at ambient temperature. Furthermore, both the samples have an ability to switch between the two states viz. hydrophilic to hydrophobic state based on thermal stimulus. The core-shell fibers are shown to have higher moisture sorption ability compared to the blend fibers. This study investigates the mechanism behind the switchable wettability behaviour of the core-shell fibers and demonstrates the crucial role played by the functional groups present on the surface layer of fibers in governing their moisture collection efficiency.

We report the fabrication of hierarchical poly(vinylidene fluoride) (PVDF) fibrous structures using a unique fabrication technique based on electrospinning. Electrospinning was used to fabricate aligned PVDF fibrous membranes. These membranes were then brought in contact with anodized aluminum oxide (AAO) template and then heat-treated above the glass transition temperature (T g) of the polymer to assist the flow of polymer within the cylindrical pores of AAO template. Scanning electron microscopy images confirmed that this approach lead to the growth of nanopillars on the surface of PVDF fibers. Nanoindenter was used to measure the pull-off force that was required to completely detach the indenter from the samples. To investigate the effect of hierarchy, pull-off force required to detach the indenter from neat PVDF fibers was determined and compared with the pull-off force recorded for hierarchical fibers. The effect of indentation depth was also investigated on both PVDF fibers and PVDF fiber with nanopillars. Significant pull-off force recorded indicates that these PVDF hierarchical fibrous structures can be potentially used for dry-adhesive applications.

eparation of low viscous oil from water has attracted immense attention in recent times due to the ever-increasing amount of oily industrial wastewater discharge and frequent oil spill accidents. Hence, there is a persistent demand for the fabrication of robust oil–water separation membranes. Herein, robust oil–water separation membranes are successfully fabricated by direct electrospinning of poly(vinylidene fluoride-co-hexafluoropropylene) and fluorinated polyhedral oligomeric silsesquioxane composite mixture. These hybrid membranes exhibit differential wetting (highly hydrophobic/superoleophilic) behavior for water and oil. The contact angle made by water and low viscous oil (hexane) with the membrane are measured to be 145 and 0° respectively. The nanofiber membranes efficiently separate low viscous oil from water in a single-step with separation efficiency of nearly 100%. Furthermore, the results demonstrate that the membranes are robust and durable exhibiting differential wettability even after several oil–water separation cycles. The results reveal the potential of their use for real-time industrial wastewater treatment applications.

Poly(N-isopropylacrylamide) (PNIPAM) has been used extensively for numerous biomedical applications. However, there is not enough information in the literature on the wettability and hygroscopic properties of electrospun PNIPAM fibers, relevant for water harvesting applications. This study focuses on investigating the wettability and hygroscopic properties of electrospun PNIPAM fibers at room temperature and elevated temperature. The wettability properties of electrospun PNIPAM fibers were compared to spin-coated PNIPAM thin films. The wettability properties of the electrospun fibers were enhanced by 56% compared to spin-coated films. Water contact angle (WCA) measured on electrospun fibers was determined to be 137° at elevated temperatures while WCA on spin cast PNIPAM film was determined to be 81° at elevated temperatures. Furthermore, hygroscopic properties of the electrospun PNIPAM fibers were studied using thermogravimetric analysis (TGA). The PNIPAM fibers are seen to exhibit moisture absorption capacity of about 16.6 wt. % under humid conditions.

In this study, we used electrospinning combined with template wetting method to fabricate hierarchical poly(methyl methacrylate) (PMMA) fibrous structures. The adhesion performance of these samples was investigated using a nanoindenter. A flat circular diamond indenter of 10 μm diameter was brought in contact with the sample and then retracted back. The force required to detach the indenter from the sample was determined to be the pull-off force. The effect of indentation depth on the pull-off force was also investigated. Following this, an empirical relationship to predict the pull-off strength (σ) was established for a given fibril radius (r), fibril height (l), preload (p), and effective Young's modulus (E*). The pull-off force values recorded for hierarchical PMMA fibrous structure were also used to validate the empirical relationship. The empirical relationship demonstrated good correlation between the recorded pull-off strength and system parameters. We believe that this empirical relationship will be helpful in designing high strength synthetic dry-adhesives as the relationship can be used to predict the pull-off strength a priori.

In this study, we used core-shell electrospinning to fabricate cellulose acetate-poly(N-isopropylacrylamide) (CA-PNIPAM) fibrous membranes and demonstrated the ability of these fibers to capture water from a high humid atmosphere and release it when thermally stimulated. The wettability of the fibers was controlled by using thermoresponsive PNIPAM as the shell layer. Scanning electron and fluorescence microscopes are used to investigate the microstructure of the fibers and confirm the presence of the core and shell phases within the fibers. The moisture capturing and releasing ability of these core-shell CA-PNIPAM fibers was compared with those of the neat CA and neat PNIPAM fibers at room temperature as well as at an elevated temperature. At room temperature, the CA-PNIPAM core-shell fibers are shown to have the maximum moisture uptake capacity among the three samples. The external temperature variations which trigger the moisture response behavior of these CA-PNIPAM fibers fall within the range of typical day and night cycles of deserts, demonstrating the potential use of these fibers for water harvesting applications.

Here, we combine electrospinning and replica-molding to produce hierarchical poly(methyl methacrylate) structures and investigate its adhesion behavior. Normal and shear adhesion of these biomimetic hierarchical structures was measured using nanoindentaton and a custom-built apparatus attached to Zwick tensile testing machine, respectively. Shear adhesion was measured by sliding the samples along the glass slide under a predefined normal preload. Normal adhesion was measured by indenting the surface of the sample with the help of a diamond indenter tip and retracting it back to determine the pull-off force needed to detach it from the sample. These experiments were also conducted on neat PMMA fibers to investigate the effect of hierarchy on the adhesion performance of the samples. Our results show that the shear adhesion strength and pull-off forces recorded for the hierarchical samples are higher than those recorded for neat fibers.

In a hospital environment, textile substrates have been implicated as a vector in the transmission of disease. To mitigate the harmful spread of disease via textile substrates, an effective measure is treatment of textiles with antimicrobial agents. The current investigation compares one of the most widely used chemically synthesized antimicrobial agents, triclosan with chitosan, a naturally occurring antimicrobial agent. For the study, samples of a common polyester/cotton textile used in hospital settings were treated with triclosan and chitosan based antimicrobial agents. Following treatment, the samples were analyzed for their effectiveness against Staphylococcus aureus and Escherichia coli using standard AATCC Test Methods. The efficacy of the treatment to laundering was then evaluated by subjecting the treated samples to 50 washings and repeating the tests against the challenge microorganisms. Data obtained were statistically analyzed at a 95% confidence interval. Results showed that before laundering both triclosan and chitosan treated samples were extremely effective as antimicrobial agents. After laundering, chitosan was less effective against E.coli but maintained efficacy against S. aureus. The effectiveness of triclosan was not adversely affected after the laundering treatments.

Polypropylene nonwoven fabrics samples were modified using poly(2-(N,N-dimethyloamino ethyl) methacrylate) (PDAMA) and silver-containing layers. The structure of the material after modification was confirmed using scanning electron mocroscope, energy-dispersive X-ray spectroscopy, Fourier Transfer Infrared Spectroscopy (FTIR), and electro-kinetic measurements. It was found that samples with external PDAMA layers have excellent activity against Staphylococcus aureus under dynamic contact conditions. In contrast, samples finished with deposited silver showed little antimicrobial effect. Antibacterial tests conducted under static conditions showed no antibacterial activity irrespective of the deposited layers.

Herein, the fabrication of poly(vinylidene fluoride) (PVDF) fibrous membrane using electrospinning is reported and its use for dry-adhesive applications is demonstrated. The shear and normal adhesion performance of the samples was investigated using an Instron tensile tester and an atomic force microscope (AFM) respectively. For shear adhesion measurements, the electrospun membrane was finger pressed on to a glass slide and pulled in shear mode using a tensile tester. The thickness of the electrospun membrane was varied and the effect of thickness on shear adhesion was investigated. The shear adhesion strength increased when the thickness of the samples was reduced. Shear adhesion strength of a 200 µm thick sample was determined to be approximately 0.165 N/cm. For normal adhesion measurements, a flat tipless cantilever was used to indent the sample and then retract back to measure the pull-off force. High shear adhesion strength and normal pull-off force recorded are attributed to the fine size of the fibers that conform to the asperities present on the surfaces of the glass slide and the AFM cantilever. The durability of the adhesive was also verified by repeating the AFM adhesion measurements over 1000 consecutive attachment–detachment cycles. The pull-off force was seen to be constant over 1000 attachment–detachment cycles. Our results indicate that these electrospun fibrous membranes can potentially be used as reusable dry-adhesives. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44393.

Temperature-triggered switchable nanofibrous membranes are successfully fabricated from a mixture of cellulose acetate (CA) and poly(N-isopropylacrylamide) (PNIPAM) by employing a single-step direct electrospinning process. These hybrid CA-PNIPAM membranes demonstrate the ability to switch between two wetting states viz. superhydrophilic to highly hydrophobic states upon increasing the temperature. At room temperature (23 °C) CA-PNIPAM nanofibrous membranes exhibit superhydrophilicity, while at elevated temperature (40 °C) the membranes demonstrate hydrophobicity with a static water contact angle greater than 130°. Furthermore, the results here demonstrate that the degree of hydrophobicity of the membranes can be controlled by adjusting the ratio of PNIPAM in the CA-PNIPAM mixture.

Quest for efficient fog harvesting methods has drawn immense attention in recent times. In this study, electrospinning is used to fabricate three different sets of membranes that are based on pristine poly(N-isopropylacrylamide) (PNIPAM) fibers, pristine polyvinylidene fluoride (PVDF) fibers, and PNIPAM-PVDF bead-on-string fibers. The wettability of these membranes is investigated as a function of temperature and the effect of their wettability on the fog collection efficiency is determined. Membranes based on pristine PNIPAM and pristine PVDF fibers are fabricated using conventional electrospinning and are shown to have a smooth surface morphology. On the other hand, PNIPAM-PVDF bead-on-string fibers are fabricated using core–shell electrospinning. Water collection efficiency of the membranes is compared to investigate the influence of microstructures and wettability gradient on fog harvesting ability of the samples. Among the three samples, the bead-on-string hierarchical fibrous membrane demonstrates the highest fog harvesting rate of 1150 ± 28 mg cm−2 h−1 at 25 °C and 909 ± 31 mg cm−2 h−1 at 40 °C. Furthermore, the results demonstrate that the presence of microstructures on the nanofibers improve the fog harvesting efficiency of PNIPAM-PVDF bead-on-string fibers.

Collection of clean water from humid air has attracted immense attention in recent years due to the lack of access to pure drinking water among large section of population in several parts of the world. Hence, there is a persistent demand for the fabrication of robust, scalable membranes for efficient harvesting of pure water, especially in fog-laden areas. Herein, three different membranes based on neat nanofibers, nanofibers with microparticles, and nanofibers with hierarchical structures (nanopillars) are successfully fabricated using poly(vinylidene fluoride-co-hexafluoropropylene) and fluorinated polyhedral oligomeric silsesquioxane composite mixture. Neat nanofibers and nanofibers with microparticles are fabricated by employing direct electrospinning and electrospinning combined with electrospraying process, respectively. Hierarchical structured fibers are fabricated by growing nanopillars on the surface of the fibers using electrospinning combined with template-wetting method. The wettability properties including water contact angle and hysteresis of these membranes are investigated. Due to the increased surface roughness and low surface energy, the hierarchical fibers exhibit higher contact angle (153°) and lower hysteresis (3°) compared to the neat nanofibers and nanofibers with microparticles. Furthermore, the results demonstrate that the presence of nanopillars on the surface of the nanofibers improves the membrane's water collection efficiency when exposed to humid air.

This study investigated the switchable wettability behavior of poly-N-(isopropyl acrylamide) (PNIPAM) and poly-(vinylidene fluoride) (PVDF) blend membranes that were fabricated using electrospinning. The wettability of the membranes was determined by water contact angle measurements. The wettability of the membranes was controlled by varying the concentration of PNIPAM in the blend. The results demonstrated that the addition of PVDF to the PNIPAM did not change the thermoresponsive behavior of PNIPAM. All PNIPAM/PVDF blend samples switched from hydrophilic to hydrophobic state when the temperature was increased from room temperature to 40 °C. However, blend samples with 25 wt% PNIPAM were demonstrated to be more hydrophilic and hydrophobic compared to other samples at room temperature and elevated temperature respectively. This was attributed to the phase separation of the polymers that resulted in domains with drastically different surface energies on the surface of the fibers.

Reconfigurable metamaterials require constituent nanostructures to demonstrate switching of shapes with external stimuli. For generality, such nanostructures would touch and stick to other surfaces in one of its configurations. Yet, a longstanding challenge is in overcoming this stiction caused by Van der Waals forces, which impedes shape recovery. Here, we introduce a stiff yet self-recovering material system based on acrylic acid, and tested it in high-aspect ratio structures, where recovery is weak. This designer material has a storage modulus of ~5.2 GPa at room temperature and ~90 MPa in the rubbery state at 150 Celsius, an order of magnitude higher than previous reports. A high-resolution resin for two-photon lithography was developed based on this polymer system, enabling 3D printing of nanopillars with diameters of ~400 nm and aspect ratio as high as ~10. Experimentally, we observed self-recovery as collapsed and touching structures overcome stiction to stand back up. We developed a theoretical model to explain the recoverability of these sub-micron structures. Reconfigurable structural colour prints and holograms were demonstrated, indicating potential applications of the material system as a shape memory polymer suitable for sub-micron reconfigurable metamaterials.