Transferring the structure of paper for mechanically durable superhydrophobic surfaces

© 2020 Elsevier B.V.Solution-phase deposition of nanomaterials represents a highly promising technology with strong industrial application potential for the fabrication of superhydrophobic surfaces. An important barrier towards the adaptation of such materials and processes in a broad range of applications is the limited mechanical durability of the nanostructures. Herein, we present a universal solution to this challenge by benefiting from the unique micro-structure of paper. Our approach is based on transferring the structure of paper into a target material, to form a mechanical protection layer for nanomaterials that were deposited from solution-phase, i.e. spray-coating. We demonstrate this concept through the transfer of the structure of paper to a free-standing PDMS film using a simple molding process. Spraying a dispersion of alkyl-silane functionalized silica nanoparticles on the structured free-standing film results in a hierarchically structured superhydrophobic surface with a water contact angle of 175° ± 2° and a sliding angle <2° ± 1°. The fabricated superhydrophobic surface displays high levels of mechanical, chemical and thermal stability. The robust, inexpensive, scalable, flexible, and environmentally friendly nature of the presented approach may be a key enabler in superhydrophobic coating applications

Robust superhydrophobic fabrics by infusing structured polydimethylsiloxane films

Superhydrophobic coatings have large application potential in self-cleaning textiles. Low durability, high cost of fabrication, and environmental concerns over the usage of chemicals such as fluorocarbons limit the utilization of superhydrophobic coatings. This study reports a convenient and inexpensive approach to fabricate robust and fluorine-free superhydrophobic fabrics based on the transfer of structured polymer films and hydrophobic nanoparticles. In this approach, polydimethylsiloxane (PDMS) is infused between sheets of fabric and paper, followed by curing and removal of the paper. This process results in a fabric infused with PDMS whose structure is a negative replica of the paper surface. Then, hydrophobic nanoparticles are sprayed onto the structured PDMS side of the fabric. The infusion of PDMS and subsequent deposition of the hydrophobic nanoparticles enables strong bonding, as shown by the excellent solvent stability of the superhydrophobic fabric under ultrasonication. The proposed approach is universal in that it can be applied to almost any textiles, which upon coating, exhibited superhydrophobicity with a water contact angle of 172 degrees and a sliding angle of 3 degrees. Furthermore, the superhydrophobic fabric showed robust durability against water spray impact and mechanical bending where it can keep superhydrophobicity for at least 200 cycles of each test

pH Tunable Patterning of Quantum Dots

Patterning of quantum dots (QDs) is essential for many, especially high-tech, applications. Here, pH tunable assembly of QDs over functional patterns prepared by electrohydrodynamic jet printing of poly(2-vinylpyridine) is presented. The selective adsorption of QDs from water dispersions is mediated by the electrostatic interaction between the ligand composed of 3-mercaptopropionic acid and patterned poly(2-vinylpyridine). The pH of the dispersion provides tunability at two levels. First, the adsorption density of QDs and fluorescence from the patterns can be modulated for pH > approximate to 4. Second, patterned features show unique type of disintegration resulting in randomly positioned features within areas defined by the printing for pH <= approximate to 4. The first capability is useful for deterministic patterning of QDs, whereas the second one enables hierarchically structured encoding of information by generating stochastic features of QDs within areas defined by the printing. This second capability is exploited for generating addressable security labels based on unclonable features. Through image analysis and feature matching algorithms, it is demonstrated that such patterns are unclonable in nature and provide a suitable platform for anti-counterfeiting applications. Collectively, the presented approach not only enables effective patterning of QDs, but also establishes key guidelines for addressable assembly of colloidal nanomaterials

Fabrication of robust superhydrophobic surfaces by one-step spray coating: Evaporation driven self-assembly of wax and nanoparticles into hierarchical structures

Mechanically durable superhydrophobic coatings have enormous application potential in almost all aspects of our daily lives. In this study, we present a practical strategy for one-step fabrication of robust superhydrophobic coatings based on evaporation driven self-assembly of hydrophobic nanoparticles and wax into hierarchical structures. Depending on the solvent and coating distance, spray-coating a dispersion composed of alkyl-silane functionalized nanoparticles and wax results in extremely water repellent surfaces with a water contact angle of 175 degrees and a sliding angle of 3 degrees. The formation of hierarchically structured surfaces upon evaporation of the solvent enables fabrication of fluorine-free, highly water repellent surfaces and provides high level of structural protection against mechanical abrasion. The coating retains its superhydrophobicity even after 1000 cycles of water spray impact, 45 min of water jet impact, and 180 cm of linear abrasion. The low-cost, scalable, one-step, and fluorine-free fabrication of superhydrophobic coatings that can be applied onto virtually any type of material surface with a satisfactory mechanical robustness based on eco-friendly and industrially available materials presents promising avenues for practical applications

Physically Unclonable Surfaces via Dewetting of Polymer Thin Films

From anti-counterfeiting to biotechnology applications, there is a strong demand for encoded surfaces with multiple security layers that are prepared by stochastic processes and are adaptable to deterministic fabrication approaches. Here, we present dewetting instabilities in nanoscopic (thickness <100 nm) polymer films as a form of physically unclonable function (PUF). The inherent randomness involved in the dewetting process presents a highly suitable platform for fabricating unclonable surfaces. The thermal annealing-induced dewetting of poly(2-vinyl pyridine) (P2VP) on polystyrene-grafted substrates enables fabrication of randomly positioned functional features that are separated at a microscopic length scale, a requirement set by optical authentication systems. At a first level, PUFs can be simply and readily verified via reflection of visible light. Area-specific electrostatic interactions between P2VP and citrate-stabilized gold nanoparticles allow for fabrication of plasmonic PUFs. The strong surface-enhanced Raman scattering by plasmonic nanoparticles together with incorporation of taggants facilitates a molecular vibration-based security layer. The patterning of P2VP films presents opportunities for fabricating hybrid security labels, which can be resolved through both stochastic and deterministic pathways. The adaptability to a broad range of nanoscale materials, simplicity, versatility, compatibility with conventional fabrication approaches, and high levels of stability offer key opportunities in encoding applications