Surface Reconstruction of Fluoropolymers in Liquid Media.

Surface reconstruction is the rearrangement of atoms or molecules at an interface in response to a stimulus, driven by lowering the overall free energy of the system. Perfluoroalkyl acrylate polymers with short side chains undergo reconstruction at room temperature when exposed to water. Here, we use contact angle aging to examine the liquid- and temperature- dependency of surface reconstruction of plasma polymerized perfluoroalkyl acrylates. We use a first order kinetic model to examine the dynamics of reconstructive processes. Our results show that, above the bulk melting point of the polymers, the contact angles of both polar and nonpolar (hydrocarbon) liquids show a time dependency well fit by the model. We conclude that surface reconstruction can be driven by the preferential segregation of hydrocarbon and fluorocarbon moieties as well as by polar interactions. This has implications in terms of using fluorocarbons to design oleophobic surfaces (and vice versa) and in terms of designing fluorocarbon and/or hydrocarbon surfaces with switchable wettability.

Droplet impact dynamics on textiles.

The development of textiles that repel droplets following droplet impact at a high velocity is a common requirement in a number of applications, ranging from waterproof clothing to inkjet printing, yet the underpinning physical mechanisms are not entirely understood. The impact of a droplet on the surface of a textile produces two simultaneous yet separate flows, occurring above and below the surface, and which are associated with the spreading and penetration dynamics. In this paper, we study the temporal evolution of the lateral spreading diameter of a droplet impacting both hydrophobic and hydrophilic textiles. We show that the impact on textiles at short timescales involves no deformation of the droplet shape if the textile's porosity is sufficiently low. We show that the early-stage impact penetration is solely driven by inertia and no lamella is visible. We also show that for hydrophilic textiles, depending on the impact conditions, a droplet can be captured by the textile or penetrate it. We show by balancing the dynamic impact and capillary pressures that the penetration behaviour is governed by a threshold pore size, the liquid characteristics and the droplet diameter. Our conclusions highlight that the ability of a textile to repel water is controlled by the mesh size. Our experiments and analysis were carried out on coated hydrophobic and non-coated hydrophilic textiles with four corresponding mesh sizes, and are in agreement with the previous findings on hydrophobic metallic (copper) meshes.

X-ray Imaging of Transplanar Liquid Transport Mechanisms in Single Layer Textiles.

Understanding the penetration of liquids within textile fibers is critical for the development of next-generation smart textiles. Despite substantial research on liquid penetration in the plane of the textile, little is known about how the liquid penetrates in the thickness direction. Here we report a time-resolved high-resolution X-ray measurement of the motion of the liquid-air interface within a single layer textile, as the liquid is transported across the textile thickness following the deposition of a droplet. The measurement of the time-dependent position of the liquid meniscus is made possible by the use of ultrahigh viscosity liquids (dynamic viscosity from 105 to 2.5 × 106 times larger than water). This approach enables imaging due to the slow penetration kinetics. Imaging results suggest a three-stage penetration process with each stage being associated with one of the three types of capillary channels existing in the textile geometry, providing insights into the effect of the textile structure on the path of the three-dimensional liquid meniscus. One dimensional kinetics studies show that our data for the transplanar penetration depth ΔxL vs time do not conform to a power law, and that the measured rate of penetration for long times is smaller than that predicted by Lucas-Washburn kinetics, challenging commonly held assumptions regarding the validity of power laws when applied to relatively thin textiles.

Enhanced stability of Cu-BTC MOF via perfluorohexane plasma-enhanced chemical vapor deposition.

Metal organic frameworks (MOFs) are a leading class of porous materials for a wide variety of applications, but many of them have been shown to be unstable toward water. Cu-BTC (1,3,5 benzenetricarboxylic acid, BTC) was treated with a plasma-enhanced chemical vapor deposition (PECVD) of perfluorohexane creating a hydrophobic form of Cu-BTC. It was found that the treated Cu-BTC could withstand high humidity and even submersion in water much better than unperturbed Cu-BTC. Through Monte Carlo simulations it was found that perfluorohexane sites itself in such a way within Cu-BTC as to prevent the formation of water clusters, hence preventing the decomposition of Cu-BTC by water. This PECVD of perfluorohexane could be exploited to widen the scope of practical applications of Cu-BTC and other MOFs.

Effect of Relative Humidity on Transfer of Aerosol-Deposited Artificial and Human Saliva from Surfaces to Artificial Finger-Pads.

Surface to hand transfer of viruses represents a potential mechanism for human exposure. An experimental process for evaluating the touch transfer of aerosol-deposited material is described based on controlling surface, tribological, and soft matter components of the transfer process. A range of high-touch surfaces were evaluated. Under standardized touch parameters (15 N, 1 s), relative humidity (RH) of the atmosphere around the contact transfer event significantly influenced transfer of material to the finger-pad. At RH < 40%, transfer from all surfaces was <10%. Transfer efficiency increased markedly as RH increased, reaching a maximum of approximately 50%. The quantity of material transferred at specific RHs above 40% was also dependent on roughness of the surface material and the properties of the aerosol-deposited material. Smooth surfaces, such as melamine and stainless steel, generated higher transfer efficiencies compared to those with textured roughness, such as ABS pinseal and KYDEX® plastics. Pooled human saliva was transferred at a lower rate compared to artificial saliva, indicating the role of rheological properties. The artificial saliva data were modeled by non-linear regression and the impact of environmental humidity and temperature were evaluated within a Quantitative Microbial Risk Assessment model using SARS-CoV-2 as an example. This illustrated that the trade-off between transfer efficiency and virus survival may lead to the highest risks of fomite transmissions in indoor environments with higher humidity.

A polymer coating which is sticky yet repulsive to water and slippery yet attractive for oils.

A one-step process has been developed to produce a polymer coating which is hydrophobic and oleophilic, but which oil slides off and water adheres to at all tilt angles - including when vertically inclined or inverted. The polymer is transparent, and the plasma coating process is independent of substrate composition and geometry.

Exploring Structure⁻Property Relationships in Aromatic Polybenzoxazines Through Molecular Simulation.

A series of commercial difunctional benzoxazine monomers are characterized using thermal and thermo-mechanical techniques before constructing representative polymer networks using molecular simulation techniques. Good agreement is obtained between replicate analyses and for the kinetic parameters obtained from differential scanning calorimetry data (and determined using the methods of Kissinger and Ozawa). Activation energies range from 85 to 108 kJ/mol (Kissinger) and 89 to 110 kJ/mol (Ozawa) for the uncatalyzed thermal polymerization reactions, which achieve conversions of between 85% and 97%. Glass transition temperatures determined from differential scanning calorimetry and dynamic mechanical thermal analysis are comparable, ranging from BA-a (151 °C, crosslink density 3.6 × 10-3 mol cm-3) containing the bisphenol A moiety to BP-a, based on a phenolphthalein bridge (239 to 256 °C, crosslink density 5.5 to 18.4 × 10-3 mol cm-3, depending on formulation). Molecular dynamics simulations of the polybenzoxazines generally agree well with empirical data, indicating that representative networks have been modelled.

Hydrolytic stability in hemilabile metal-organic frameworks.

Highly porous metal-organic frameworks (MOFs), which have undergone exciting developments over the past few decades, show promise for a wide range of applications. However, many studies indicate that they suffer from significant stability issues, especially with respect to their interactions with water, which severely limits their practical potential. Here we demonstrate how the presence of 'sacrificial' bonds in the coordination environment of its metal centres (referred to as hemilability) endows a dehydrated copper-based MOF with good hydrolytic stability. On exposure to water, in contrast to the indiscriminate breaking of coordination bonds that typically results in structure degradation, it is non-structural weak interactions between the MOF's copper paddlewheel clusters that are broken and the framework recovers its as-synthesized, hydrated structure. This MOF retained its structural integrity even after contact with water for one year, whereas HKUST-1, a compositionally similar material that lacks these sacrificial bonds, loses its crystallinity in less than a day under the same conditions.

Wetting Hierarchy in Oleophobic 3D Electrospun Nanofiber Networks.

Wetting behavior between electrospun nanofibrous networks and liquids is of critical importance in many applications including filtration and liquid-repellent textiles. The relationship between intrinsic nanofiber properties, including surface characteristics, and extrinsic nanofibrous network organization on resultant wetting characteristics of the nanofiber network is shown in this work. Novel 3D imaging exploiting focused ion beam (FIB) microscopy and cryo-scanning electron microscopy (cryo-SEM) highlights a wetting hierarchy that defines liquid interactions with the network. Specifically, small length scale partial wetting between individual electrospun nanofibers and low surface tension liquids, measured both using direct SEM visualization and a nano Wilhelmy balance approach, provides oleophobic surfaces due to the high porosity of electrospun nanofiber networks. These observations conform to a metastable Cassie-Baxter regime and are important in defining general rules for understanding the wetting behavior between fibrous solids and low surface tension liquids for omniphobic functionality.

Acid loaded porphyrin-based metal-organic framework for ammonia uptake.

A porphyrin-based metal-organic framework is shown to be structurally stable towards acid loading using either hydrochloric or formic acid. The capacity of this material as an ammonia sorbent was analysed using micro-breakthrough experiments in both dry and humid ammonia flows. The acid loaded material exhibited excellent uptake in comparison with the parent MOF.

Reversible water uptake by a stable imine-based porous organic cage.

A crystalline porous organic cage molecule, CC3, is shown to adsorb up to 20.1 wt% water reversibly. This was confirmed by both gravimetric sorption and by crystallographic analysis. Crystals of CC3 are stable in boiling water for at least 4 h. The surprising chemical and supramolecular stability of these imine-based molecular crystals suggests scope for practical applications in humid environments.