NaCl aerosol filtration over filter media with intrafiber porosity: can filtrate capacity be increased by wicking into this pore volume?

This paper investigates a novel fiber-based filter media wherein a NaCl filtrate is collected and reservoired not only onto the surfaces of the fibers and within their inter-fiber voidage but also within the internal porosity of high pore volume nanoporous fibers or vapor grown carbon nanofibers (VGCF) floc used to fabricate the media. This transport process is shown to occur through a NaCl dissolution into the water-filled nanopores of the fiber and a subsequent intra-fiber wicking phenomenon. The study further elucidates two distinct NaCl accommodation mechanisms which are uniquely available to filter media containing nanoporous intrafiber porosity: (1) wicking and capillary condensation of liquid NaCl aerosols directly into the intrafiber pores at high RH, and (2) dissolution of otherwise solid NaCl aerosols deposited onto fiber surfaces (at low RH) into the interior nanopores of the fiber because these pores (when hydrophilic) are saturated with water (even at low RH). To investigate these two mechanistic regimes, various media were fabricated possessing multiscale porosity in the form of: (i) embedded flocs of VGCFs (4.108 cm3gm-1pore volume), (ii) hydrophilic and high pore volume activated carbon fibers (ACFs, 0.950 cm3gm-1) and (iii) solid graphite fibers. These media were then comparatively evaluated toward NaCl aerosol filtration at different relative humidities. Pressure drop measurements versus filtrate accumulation and SEM-EDAX VGCF demonstrated the location and transport of NaCl into the intrafiber voidage. Media containing both VGCF floc and ACF accumulated 1200% more NaCl at low RH (and a specified pressure drop) than similar media prepared from non-porous graphite fibers, with an additional 315% increase from low to high RH. A Gibbs free energy driving force model is provided to illustrate the driving forces favoring water condensation into the nanopores and solid NaCl aerosol dissolution into the water phase. Filtration efficiency and quality factor assessments for the various media are also systematically evaluated to demonstrate the observed mechanistics.

Capillary Condensation of Water in Graphene Nanocapillaries.

Recent experiments have revealed that the macroscopic Kelvin equation remains surprisingly accurate even for nanoscale capillaries. This phenomenon was so far explained by the oscillatory behavior of the solid-liquid interfacial free energy. We here demonstrate thermodynamic and capillarity inconsistencies with this explanation. After revising the Kelvin equation, we ascribe its validity at nanoscale confinement to the effect of disjoining pressure. To substantiate our hypothesis, we employed molecular dynamics simulations to evaluate interfacial heat transfer and wetting properties. Our assessments unveil a breakdown in a previously established proportionality between the work of adhesion and the Kapitza conductance at capillary heights below 1.3 nm, where the dominance of the work of adhesion shifts primarily from energy to entropy. Alternatively, the peak density of the initial water layer can effectively probe the work of adhesion. Unlike under bulk conditions, high confinement renders the work of adhesion entropically unfavorable.

Water-Induced Separation of Polymers from High Nanoparticle-Content Nanocomposite Films.

Polymer nanocomposites with high loadings of nanoparticles (NPs) exhibit exceptional mechanical and transport properties. Separation of polymers and NPs from such nanocomposites is a critical step in enabling the recycling of these components and reducing the potential environmental hazards that can be caused by the accumulation of nanocomposite wastes in landfills. However, the separation typically requires the use of organic solvents or energy-intensive processes. Using polydimethylsiloxane (PDMS)-infiltrated SiO2 NP films, we demonstrate that the polymers can be separated from the SiO2 NP packings when these nanocomposites are exposed to high humidity and water. The findings indicate that the charge state of the NPs plays a significant role in the propensity of water to undergo capillary condensation within the PDMS-filled interstitial pores. We also show that the size of NPs has a crucial impact on the kinetics and extent of PDMS expulsion, illustrating the importance of capillary forces in inducing PDMS expulsion. We demonstrate that the separated polymer can be collected and reused to produce a new nanocomposite film. The work provides insightful guidelines on how to design and fabricate end-of-life recyclable high-performance nanocomposites.

A Synergistic Approach to Atmospheric Water Scavenging.

An abundant supply of fresh water is one of the leading challenges of the 21st century (UNESCO. The United Nations World Water Development Report 2018: Nature-Based Solutions for Water;UNESCO: Paris, France, 2018; p 154). Here we describe a new approach to scavenge atmospheric water that employs a hierarchically ordered porous material with embedded particles (Lash, M. H.; Jordan, J. C.; Blevins, L. C.; Fedorchak, M. V.; Little, S. R.; McCarthy, J. J.Non-Brownian Particle-Based Materials with Microscale and Nanoscale Hierarchy. Ang. Chem. Int. Ed.201554, 5854-5858). This composite uses structure to amplify native material performance to realize synergy between the capture and storage and to ultimately qualitatively change the adsorption behavior of the hydrogel (from unfavorable to favorable). In this way we can capture moisture at significantly lower relative humidities than would otherwise be feasible with the native materials. Not only does this approach pose the potential for a cheap and low-energy source of clean water but it could also be modified for application across a variety of condensable vapor reclamations.

Liquid-dependent impedance induced by vapor condensation and percolation in nanoparticle film.

A liquid-dependent impedance is observed by vapor condensation and percolation in the void space between nanoparticles. Under the Laplace pressure, vapor is effectively condensed into liquid to fill the nanoscale voids in an as-deposited nanoparticle film. Specifically, the transient impedance of the nanoparticle film in organic vapor is dependent on the vapor pressure and the conductivity of the condensed liquid. The response follows a power law that can be explained by the classical percolation theory. The condensed vapor gradually percolates into the void space among nanoparticles. A schematic is proposed to describe the vapor condensation and percolation dynamics among the nanoparticles. These findings offer insights into the behavior of vapor adsorbates in nanomaterial assemblies that contain void space.

In Situ Atomic-Scale Imaging of Interfacial Water under 3D Nanoscale Confinement.

Capillary condensation of water from vapor is an everyday phenomenon which has a wide range of scientific and technological implications. Many aspects of capillary condensation are not well understood such as the structure of interfacial water, the existence of distinct properties of confined water, or the validity of the Kelvin equation at nanoscale. We note the absence of high-spatial resolution images inside a meniscus. Here, we develop an AFM-based method to provide in situ atomic-scale resolution maps of the solid-water interface of a nanomeniscus (80-250 nm3). The separation between the first two hydration layers on graphite is 0.30 nm, while on mica it is 0.28 nm. Those values are very close to the ones expected for the same surfaces immersed in bulk water. Thus, the hydration layer structure on a crystalline surface is independent of the water volume.

Discussion on Water Condensation in Membrane Pores during CO2 Absorption at High Temperature.

Water condensation is a possible cause of membrane wetting in the operation of membrane contactors, especially under high-temperature conditions. In this study, water condensation in pores of polytetrafluoroethylene (PTFE) hollow fiber membranes was investigated during high-pressure CO2 absorption around 70 °C. It was found that the liquid accumulation rate in the treated gas knock-out drum was constant during continuous operation for 24 h when all experimental conditions were fixed, indicating a stable degree of membrane wetting. However, as the operating parameters were changed, the equilibrium vapor pressure of water within membrane pores could change, which may result in a condensation-conducive environment. Water condensation in membrane pores was detected and proven indirectly through the increase in liquid accumulation rate in the treated gas knock-out drum. The Hagen-Poiseuille equation was used to correlate the liquid accumulation rate with the degree of membrane wetting. The degree of membrane wetting increased significantly from 1.8 × 10-15 m3 to 3.9 × 10-15 m3 when the feed gas flow rate was reduced from 1.45 kg/h to 0.40 kg/h in this study due to water condensation in membrane pores. The results of this study provide insights into potential operational limitations of membrane contactor for CO2 absorption under high-temperature conditions.

Bubble Seeding Nanocavities: Multiple Polymer Foam Cell Nucleation by Polydimethylsiloxane-Grafted Designer Silica Nanoparticles.

We describe a successful strategy to substantially enhance cell nucleation efficiency in polymer foams by using designer nanoparticles as nucleating agents. Bare and poly(dimethylsilane) (PDMS)-grafted raspberry-like silica nanoparticles with diameters ranging from ∼80 nm to ∼200 nm were synthesized and utilized as highly efficient cell nucleators in CO2-blown nanocellular polymethyl methacrylate (PMMA) foams. The successful synthesis of core-shell nanoparticles was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, Brunauer-Emmett-Teller measurements, and transmission electron microscopy. The cell size and cell density of the obtained PMMA micro- and nanocellular foams were determined by scanning electron microscopy. The results show that increased surface roughness enhances the nucleation efficiency of the designer silica particles. This effect is ascribed to a decreased nucleation free energy for foam cell nucleation in the nanocavities at the melt-nucleator interface. For PDMS grafted raspberry-like silica nanoparticles with diameters of 155 and 200 nm, multiple cell nucleation events were observed. These hybrid particles had nucleation efficiencies of 3.7 and 6.2, respectively. The surprising increase in nucleation efficiency to above unity is ascribed to the significant increase in CO2 absorption and capillary condensation in the corresponding PMMA during saturation. This increase results in the presence of large amounts of the physical blowing agent close to energetically favorable nucleation points. Additionally, it is shown that as a consequence of cell coalescence, the increased number of foam cells is rapidly reduced during the first seconds of foaming. Hence, the design of highly efficient nucleating particles, as well as careful selection of foam matrix materials, seems to be of pivotal importance for obtaining polymer cellular materials with cell dimensions at the nanoscale. These findings contribute to the fabrication of polymer foams with high thermal insulation capacity and have relevance in general to the area of cellular materials.

Modeling the Reflectance Changes Induced by Vapor Condensation in Lycaenid Butterfly Wing Scales Colored by Photonic Nanoarchitectures.

Gas/vapor sensors based on photonic band gap-type materials are attractive as they allow a quick optical readout. The photonic nanoarchitectures responsible for the coloration of the wing scales of many butterfly species possessing structural color exhibit chemical selectivity, i.e., give vapor-specific optical response signals. Modeling this complex physical-chemical process is very important to be able to exploit the possibilities of these photonic nanoarchitectures. We performed measurements of the ethanol vapor concentration-dependent reflectance spectra of the Albulina metallica butterfly, which exhibits structural color on both the dorsal (blue) and ventral (gold-green) wing sides. Using a numerical analysis of transmission electron microscopy (TEM) images, we revealed the details of the photonic nanoarchitecture inside the wing scales. On both sides, it is a 1D + 2D structure, a stack of layers, where the layers contain a quasi-ordered arrangement of air voids embedded in chitin. Next, we built a parametric simulation model that matched the measured spectra. The reflectance spectra were calculated by ab-initio methods by assuming variable amounts of vapor condensed to liquid in the air voids, as well as vapor concentration-dependent swelling of the chitin. From fitting the simulated results to the measured spectra, we found a similar swelling on both wing surfaces, but more liquid was found to concentrate in the smaller air voids for each vapor concentration value measured.

Highly Sensitive and Discriminative Detection of BTEX in the Vapor Phase: A Film-Based Fluorescent Approach.

BTEX (benzene, toluene, ethylbenzene, o-xylene, m-xylene, and p-xylene) represents a group of volatile organic compounds (VOCs) and constitutes a great threat to human health. However, sensitive, selective, and speedy detection of them on-site and in the vapor phase remains a challenge for years. Herein, we report a film-based fluorescent approach and a conceptual sensor, which shows unprecedented sensitivity, speed, and reversibility to the aromatic hydrocarbons in the vapor phase. In the studies, pentiptycene was employed to produce a nonplanar perylene bisimide (PBI) derivative, P-PBI. The compound was further utilized to fabricate the film. The novelty of the design is the combination of capillary condensation and solvent effect, which is expected to enrich the analytes from vapor phase and shows outputs at the same time. Importantly, the film permits instant response (∼3 s) and real-time identification (<1 min) of benzene and toluene from other aromatic hydrocarbons. The experimental detection limits (DLs) of the six analytes are lower than 9.2, 2.7, 1.9, 0.2, 0.4, and 0.4 ppm, which with the exception of benzene, are significantly lower than the NIOSH recommended long-term exposure limits. More importantly, the film is photochemically stable, and more than 300 repetitive tests showed no observable bleaching. In addition, the sensing is fully reversible. The superior performance of the film device is in support of the assumption that the combination of capillary condensation and solvation effect would constitute an effective way to design high-performance fluorescent films, especially for challenging chemical inert and photoelectronically inactive VOCs.

Inferring pore connectivity from sorption hysteresis in multiscale porous media.

HYPOTHESIS: Vapor adsorption experiments are widely used to assess pore size distributions, but the large hysteresis sometimes observed between sorption and desorption isotherms remains difficult to interpret. Such hysteresis is influenced pore network connectivity, which has previously been modeled by percolation on infinite lattices. Our hypothesis is that percolation occurs instead through finite networks of micropores connecting accessible macropores, always exposed to the outside environment. THEORY: We derive a general formula for sorption/desorption isotherms that introduces a simple measure of hierarchical pore connectivity - the fraction of always exposed pores. The model thus accounts for "small world" connections in finite-size percolation, while also incorporating other hysteresis mechanisms, in single-pore filling, liquid insertion into the solid matrix, and cavitation. FINDINGS: Our formula is able to fit and interpret both primary and scanning sorption/desorption isotherms for a variety of adsorbates (noble gases, water, and organics) and porous materials (cement pastes, dental enamels, porous glasses, carbon black and nanotubes), including cases with broad pore-size distributions and large hysteresis. It allows quantification of the prevalence of percolating macropores in the material, even though these pores are never filled during the sorption experiments. A distinct bump in sorption isotherms is explained as a lowering of the barrier to nucleation of the vapor phase with a universal temperature scaling.

Polystyrene Opals Responsive to Methanol Vapors.

Photonic crystals (PCs) show reflectance spectra depending on the geometrical structure of the crystal, the refractive index (neff), and the light incident angle, according to the Bragg-Snell law. Three-dimensional photonic crystals (3D-PCs) composed of polymeric sub-micrometer spheres, are arranged in an ordered face cubic centered (fcc) lattice and are good candidates for vapor sensing by exploiting changes of the reflectance spectra. We synthesized high quality polystyrene (PS) 3D-PCs, commonly called opals, with a filling factor f near to the ideal value of 0.74 and tested their optical response in the presence of different concentrations of methanol (MeOH) vapor. When methanol was present in the voids of the photonic crystals, the reflectance spectra experienced energy shifts. The concentration of methyl alcohol vapor can be inferred, due to a linear dependence of the reflectance band maximum wavelength as a function of the vapor concentration. We tested the reversibility of the process and the time stability of the system. A limit of detection (LOD) equal to 5% (v/v0), where v was the volume of methanol and v0 was the total volume of the solution (methanol and water), was estimated. A model related to capillary condensation for intermediate and high methanol concentrations was discussed. Moreover, a swelling process of the PS spheres was invoked to fully understand the unexpected energy shift found for very high methanol content.

Disordered Nanoparticle Packings under Local Stress Exhibit Avalanche-Like, Environmentally Dependent Plastic Deformation.

Nanoindentation experiments on disordered nanoparticle packings performed both in an atomic force microscope and in situ in a transmission electron microscope are used to investigate the mechanics of plastic deformation. Under an applied load, these highly porous films exhibit load drops, the magnitudes of which are consistent with an exponential population distribution. These load drops are attributed to local rearrangements of a small number of particles, which bear similarities to shear transformation zones and to the T1 process, both of which have been previously predicted for disordered packings. An increase in the relative humidity results in an increase in the number of observed load drops, indicating that the strength of the particle interactions has a significant effect on the modes of plastic deformation. These results suggest how disordered nanoparticle packings may be expected to behave in devices operating under varying environments.

Nature-Inspired Capillary-Driven Welding Process for Boosting Metal-Oxide Nanofiber Electronics.

Recently, semiconducting nanofiber networks (NFNs) have been considered as one of the most promising platforms for large-area and low-cost electronics applications. However, the high contact resistance among stacking nanofibers remained to be a major challenge, leading to poor device performance and parasitic energy consumption. In this report, a controllable welding technique for NFNs was successfully demonstrated via a bioinspired capillary-driven process. The interfiber connections were well-achieved via a cooperative concept, combining localized capillary condensation and curvature-induced surface diffusion. With the improvements of the interfiber connections, the welded NFNs exhibited enhanced mechanical property and high electrical performance. The field-effect transistors (FETs) based on the welded Hf-doped In2O3 (InHfO) NFNs were demonstrated for the first time. Meanwhile, the mechanisms involved in the grain-boundary modulation for polycrystalline metal-oxide nanofibers were discussed. When the high-k ZrO x dielectric thin films were integrated into the FETs, the field-effect mobility and operating voltage were further improved to be 25 cm2 V-1 s-1 and 3 V, respectively. This is one of the best device performances among the reported nanofibers-based FETs. These results demonstrated the potencies of the capillary-driven welding process and grain-boundary modulation mechanism for metal-oxide NFNs, which could be applicable for high-performance, large-scale, and low-power functional electronics.

Capillary condensation and gelling of microemulsions with clay additives.

The capillary condensation in bicontinuous microemulsions takes place when two parallel surfaces are narrowed that result in a completely lamellar microemulsion. We expected that this phase transition is also observable when the amount of hydrophilic surfaces from clay particles is raised, because hydrophilic surfaces induce lamellar ordering locally. Using small angle neutron scattering, the structure of microemulsions was observed as a function of clay content. The critical concentration is indicated by discontinuous structural changes and depends on the platelet diameter and is explained by the free energy of the platelets competing with the fluctuating medium. The gel phase transition is observed in the spectroscopic measurements where the diffusion motion is widely suppressed in the gel phase, but otherwise superimposes with the membrane undulations.

Robust Operation of Mesoporous Antireflective Coatings under Variable Ambient Conditions.

Generating mesoporous films with adequate film thickness and refractive index is a common method to achieve amplitude and phase matching in low-cost interference-based antireflective coatings (ARCs). For high-surface-energy materials, pores on the 2-50 nm (i.e., on the subwavelength scale) are subject to capillary condensation by surrounding gas phase water molecules, which hampers their functioning. In this work, we examine the effect of relative humidity on mesoporous ARCs and present a simple method for the preparation of ARCs with robust operation under variable conditions. The materials route is based on the generation of well-defined porous aluminosilicate networks by block copolymer co-assembly with poly(isobutylene)- block-poly(ethylene oxide) and postsynthesis grafting of trichloro(octyl)silane molecules to the pore walls. The functionalized films exhibited a maximum transmittance value of 99.8%, with an average transmittance of 99.1% in the visible wavelength range from 400 to 700 nm. Crucially, the antireflection performance was maintained at high humidity values, with an average transmittance decrease of only 0.2% and maximum values maintained at 99.7%. This compared to maximum and average losses of 3.6 and 2.7%, respectively, for nonfunctionalized reference samples. The ARCs were shown to retain their optical properties within 50 humidity cycles, indicating long-term stability against fluctuating environmental conditions.

Room-Temperature Chemical Welding and Sintering of Metallic Nanostructures by Capillary Condensation.

Room-temperature welding and sintering of metal nanostructures, nanoparticles and nanowires, by capillary condensation of chemical vapors have successfully been demonstrated. Nanoscale gaps or capillaries that are abundant in layers of metal nanostructures have been found to be the preferred sites for the condensation of chemically oxidizing vapor, H2O2 in this work. The partial dissolution and resolidification at such nanogaps completes the welding/sintering of metal nanostructures within ∼10 min at room-temperature, while other parts of nanostructures remain almost intact due to negligible amount of condensation on there. The welded networks of Ag nanowires have shown much improved performances, such as high electrical conductivity, mechanical flexibility, optical transparency, and chemical stability. Chemically sintered layers of metal nanoparticles, such as Ag, Cu, Fe, Ni, and Co, have also shown orders of magnitude increase in electrical conductivity and improved environmental stability, compared to nontreated ones. Pertinent mechanisms involved in the chemical welding/sintering process have been discussed. Room-temperature welding and sintering of metal nanostructures demonstrated here may find widespread application in diverse fields, such as displays, deformable electronics, wearable heaters, and so forth.

Frictional behavior of micro-patterned silicon surface.

A micro-patterned silicon surface, consisting of depressions with walls having a tilt angle of 30°, was created by photolithography followed by etching. The friction forces in single asperity contact acting between such a surface and an AFM tip was measured in air. This allowed elucidation of the validity of some common friction rules for this particular situation where a small tip traces a surface having roughness features that are significantly larger than the tip itself. The rules that was compared with our data were Amontons' first rule of friction stating that the friction force should be proportional to the load; Amontons' third rule stating that the friction force should be independent of sliding speed, and Euler's rule providing a relation between slope angle and friction coefficient. We found that both nanoscale surface heterogeneities and the µm-sized depressions affect friction forces, and considerable reproducible variations were found along a particular scan line. Nevertheless Amontons' first rule described average friction forces well. Amontons' third rule and Euler's rule were found to be less applicable to our system.

Chromogenic Photonic Crystals Enabled by Novel Vapor-Responsive Shape-Memory Polymers.

A new type of shape-memory polymer (SMP) is developed by integrating scientific principles drawn from two disparate fields: the fast-growing photonic crystal and SMP technologies. This new SMP enables room-temperature operation for the entire shape-memory cycle and instantaneous shape recovery triggered by exposure to a variety of organic vapors.

Effect of relative humidity on onset of capillary forces for rough surfaces.

Atomic force microscopy (AFM) was used to investigate the effect of relative humidity (RH) on the adhesion forces between silicon nitride AFM probes, hydrophilic stainless steel, and hydrophobic Perspex® (polymethylmethacrylate, PMMA). In addition, AFM-based phase contrast imaging was used to quantify the amount and location of adsorbed water present on these substrates at RH levels ranging from 15% to 65% at 22°C. Both the adhesion forces and the quantities of adsorbed moisture were seen to vary with RH, and the nature of this variation depended on the hydrophobicity of the substrate. For the Perspex®, both the adhesion force and the amount of adsorbed moisture were essentially independent of RH. For the stainless steel substrate, adsorbed moisture increased continuously with increasing RH, while the adhesion force rose from a minimum at 15% RH to a broad maximum between 25% and 35% RH. From 35% to 55% RH, the adhesion force dropped continuously to an intermediate level before rising again as 65% RH was approached. The changes in adhesion force with increasing relative humidity in the case of the stainless steel substrate were attributed to a balance of effects associated with adsorbed, sub-continuum water on the cantilever and steel. Hydrogen bonding interactions between these adsorbed water molecules were thought to increase the adhesion force. However, when significant quantities of molecular water adsorbed, these molecules were expect to decrease adhesion by screening the van der Waals interactions between the steel and the cantilever tip, and by increasing the separation distance between these solid surfaces when they were 'in contact'. Finally, the slight increase in adhesion between 55% and 65% RH was attributed to true capillary forces exerted by continuum water on the two solid surfaces.