Continuous Liquid-Liquid Extraction and in-Situ Membrane Separation of Miscible Liquid Mixtures.

Separation operations are critical across a wide variety of manufacturing industries and account for about one-quarter of all in-plant energy consumption in the United States. Conventional liquid-liquid separation operations require either thermal or chemical treatment, both of which have a large environmental impact and carbon footprint. Consequently, there is a great need to develop sustainable, clean methodologies for separation of miscible liquid mixtures. The greatest opportunities to achieve this lie in replacing high-energy separation operations (e.g., distillation) with low-energy alternatives such as liquid-liquid extraction. One of the primary design challenges in liquid-liquid extraction is to maximize the interfacial area between two immiscible (e.g., polar and nonpolar) liquids for efficient mass transfer. However, this often involves energy-intensive methods including ultrasonication, pumping the feed and the extractant through packed columns with high tortuosity, or using a supercritical fluid as an extractant. Emulsifying the feed and the extractant, especially with a surfactant, offers a large interfacial area, but subsequent separation of emulsions can be energy-intensive and expensive. Thus, emulsions are typically avoided in conventional extraction operations. Herein, we discuss a novel, easily scalable, platform separation methodology termed CLEANS (continuous liquid-liquid extraction and in-situ membrane separation). CLEANS integrates emulsion-enhanced extraction with continuous, gravity-driven, membrane-based separation of emulsions into a single unit operation. Our results demonstrate that the addition of a surfactant and emulsification significantly enhance extraction (by >250% in certain cases), even for systems where the best extractants for miscible liquid mixtures are known. Utilizing the CLEANS methodology, we demonstrate continuous separation of a wide range of miscible liquid mixtures, including soluble organic molecules from oils, alcohols from esters, and even azeotropes.

Coalescence-induced jumping of droplets on superomniphobic surfaces with macrotexture.

When two liquid droplets coalesce on a superrepellent surface, the excess surface energy is partly converted to upward kinetic energy, and the coalesced droplet jumps away from the surface. However, the efficiency of this energy conversion is very low. In this work, we used a simple and passive technique consisting of superomniphobic surfaces with a macrotexture (comparable to the droplet size) to experimentally demonstrate coalescence-induced jumping with an energy conversion efficiency of 18.8% (i.e., about 570% increase compared to superomniphobic surfaces without a macrotexture). The higher energy conversion efficiency arises primarily from the effective redirection of in-plane velocity vectors to out-of-plane velocity vectors by the macrotexture. Using this higher energy conversion efficiency, we demonstrated coalescence-induced jumping of droplets with low surface tension (26.6 mN m-1) and very high viscosity (220 mPa·s). These results constitute the first-ever demonstration of coalescence-induced jumping of droplets at Ohnesorge number >1.

Smooth, All-Solid, Low-Hysteresis, Omniphobic Surfaces with Enhanced Mechanical Durability.

The utility of omniphobic surfaces stems from their ability to repel a multitude of liquids, possessing a broad range of surface tensions and polarities, by causing them to bead up and either roll or slide off. These surfaces may be self-cleaning, corrosion-resistant, heat-transfer enhancing, stain-resistant or resistant to mineral- or biofouling. The majority of reported omniphobic surfaces use texture, lubricants, and/or grafted monolayers to engender these repellent properties. Unfortunately, these approaches often produce surfaces with deficiencies in long-term stability, durability, scalability, or applicability to a wide range of substrates. To overcome these limitations, we have fabricated an all-solid, substrate-independent, smooth, omniphobic coating composed of a fluorinated polyurethane and fluorodecyl polyhedral oligomeric silsesquioxane. Liquids of varying surface tension, including water, hexadecane, ethanol, and silicone oil, exhibit low-contact-angle hysteresis (<15°) on these surfaces, allowing liquid droplets to slide off, leaving no residue. Moreover, we demonstrate that these robust surfaces retained their repellent properties more effectively than textured or lubricated omniphobic surfaces after being subjected to mechanical abrasion.

Coalescence-Induced Self-Propulsion of Droplets on Superomniphobic Surfaces.

We utilized superomniphobic surfaces to systematically investigate the different regimes of coalescence-induced self-propulsion of liquid droplets with a wide range of droplet radii, viscosities, and surface tensions. Our results indicate that the nondimensional jumping velocity Vj* is nearly constant (Vj* ≈ 0.2) in the inertial-capillary regime and decreases in the visco-capillary regime as the Ohnesorge number Oh increases, in agreement with prior work. Within the visco-capillary regime, decreasing the droplet radius R0 results in a more rapid decrease in the nondimensional jumping velocity Vj* compared to increasing the viscosity µ. This is because decreasing the droplet radius R0 increases the inertial-capillary velocity Vic in addition to increasing the Ohnesorge number Oh.

Designing Self-Healing Superhydrophobic Surfaces with Exceptional Mechanical Durability.

The past decade saw a drastic increase in the understanding and applications of superhydrophobic surfaces (SHSs). Water beads up and effortlessly rolls off a SHS due to its combination of low surface energy and texture. Whether being used for drag reduction, stain repellency, self-cleaning, fog harvesting, or heat transfer applications (to name a few), the durability of a SHS is critically important. Although a handful of purportedly durable SHSs have been reported, there are still no criteria available for systematically designing a durable SHS. In the first part of this work, we discuss two new design parameters that can be used to develop mechanically durable SHSs via the spray coating of different binders and fillers. These parameters aid in the rational selection of material components and allow one to predict the capillary resistance to wetting of any SHS from a simple topographical analysis. We show that not all combinations of sprayable components generate SHSs, and mechanically durable components do not necessarily generate mechanically durable SHSs. Moreover, even the most durable SHSs can eventually become damaged. In the second part, utilizing our new parameters, we design and fabricate physically and chemically self-healing SHSs. The most promising surface is fabricated from a fluorinated polyurethane elastomer (FPU) and the extremely hydrophobic small molecule 1H,1H,2H,2H-heptadecafluorodecyl polyhedral oligomeric silsesquioxane (F-POSS). A sprayed FPU/F-POSS surface can recover its superhydrophobicity even after being abraded, scratched, burned, plasma-cleaned, flattened, sonicated, and chemically attacked.

Designing durable icephobic surfaces.

Ice accretion has a negative impact on critical infrastructure, as well as a range of commercial and residential activities. Icephobic surfaces are defined by an ice adhesion strength τice < 100 kPa. However, the passive removal of ice requires much lower values of τice, such as on airplane wings or power lines (τice < 20 kPa). Such low τice values are scarcely reported, and robust coatings that maintain these low values have not been reported previously. We show that, irrespective of material chemistry, by tailoring the cross-link density of different elastomeric coatings and by enabling interfacial slippage, it is possible to systematically design coatings with extremely low ice adhesion (τice < 0.2 kPa). These newfound mechanisms allow for the rational design of icephobic coatings with virtually any desired ice adhesion strength. By using these mechanisms, we fabricate extremely durable coatings that maintain τice < 10 kPa after severe mechanical abrasion, acid/base exposure, 100 icing/deicing cycles, thermal cycling, accelerated corrosion, and exposure to Michigan wintery conditions over several months.

A high-performance renewable thermosetting resin derived from eugenol.

A renewable bisphenol, 4,4'-(butane-1,4-diyl)bis(2-methoxyphenol), was synthesized on a preparative scale by a solvent-free, Ru-catalyzed olefin metathesis coupling reaction of eugenol followed by hydrogenation. After purification, the bisphenol was converted to a new bis(cyanate) ester by standard techniques. The bisphenol and cyanate ester were characterized rigorously by NMR spectroscopy and single-crystal X-ray diffraction studies. After complete cure, the cyanate ester exhibited thermal stability in excess of 350 °C and a glass transition temperature (Tg ) of 186 °C. As a result of the four-carbon chain between the aromatic rings, the thermoset displayed a water uptake of only 1.8% after a four day immersion in 85 °C water. The wet Tg of the material (167 °C) was only 19 °C lower than the dry Tg , and the material showed no significant degradation as a result of the water treatment. These results suggest that this resin is well suited for maritime environments and provide further evidence that full-performance resins can be generated from sustainable feedstocks.

Di(cyanate Ester) Networks Based on Alternative Fluorinated Bisphenols with Extremely Low Water Uptake.

A new polycyanurate network exhibiting extremely low moisture uptake has been produced via the treatment of perfluorocyclobutane-containing Bisphenol T with cyanogen bromide and subsequent thermal cyclotrimerization. The water uptake, at 0.56 ± 0.10% after immersion in water at 85 °C for 96 h, represents some of the most promising moisture resistance observed to date in polycyanurate networks. This excellent performance derives from a near optimal value of the glass transition at 190 °C at full cure. Superior dielectric loss characteristics compared to commercial polycyanurate networks based on Bisphenol E were also observed. Polycyanurate networks derived from this new monomer appear particularly well-suited for applications such as radomes and spacecrafts where polycyanurates are already widely recognized as providing outstanding properties.

Transparent, flexible, superomniphobic surfaces with ultra-low contact angle hysteresis.

See-through surfaces: High transparency is required to use superomniphobic surfaces, which can be self-cleaning, stain-proof, anti-bio-fouling, drag-reducing, or anti-fogging, for smartphone screens, eye glasses, windshields, or flat panel displays. A spray-based method has now been developed that can fabricate transparent, flexible, and highly superomniphobic surfaces. HD=hexadecane.

Curing of a bisphenol E based cyanate ester using magnetic nanoparticles as an internal heat source through induction heating.

We report on the control of cyclotrimerization forming a polycyanurate polymer using magnetic iron oxide nanoparticles in an alternating-current (ac) field as an internal heat source, starting from a commercially available monomer. Magnetic nanoparticles were dispersed in the monomer and catalytic system using sonication, and the mixture was subjected to an alternating magnetic field, causing the magnetic nanoparticles to dissipate the energy of the magnetic field in the form of heat. Internal heating of the particle/monomer/catalyst system was sufficient to start and sustain the polymerization reaction, producing a cyanate ester network with conversion that compared favorably to polymerization through heating in a conventional laboratory oven. The two heating methods gave similar differential scanning calorimetry temperature profiles, conversion rates, and glass transition temperatures when using the same temperature profile. The ability of magnetic nanoparticles in an ac field to drive the curing reaction should allow for other reactions forming high-temperature thermosetting polymers and for innovative ways to process such polymers.

Utilizing dynamic tensiometry to quantify contact angle hysteresis and wetting state transitions on nonwetting surfaces.

Goniometric techniques traditionally quantify two parameters, the advancing and receding contact angles, that are useful for characterizing the wetting properties of a solid surface; however, dynamic tensiometry, which measures changes in the net force on a surface during the repeated immersion and emersion of a solid into a probe liquid, can provide further insight into the wetting properties of a surface. We detail a framework for analyzing tensiometric results that allows for the determination of wetting hysteresis, wetting state transitions, and characteristic topographical length scales on textured, nonwetting surfaces, in addition to the more traditional measurement of apparent advancing and receding contact angles. Fluorodecyl POSS, a low-surface-energy material, was blended with commercially available poly(methyl methacrylate) (PMMA) and then dip- or spray-coated onto glass substrates. These surfaces were probed with a variety of liquids to illustrate the effects of probe liquid surface tension, solid surface chemistry, and surface texture on the apparent contact angles and wetting hysteresis of nonwetting surfaces. Woven meshes were then used as model structured substrates to add a second, larger length scale for the surface texture. When immersed into a probe liquid, these spray-coated mesh surfaces can form a metastable, solid-liquid-air interface on the largest length scale of surface texture. The increasing hydrostatic pressure associated with progressively greater immersion depths disrupts this metastable, composite interface and forces penetration of the probe liquid into the mesh structure. This transition is marked by a sudden change in the wetting hysteresis, which can be systematically probed using spray-coated, woven meshes of varying wire radius and spacing. We also show that dynamic tensiometry can accurately and quantitatively characterize topographical length scales that are present on microtextured surfaces.

Synergistic physical properties of cocured networks formed from di- and tricyanate esters.

The co-cyclotrimerization of two tricyanate ester monomers, Primaset PT-30 and 1,2,3-tris(4-cyanato)propane (FlexCy) in equal parts by weight with Primaset LECy, a liquid dicyanate ester, was investigated for the purpose of exploring synergistic performance benefits. The monomer mixtures formed stable, homogeneous blends that remained in the supercooled liquid state for long periods at room temperature, thereby providing many of the processing advantages of LECy in combination with significantly higher glass transition temperatures (315-360 °C at full cure) due to the presence of the tricyanate-derived segments in the conetwork. Interestingly, the glass transition temperatures of the conetworks after cure at 210 °C, at full cure, and after immersion in 85 °C water for 96 h were all higher than predicted by the Flory-Fox equation, most significantly for the samples immersed in hot water. Conetworks comprising equal parts by weight of PT-30 and LECy retained a "wet" glass transition temperature near 270 °C. The onset of thermochemical degradation for conetworks was dominated by that of the thermally less stable component, while char yields after the initial degradation step were close to values predicted by a linear rule of mixtures. Values for moisture uptake and density in the conetworks also showed behavior that was not clearly different from a linear rule of mixtures. An analysis of the flexural properties of catalyzed versions of these conetworks revealed that, when cured under the same conditions, conetworks containing 50 wt % PT-30 and 50 wt % LECy exhibited higher modulus than networks containing only LECy while conetworks containing 50 wt % FlexCy and 50 wt % LECy exhibited a lower modulus but significantly higher flexural strength and strain to failure. Thus, in the case of "FlexCy", LECy was copolymerized with a tricyanate that provided both improved toughness and a higher glass transition temperature.

Synthesis, characterization, and cure chemistry of renewable bis(cyanate) esters derived from 2-methoxy-4-methylphenol.

A series of renewable bis(cyanate) esters have been prepared from bisphenols synthesized by condensation of 2-methoxy-4-methylphenol (creosol) with formaldehyde, acetaldehyde, and propionaldehyde. The cyanate esters have been fully characterized by infrared spectroscopy, (1)H and (13)C NMR spectroscopy, and single crystal X-ray diffraction. These compounds melt from 88 to 143 °C, while cured resins have glass transition temperatures from 219 to 248 °C, water uptake (96 h, 85 °C immersion) in the range of 2.05-3.21%, and wet glass transition temperatures from 174 to 193 °C. These properties suggest that creosol-derived cyanate esters may be useful for a wide variety of military and commercial applications. The cure chemistry of the cyanate esters has been studied with FTIR spectroscopy and differential scanning calorimetry. The results show that cyanate esters with more sterically demanding bridging groups cure more slowly, but also more completely than those with a bridging methylene group. In addition to the structural differences, the purity of the cyanate esters has a significant effect on both the cure chemistry and final Tg of the materials. In some cases, post-cure of the resins at 350 °C resulted in significant decomposition and off-gassing, but cure protocols that terminated at 250-300 °C generated void-free resin pucks without degradation. Thermogravimetric analysis revealed that cured resins were stable up to 400 °C and then rapidly degraded. TGA/FTIR and mass spectrometry results showed that the resins decomposed to phenols, isocyanic acid, and secondary decomposition products, including CO2. Char yields of cured resins under N2 ranged from 27 to 35%, while char yields in air ranged from 8 to 11%. These data suggest that resins of this type may potentially be recycled to parent phenols, creosol, and other alkylated creosols by pyrolysis in the presence of excess water vapor. The ability to synthesize these high temperature resins from a phenol (creosol) that can be derived from lignin, coupled with the potential to recycle the composites, provides a possible route to the production of sustainable, high-performance, thermosetting resins with reduced environmental impact.

Superomniphobic surfaces for effective chemical shielding.

Superomniphobic surfaces display contact angles >150° and low contact angle hysteresis with essentially all contacting liquids. In this work, we report surfaces that display superomniphobicity with a range of different non-Newtonian liquids, in addition to superomniphobicity with a wide range of Newtonian liquids. Our surfaces possess hierarchical scales of re-entrant texture that significantly reduce the solid-liquid contact area. Virtually all liquids including concentrated organic and inorganic acids, bases, and solvents, as well as viscoelastic polymer solutions, can easily roll off and bounce on our surfaces. Consequently, they serve as effective chemical shields against virtually all liquids--organic or inorganic, polar or nonpolar, Newtonian or non-Newtonian.

Hygro-responsive membranes for effective oil-water separation.

There is a critical need for new energy-efficient solutions to separate oil-water mixtures, especially those stabilized by surfactants. Traditional membrane-based separation technologies are energy-intensive and limited, either by fouling or by the inability of a single membrane to separate all types of oil-water mixtures. Here we report membranes with hygro-responsive surfaces, which are both superhydrophilic and superoleophobic, in air and under water. Our membranes can separate, for the first time, a range of different oil-water mixtures in a single-unit operation, with >99.9% separation efficiency, by using the difference in capillary forces acting on the two phases. Our separation methodology is solely gravity-driven and consequently is expected to be highly energy-efficient. We anticipate that our separation methodology will have numerous applications, including the clean-up of oil spills, wastewater treatment, fuel purification and the separation of commercially relevant emulsions.

Hierarchically structured superoleophobic surfaces with ultralow contact angle hysteresis.

Hierarchically structured, superoleophobic surfaces are demonstrated that display one of the lowest contact angle hysteresis values ever reported - even with extremely low-surface-tension liquids such as n-heptane. Consequently, these surfaces allow, for the first time, even ≈2 µL n-heptane droplets to bounce and roll-off at tilt angles. ≤ 2°.

On-demand separation of oil-water mixtures.

In this work, the first-ever membrane-based single unit operation that enables gravity driven, on-demand separation of various oil-water mixtures is developed. Using this methodology, the on-demand separation of free oil and water, oil-in-water emulsions, and water-in-oil emulsions is demonstrated, with ≥99.9% separation efficiency. A scaled-up apparatus to separate larger quantities (several liters) of oil-water emulsions is also developed.

Superoleophobic surfaces through control of sprayed-on stochastic topography.

The liquid repellency and surface topography characteristics of coatings comprising a sprayed-on mixture of fluoroalkyl-functional precipitated silica and a fluoropolymer binder were examined using contact and sliding angle analysis, electron microscopy, and image analysis for determination of fractal dimensionality. The coatings proved to be an especially useful class of liquid repellent materials due to their combination of simple and scalable deposition process, low surface energy, and the roughness characteristics of the aggregates. These characteristics interact in a unique way to prevent the buildup of binder in interstitial regions, preserving re-entrant curvature across multiple length scales, thereby enabling a wide range of liquid repellency, including superoleophobicity. In addition, rather than accumulating in the interstices, the binder becomes widely distributed across the surface of the aggregates, enabling a mechanism in which a simple shortage or excess of binder controls the extent of coating roughness at very small length scales, thereby controlling the extent of liquid repellence.

Effect of chemical structure and network formation on physical properties of di(cyanate ester) thermosets.

Key physical properties of three dicyanate ester monomers, bisphenol A dicyanate (BADCy), bisphenol E dicyanate (LECy), and the dicyanate of a silicon-containing analogue of bisphenol A (SiMCy) were investigated as a function of cyanurate conversion at conversions ranging from approximately 70% to greater than 90% in order to assess the range of applicability of both traditional and more unusual structure-property-process relationships known for cyanate ester resins. A more complete understanding of these relationships is essential for the continued development of cyanate ester resins and their composites for a wide variety of aerospace applications. The degree of cure in each system was determined by differential scanning calorimetry (DSC). The degree of conversion achieved at a given temperature was dependent on the structure of the repeat unit, with SiMCy displaying the highest relative ease of cure. The density at room temperature was found to decrease monotonically with increasing conversion for all monomer types studied. In contrast, the water uptake decreased with increasing cure for all three materials over most or all of the conversion range studied, but leveled off or began to increase with increasing conversion at conversions of approximately 90%. The T(g) decreased after exposure to hot water in resins with greater than 85% conversion, but unexpectedly increased in samples with lower conversions. An investigation of the effect of hot water exposure on network chemistry via infrared spectroscopy indicated that carbamate formation varied with both monomer chemistry and extent of cure, but was greatest for the BADCy polycyanurates. On the other hand, the unreacted cyanate ester band tended to disappear uniformly, suggesting that reactions other than carbamate formation (such as cyclotrimerization) may also take place during exposure to hot water, possibly giving rise to the observed unusual increases in T(g) upon exposure.