Development of CuO/Cu4(OH)6SO4 Nanoparticle Mixtures to Optimize the H2S Adsorption.

In this paper, we report the H2S adsorption behavior of a sorbent composed of mixtures of tenorite (CuO) and brochantite [Cu4(OH)6SO4]. These materials are readily prepared through the addition of NaOH(aq) to CuSO4(aq). They can be loaded onto polymer foams to create effective filters that can remove malodorous H2S gas, as evidenced by breakthrough tests. X-ray diffraction shows that the ratio of the two compounds in the mixture can be finely tuned by varying the amount of NaOH(aq) that is added to the reaction mixture. X-ray photoelectron spectroscopy shows that brochantite, like tenorite, has the ability to chemically adsorb H2S. Correlation of the H2S breakthrough data with scanning transmission electron microscopy measurements shows that the most effective sorbents contain nanoscale needle-like particles. These are likely to be formed largely by the tenorite phase. The samples with the greatest H2S adsorption efficacy contained less than 20% tenorite in the mixture, where these particles had the greatest abundance. The application of this sorbent onto porous substrates to create effective filters, along with the synthetic ease of its production, could allow this methodology to find use in a number of areas where H2S poses a problem. This could include areas where protective clothing is required to adsorb the gas from environments where there is a high level of H2S, for example, in wastewater treatment plants, oil and gas wells, or in the medical sector, where it could be deployed as filter media.

Slippery Alkoxysilane Coatings for Antifouling Applications.

Herein, we report the wettability and antifouling behavior of a range of different siloxane coatings on plastic and glass substrates. The films investigated are prepared using trimethoxysilane precursors with different alkyl chain lengths (1-18 C atoms) in order to study how the nature of the hydrophobic group affects the different parameters used to characterize wettability (contact angles, sliding angles, and contact angle hysteresis). Atomic force microscopy analysis shows that the coatings possess low surface topography [root mean squared roughness (rms) < 50 nm] and are highly transparent as studied using UV-vis spectroscopy. The sliding properties of H2O, CH2I2, methanol, and ethylene glycol were observed to be strongly influenced by the chain length of the alkoxysilane precursor used. The coatings formed from the longer chain analogues show comparable water sliding angles to superhydrophobic surfaces. These coatings show similar performance to analogous alkoxysilane coating-bearing fluorinated groups, indicating that they could act as viable environmentally friendly alternatives to some of the fluorinated films that have been widely adopted. Furthermore, these surfaces are highly durable toward common forms of abrasion and are observed to show low adhesion toward synthetic feces, indicating that their utility extends further than repelling liquids alone. Consequently, these coatings could show promise for potential use in applications in the medical sector where fouling by biological mixtures leads to an unsustainable use of materials.

Interaction of Surface-Modified Alumina Nanoparticles and Surfactants at an Oil/Water Interface: A Neutron Reflectometry, Scattering, and Enhanced Oil Recovery Study.

The evaluation of the mechanism of nanoparticle (NP)/surfactant complex adsorption at the critical oil/water interface was studied. A sophisticated technique (neutron reflectometry) was used to give a unique insight on NP/oil interactions in oil recovery systems. Herein, the adsorption of two modified alumina NPs with different degrees of hydrophobicity [hydrophilic = 2-[2-(2-methoxyethoxy)ethoxy]acetic acid and hydrophobic = octanoic acid (OCT)] stabilized with two different surfactants were studied at the oil/water interface. A thin layer of deuterated (D) and hydrogenated (H) hexadecane (contrast matching silicon substrate) oil was formed on a silicon block by a spin coating freeze process. The distribution of the NPs across the oil/water interface with the CTAB surfactant is similar between the two systems. NPs coated with CTAB have more affinity toward the oil/water interface, which explains the oil recovery increase by around 5% when flooding the core with the OCT-NP/CTAB system compared to the surfactant flooding alone. These results suggest that the NP/surfactant complexes can have potential usage in EOR recovery applications.

Water-in-CO2 Microemulsions Stabilized by an Efficient Catanionic Surfactant.

To facilitate potential applications of water-in-supercritical CO2 microemulsions (W/CO2 µEs) efficient and environmentally responsible surfactants are required with low levels of fluorination. As well as being able to stabilize water-CO2 interfaces, these surfactants must also be economical, prevent bioaccumulation and strong adhesion, deactivation of enzymes, and be tolerant to high salt environments. Recently, an ion paired catanionic surfactant with environmentally acceptable fluorinated C6 tails was found to be very effective at stabilizing W/CO2 µEs with high water-to-surfactant molar ratios (W0) up to ∼50 (Sagisaka, M.; et al. Langmuir 2019, 35, 3445-3454). As the cationic and anionic constituent surfactants alone did not stabilize W/CO2 µEs, this was the first demonstration of surfactant synergistic effects in W/CO2 microemulsions. The aim of this new study is to understand the origin of these intriguing effects by detailed investigations of nanostructure in W/CO2 microemulsions using high-pressure small-angle neutron scattering (HP-SANS). These HP-SANS experiments have been used to determine the headgroup interfacial area and volume, aggregation number, and effective packing parameter (EPP). These SANS data suggest the effectiveness of this surfactant originates from increased EPP and decreased hydrophilic/CO2-philic balance, related to a reduced effective headgroup ionicity. This surfactant bears separate C6F13 tails and oppositely charged headgroups, and was found to have a EPP value similar to that of a double C4F9-tail anionic surfactant (4FG(EO)2), which was previously reported to be one of most efficient stabilizers for W/CO2 µEs (maximum W0 = 60-80). Catanionic surfactants based on this new design will be key for generating superefficient W/CO2 µEs with high stability and water solubilization.

New insights into the interactions between asphaltene and a low surface energy anionic surfactant under low and high brine salinity.

HYPOTHESIS: The hyperbranched chains on the tail of low surface energy surfactants (LSES) causes lowering of surface free energy and rock wettability alteration, offering significant improvement in oil recovery in asphaltene oil reservoirs. EXPERIMENTS: Oil sweep efficiency was determined by fluid displacement in pure brine and LSES-brine solutions in a microfluidic pattern that was representative of a sandstone cross-section. Interfacial tension (IFT), wettability alteration, Raman and X-ray photoelectron spectroscopy (XPS) were used to measure the changes of asphaltene interactions with oil-aged substrate after surface treating with brine and surfactant-brine solutions. FINDINGS: The hyperbranched LSES yielded a significant increase in the original-oil-in-place (OOIP) recovery (58%) relative to brine flooding (25%), even in the presence of asphaltene. Raman spectra showed the LSES-brine solutions to be capable of causing change to the asphaltene aggregate size after centrifugation treatment.

Controlling the wettability of plastic by thermally embedding coated aluminium oxide nanoparticles into the surface.

HYPOTHESIS: Nanoparticle embedding into the surface of plastics provides an effective anchor that improves the durability of coatings formed from functionalized nanoparticles. Coatings formed from thermally embedded particles show superior wear resistance relative to coatings formed from non-embedded particles. As a consequence of this, embedded nanoparticles functionalized with hydrophilic and hydrophobic carboxylates are better suited for controlling the wettability of plastics than when the nanoparticles are deposited onto the plastic under ambient conditions. EXPERIMENTS: Carboxylate-functionalized Al2O3 nanoparticles were embedded into ethylene vinyl acetate through spray coating the particles onto the substrate during heating. Sonication was used to remove excess particles that did not become embedded into the material. Coatings formed from the embedded particles were characterized through scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). The wettability of the coatings was characterized using static and dynamic contact angle (CA) measurements to measure the apparent water contact angles, and sliding angle measurements, whilst the durability of the coatings was studied using scratch testing, tape peel tests, and abrasion tests. The build-up of fog on the substrates was also studied through exposing the surfaces to water vapour. FINDINGS: Thermal embedding of the particles into the surface of the plastic was observed to occur when the material was heated to temperatures around its melting temperature. AFM and SEM showed that plastic embedded with the nanoparticles possessed a morphology that was substantially rougher than the untreated plastic. CA measurements showed that plastic embedded with hydrophobic isostearate functionalized nanoparticles was highly hydrophobic and displayed a CA of approximately 152°. Dynamic CA measurements and sliding angle measurements revealed that plastic embedded with the isostearate functionalized nanoparticles showed petal-like wetting behavior. Furthermore, it was observed that the CA of the plastic could be varied from highly hydrophobic to highly hydrophilic through embedding varying amounts of isostearate and hydrophilic 2-[2-(2-methoxyethoxy)ethoxy]acetate functionalized Al2O3 nanoparticles into the surface of the material. Scratch testing showed that thermally embedding the nanoparticles into the plastic substantially improved their abrasion resistance, relative to when the nanoparticles are deposited onto the non-heated material. This methodology indicates that embedding nanoparticles into plastics creates durable coatings that can display variable wettability. Consequently, this methodology could be useful in applications where it is desirable to keep plastics dry, such as for food packaging or medical devices.

Comparison of hydrophobicity and durability of functionalized aluminium oxide nanoparticle coatings with magnetite nanoparticles-links between morphology and wettability.

HYPOTHESIS: The wetting characteristics of coatings created using functionalised nanoparticles and adhesive resins, depends strongly on the particle distribution within the surface layers. Although it has been shown that commercially available adhesives improve the durability of hydrophobic nanoparticle coatings, the wettability of these surfaces is governed by the agglomeration behaviour of the particles within the adhesive. As a consequence of this, coatings where the particles are highly agglomerated within the adhesive show lower hydrophobicity. EXPERIMENTS: The morphology and chemical composition of coatings formed from carboxylate functionalised Al2O3 and magnetite (Fe3O4) nanoparticles and epoxy resin on plastic was studied using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Water contact angle (WCA) measurements were used to investigate how the coatings' morphological characteristics and loading of the particles within the surface layers influenced their wettability. Infrared (IR) spectroscopy and thermogravimetric analysis (TGA) were used to study carboxylate adsorption onto the magnetite nanoparticles. FINDINGS: Combining the Al2O3 nanoparticles with epoxy resin was observed to create highly hydrophobic coatings that displayed water contact angles (WCAs) between 145 and 150°. These coatings displayed good durability when sonicated in isopropanol and wiped with tissue. By comparison, coatings formed from the magnetite nanoparticles were substantially less hydrophobic and displayed WCAs between 75 and 125° when combined with epoxy resin. SEM revealed that the magnetite nanoparticles in the coatings were present as large agglomerates. By comparison, coatings formed from the Al2O3 nanoparticles showed a more homogenous particle distribution. Furthermore, XPS showed that the resin engulfed the magnetite nanoparticles to a far greater extent. The difference in wetting behaviour of these coatings is largely attributed to their different morphologies, since the particles are similar sizes and TGA shows that the particles possess similar carboxylate grafting densities. The uneven distribution of nanoparticles in the magnetite/epoxy resin coating is due to the particles' magnetic properties, which drive nanoparticle agglomeration as the coatings solidify. This work demonstrates that it is important to consider inter-particle interactions when fabricating low wettability composite coatings.

Size and morphology dependent surface wetting based on hydrocarbon functionalized nanoparticles.

HYPOTHESIS: The wetting properties of films created using metal oxide nanoparticles can be controlled through roughness and chemical functionality; however, other variations such as the size and shape of the particles play an important role in improved understanding of the wetting behaviour of these materials. EXPERIMENTS: Infrared (IR) spectroscopy and thermogravimetric analysis (TGA) were used to study the chemisorption and grafting density of a carboxylic acid onto the surface of nanoparticles. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to investigate the morphology and roughness of the nanoparticle films. To investigate the wettability and surface energy of the films, static and dynamic contact angle (CA) measurements were used. FINDINGS: Smaller, spherical nanoparticles (<50 nm) were observed to create films that displayed greater surface roughness and showed superhydrophobic properties. By comparison, larger, 135 nm spherical nanoparticles showed reduced surface roughness and displayed water contact angles (WCAs) <150°. Since these particles showed similar carboxylate grafting densities, this suggests that there is a particle size limit above which it is not possible to deposit superhydrophobic films. This study also shows that topographical effects brought about by film roughness can be overcome through increasing the carboxylate grafting density on the surface of the nanoparticles. It was observed that films created using mix shape <50 nm nanoparticles with relatively low surface roughness displayed superhydrophobic WCAs and low hysteresis. These particles also possessed a substantially larger carboxylate grafting density, indicating that the extent of functionalization also has a large bearing on the wettability of the films. Herein, we show that particle size, morphology, and reactivity all play important roles in determining the wettability of nanoparticle films.

Aqueous electromigration of single-walled carbon nanotubes and co-electromigration with copper ions.

The electromigration behaviour of raw and acid purified single walled carbon nanotubes (SWCNTs) in dilute aqueous systems (0.0034 mg mL-1), in the absence of surfactant, with the addition of either 0.85 M acetic acid or 0.1 M CuSO4, was evaluated using a 2-inch copper cathode and either a 2-inch copper or 0.5-inch platinum anode. The results showed that the electromigration of raw SWCNTs (with a high catalyst residue) in the presence of CuSO4 resulted in the formation of a Cu-SWCNT composite material at the cathode. In contrast, acid purified SWCNTs were observed to diffuse to a copper anode, creating fibrillated agglomerates with "rice-grain"-like morphologies. Upon acidification with acetic acid (or addition of CuSO4) the direction of electromigration reversed towards the cathode as a result of coordination of Cu2+ to the functional groups on the SWCNT overcoming the inherent negative charge of the acid purified SWCNTs. The result was the co-deposition of SWCNTs and Cu metal on the cathode. Addition of 0.005 M EDTA sequesters some of the Cu2+ and resulted in the separation of metal decorated SWCNTs to the cathode and un-decorated SWCNTs to the anode. The resulting SWCNT and Cu/SWCNT deposits were characterized by Raman spectroscopy, XPS, SEM, EDS, and TEM.

A new family of urea-based low molecular-weight organogelators for environmental remediation: the influence of structure.

Gelation processes grant access to a wealth of soft materials with tailorable properties, in applications as diverse as environmental remediation, biomedicine and electronics. Several classes of self-assembling gelators have been studied and employ non-covalent bonds to direct assembly, but recently attention has come to focus on how the overall shape of the gelator molecule impacts its gelation. Here we study a new sub-family of low molecular weight organogelators and explore how steric rearrangement influences their gelation. The gels produced are characterised with X-ray diffraction and small-angle neutron scattering (SANS) to probe their ex situ and in situ gelation mechanisms. The best examples were then tested for environmental remediation applications, gelling petrol and oils in the presence of water and salts.

Tunable Surface Properties of Aluminum Oxide Nanoparticles from Highly Hydrophobic to Highly Hydrophilic.

The formation of materials with tunable wettability is important for applications ranging from antifouling to waterproofing surfaces. We report the use of various low-cost and nonhazardous hydrocarbon materials to tune the surface properties of aluminum oxide nanoparticles (NPs) from superhydrophilic to superhydrophobic through covalent functionalization. The hydrocarbon surfaces are compared with a fluorinated surface for wettability and surface energy properties. The role of NPs' hydrophobicity on their dynamic interfacial behavior at the oil-water interface and their ability to form stable emulsions is also explored. The spray-coated NPs provide textured surfaces (regardless of functionality), with water contact angles (θ) of 10-150° based on their surface functionality. The superhydrophobic NPs are able to reduce the interfacial tension of various oil-water interfaces by behaving as surfactants.

Assembly of porous hierarchical copolymers/resin proppants: New approaches to smart proppant immobilization via molecular anchors.

HYPOTHESIS: The assembly of temperature/pH sensitive complex microparticle structures through chemisorption and physisorption provides a responsive system that offers application as routes to immobilization of proppants in-situ. EXPERIMENTS: Thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) along with energy dispersive X-ray analysis (EDX) have been used to characterize a series of bi-functionalized monolayers and/or multilayers grown on alumina microparticles and investigate the reactive nature of both temperature sensitive cross-linker (epoxy resin) with the layers and pH-responsive bridging layer (polyetheramine). FINDINGS: The bifunctional acids, behaving as molecular anchors, allow for a controlled reaction with a cross-linker (resin or polymer) with the formation of networks, which is either irreversible or reversible based on the nature of the cross-linker. The networks results in formation of porous hierarchical particles that offer a potential route to the creation of immobile proppant pack.

Branched Hydrocarbon Low Surface Energy Materials for Superhydrophobic Nanoparticle Derived Surfaces.

We present a new class of superhydrophobic surfaces created from low-cost and easily synthesized aluminum oxide nanoparticles functionalized carboxylic acids having highly branched hydrocarbon (HC) chains. These branched chains are new low surface energy materials (LSEMs) which can replace environmentally hazardous and expensive fluorocarbons (FCs). Regardless of coating method and curing temperature, the resulting textured surfaces develop water contact angles (θ) of ∼155° and root-mean-square roughnesses (Rq) ≈ 85 nm, being comparable with equivalent FC functionalized surfaces (θ = 157° and Rq = 100 nm). The functionalized nanoparticles may be coated onto a variety of substrates to generate different superhydrophobic materials.

Properties of surfactant films in water-in-CO2 microemulsions obtained by small-angle neutron scattering.

HYPOTHESIS: The formation, stability and structural properties of normal liquid phase microemulsions, stabilized by hydrocarbon surfactants, comprising water and hydrocarbon oils can be interpreted in terms of the film bending rigidity (energy) model. Here, this model is tested for unusual water-in-CO2 (w/c) microemulsions, formed at high pressure with supercritical CO2 (sc-CO2) as a solvent and fluorinated surfactants as stabilizers. Hence, it is possible to explore the generality of this model for other types of microemulsions. EXPERIMENTS: High Pressure Small-Angle Neutron Scattering (HP-SANS) has been used to study w/c microemulsions, using contrast variation to highlight scattering from the stabilizing fluorinated surfactant films: these data show clear evidence for spherical core-shell structures for the microemulsion droplets. FINDINGS: The results extend understanding of w/c microemulsions since previous SANS studies are based only on scattering from water core droplets. Here, detailed structural parameters for the surfactant films, such as thickness and film bending energy, have been extracted from the core-shell SANS profiles revealed by controlled contrast variation. Furthermore, at reduced CO2 densities (∼0.7gcm(-3)), elongated cylindrical droplet structures have been observed, which are uncommon for CO2 microemulsions/emulsions. The implications of the presence of cylindrical micelles and droplets for applications of CO2, and viscosity enhancements are discussed.

Hyperbranched hydrocarbon surfactants give fluorocarbon-like low surface energies.

Two series of Aerosol-OT-analogue surfactants (sulfosuccinate-type di-BCnSS and sulfoglutarate-type di-BCnSG) with hyperbranched alkyl double tails (so-called "hedgehog" groups, carbon number n = 6, 9, 12, and 18) have been synthesized and shown to demonstrate interfacial properties comparable to those seen for related fluorocarbon (FC) systems. Critical micelle concentration (CMC), surface tension at the CMC (γCMC), and minimum area per molecule (Amin) were obtained from surface tension measurements of aqueous surfactant solutions. The results were examined for relationships between the structure of the hedgehog group and packing density at the interface. To evaluate A and B values in the Klevens equation for these hedgehog surfactants, log(CMC) was plotted as a function of the total carbon number in the surfactant double tail. A linear relationship was observed, producing B values of 0.20-0.25 for di-BCnSS and di-BCnSG, compared to a value of 0.31 for standard double-straight-tail sulfosuccinate surfactants. The lower B values of these hedgehog surfactants highlight their lower hydrophobicity compared to double-straight-tail surfactants. To clarify how hydrocarbon density in the surfactant-tail layer (ρ(layer)) affects γCMC, the ρ(layer) of each double-tail surfactant was calculated and the relationship between γCMC and ρ(layer) examined. As expected for the design of low surface energy surfactant layers, ρ(layer) was identified as an important property for controlling γCMC with higher ρ(layer), leading to a lower γCMC. Interestingly, surfactants with BC9 and BC12 tails achieved much lower γCMC, even at low ρ(layer) values of <0.55 g cm(-3). The lowest surface energy surfactant studied here was di-BC6SS, which had a γCMC of only 23.8 mN m(-1). Such a low γCMC is comparable to those obtained with short FC-tail surfactants (e.g., 22.0 mN m(-1) for the sulfosuccinate-type FC-surfactant with R = F(CF2)6CH2CH2-).

Aggregation behavior of polyisoprene-pluronic graft copolymers in selective solvents.

Novel amphiphilic graft copolymers composed of a polyisoprene (PIP) backbone with Pluronic side chains, polyisoprene-g-Pluronic, have been synthesized using a "graft onto" technique. Small-angle neutron scattering (SANS) has been used to characterize the conformation of the P123 and P103 Pluronic graft copolymers in selective solvents such as ethanol and hexane and in a nonselective solvent, tetrahydrofuran (THF). The results indicated that, in a selective solvent for the side chain Pluronics (e.g., ethanol), "crew-cut" micelles were formed with a large core of radius ∼ 120 Å; data were fitted with a core-shell model. In a good solvent for the backbone (e.g., hexane), "flowerlike" micelles were formed with a small inner radius of ∼64 Å. In the nonselective solvent, a swollen polymer coil was found, which was described using the Guinier-Debye model. As THF/ethanol and THF/hexane can be prepared in any ratio, it was possible to vary the solvent composition gradually in order to study the transition from swollen coil to micelle. When going from 100% THF to 100% ethanol, the transition to micellar behavior was observed at a ratio of 20:80 (v/v %) THF/ethanol for both grafted copolymers and 40:60 (v/v %) THF/hexane for grafted P123 copolymers.

Low-surface energy surfactants with branched hydrocarbon architectures.

Surface tensiometry and small-angle neutron scattering have been used to characterize a new class of low-surface energy surfactants (LSESs), "hedgehog" surfactants. These surfactants are based on highly branched hydrocarbon (HC) chains as replacements for environmentally hazardous fluorocarbon surfactants and polymers. Tensiometric analyses indicate that a subtle structural modification in the tails and headgroup results in significant effects on limiting surface tensions γcmc at the critical micelle concentration: a higher level of branching and an increased counterion size promote an effective reduction of surface tension to low values for HC surfactants (γcmc ∼ 24 mN m(-1)). These LSESs present a new class of potentially very important materials, which form lamellar aggregates in aqueous solutions independent of dilution.

Interaction between surfactants and colloidal latexes in nonpolar solvents studied using contrast-variation small-angle neutron scattering.

The interaction between deuterium-labeled Aerosol OT surfactant (AOT-d34) and sterically stabilized poly(methyl methacrylate) (PMMA) latex particles dispersed in nonpolar solvents has been studied using contrast-variation small-angle neutron scattering (CV-SANS). The electrophoretic mobilities (µ) of the latexes have been measured by phase-analysis light scattering, indicating that µ is negative. Two analogues of the stabilizers for the particles have been studied as free polymers in the absence of PMMA latexes: poly(12-hydroxystearic acid) (PHSA) polyester and poly(methyl methacrylate)-graft-poly(12-hydroxystearic acid) (PMMA-graft-PHSA) stabilizer copolymer. The scattering from both PHSA in dodecane and PMMA-graft-PHSA in toluene is consistent with extended polymer chains in good solvents. In dodecane, PMMA-graft-PHSA forms polymer micelles, and SANS is consistent with ellipsoidal aggregates formed of around 50 polymer chains. CV-SANS measurements were performed by measuring SANS from systems of PHSA, PMMA-graft-PHSA, and PMMA latexes with 10 and 100 mM surfactant solutions of AOT-d34 in both polymer/particle and AOT contrast-matched solvent. No excess scattering above the polymer or surfactant was found for PHSA in dodecane or PMMA-graft-PHSA in dodecane and toluene. This indicates that AOT does not significantly interact with the free polymers. Excess scattering was observed for systems with AOT-d34 and PMMA latexes dispersed in particle contrast-matched dodecane, consistent with the penetration of AOT into the PMMA latexes. This indicates that AOT does not interact preferentially with the stabilizing layers but, rather, is present throughout the colloids. Previous research ( Langmuir 2010, 26, 6967-6976 ) suggests that AOT surfactant is located in the latex PHSA-stabilizer layer, but all the results in this study are consistent with AOT poorly interacting with alkyl-stabilizer polymers.

Shape transitions in supercritical CO2 microemulsions induced by hydrotropes.

The ability to induce morphological transitions in water-in-oil (w/o) and water-in-CO2 (w/c) microemulsions stabilized by a trichain anionic surfactant 1,4-bis(neopentyloxy)-3-(neopentyloxycarbonyl)-1,4-dioxobutane-2-sulfonate (TC14) with simple hydrotrope additives has been investigated. High-pressure small-angle neutron scattering (SANS) has revealed the addition of a small mole fraction of hydrotrope can yield a significant elongation in the microemulsion water droplets. For w/o systems, the degree of droplet growth was shown to be dependent on the water content, the hydrotrope mole fraction, and chemical structure, whereas for w/c microemulsions a similar, but less significant, effect was seen. The expected CO2 viscosity increase from such systems has been calculated and compared to related literature using fluorocarbon chain surfactants. This represents the first report of hydrotrope-induced morphology changes in w/c microemulsions and is a significant step forward toward the formation of hydrocarbon worm-like micellar assemblies in this industrially relevant solvent.

Effect of temperature, cosolvent, and added drug on Pluronic-flurbiprofen micellization.

Structural changes in the micellization of Pluronics P103 and P123, as a function of temperature, cosolvent (ethanol, 10 v/v %), and the addition of the hydrophobic drug flurbiprofen, were investigated by SANS and tensiometry. Addition of ethanol increases the critical micellization concentration of the Pluronics (making the polymer more soluble), while increasing the repulsive interactions between the flurbiprofen-Pluronic spherical complexes. However, increasing temperature and addition of drug increases both the aggregation number and core radius and leads to a more dehydrated core. The addition of flurbiprofen to Pluronic P103 was also found to reduce the critical micellization temperature from between 15 and 20 °C to below 10 °C and at higher drug concentrations leads to an attractive interaction between micelles and eventually phase separation.