Residual stress is an intrinsic property of semicrystalline plastics such as polypropylene and polyethylene. However, there is no fundamental understanding of the role intrinsic residual stress plays in the generation of plastic pollutants that threaten the environment and human health. Here, we show that the processing-induced compressive residual stress typically found in polypropylene and polyethylene plastics forces internal nano and microscale segregation of low molecular weight (MW) amorphous polymer droplets onto the plastic's surface. Squeeze flow simulations reveal this stress-driven volumetric flow is consistent with that of a Bingham plastic material, with a temperature-dependent threshold yield stress. We confirm that flow is thermally activated and stress dependent, with a reduced energy barrier at higher compressive stresses. Transfer of surface segregated droplets into water generates amorphous polymer micropollutants (APMPs) that are denatured, with structure and composition different from that of traditional polycrystalline microplastics. Studies with water-containing plastic bottles show that the highly compressed bottle neck and mouth regions are predominantly responsible for the release of APMPs. Our findings reveal a stress-induced mechanism of plastic degradation and underscore the need to modify current plastic processing technologies to reduce residual stress levels and suppress phase separation of low MW APMPs in plastics.

Micro- and nanoplastics (MNPs) are pervasive micropollutants in aquatic environments and along shorelines. Their release is predominantly attributed to mechanical abrasion or ultraviolet exposure, both requiring substantial external energy inputs. The role of aquatic factors (e.g., air bubbles) in the generation of MNPs is poorly understood. Here we show microbubbles that spontaneously form on seven typical plastics across a wide temperature range (25° to 95°C) and in various water types (deionized, tap, river, and marine water) can erode plastic surfaces and drive MNP release. Nucleation, expansion, and movement of microbubbles generate shear stresses capable of dislodging polymer protrusions at surface defect sites. This sweeping action, combined with the unbalanced surface tension forces at the three-phase contact line, generates O-shaped ring structures composed of accumulated polymers, which ultimately fragment leading to the release of MNPs into the aquatic environment. Our findings demonstrate that microbubble-induced erosion represents a low-energy pathway for micropollutant release.

Earlier studies demonstrated the ability of some fluorinated surfactants to form rod-like reverse micelles with the ability to thicken water/supercritical CO2 (scCO(2)) mixtures at temperatures below 45 degree celsius [Langmuir 26 (2010) 83-88. Soft Matter 8 (2012) 7044-7055. Colloids and Surfaces B, 168 (2018), 201-210.]. Such viscosity enhancement of scCO(2) is known to increase sweep efficiency for oil recovery with CO2 flooding. However, temperatures of up to similar to 100 degree celsius in conventional reservoirs are much higher than those employed in laboratory studies, and tend to weaken inter- and intra-molecular interactions between surfactant molecules, discouraging rod-like reverse micelle formation. With the aim of designing surfactants which form rod-like reverse micelles and thicken CO2 at high temperatures, this study examined phase behavior, nanostructures of reverse micelles and thickening ability of double omega-hydroperfluorocarbon-tail anionic surfactants in W/scCO(2) mixtures at temperatures of 35 - 75 degree celsius and pressure of 80 - 400 bar with different water-to-surfactant molar ratios (W-0). The measured CO2 viscosity increased by 1.9-2.2 x for double-chain surfactants M(di-HCF6)(x) (counterion Mx+ = Ni2+ and Co2+) at 40 mM, over the experimental temperature range. On the other hand, the shorter chain H(CF2)(4)CH2 twin-tail surfactants M(di-HCF4)(x) and Na(di-HCF6) gave only 1.1-1.5 x viscosity enhancements. The maximum thickening ability of M(di-HCF6)(2) was at W-0 = 10 in the W-0 range of 5-20 75 degree celsius and 350 bar. High pressure and high temperature small-angle neutron scattering (SANS) was used determine the micellar structure in these systems, and rod micelles of aspect ratios of 4.5-6.5 were found. The results clearly suggest that omega-hydroperfluorohexyl-tails and divalent counterions induce the formation of rod-like reverse micelles in W/CO2 mixtures, even at high temperatures commensurate with in-reservoir conditions.

Abstract Microplastic release from semicrystalline plastics threaten the environment and human health. We investigated polypropylene and polyethylene plastics, which together account for 54% of the global market. Mimicking common levels of residual stress found in plastics via cantilever beam experiments, we demonstrated that compressive stress drives nano and microscale segregation of amorphous polymer droplets onto the plastic’s surface. Simulations reveal this stress-driven volumetric flow is consistent with that of a Bingham plastic material, with a temperature-dependent threshold yield stress. Flow is thermally activated and stress dependent, with a reduced energy barrier at higher compressive stresses. Transfer of surface segregated amorphous droplets into the surroundings generates microplastics. Studies with water-containing plastic bottles showed that the highly compressed neck and mouth regions were predominantly responsible for the release of microplastics.

Abstract Detecting and monitoring the presence of nanoplastics (NPs) in the environment is a challenge due to their small size compared to the diffraction limits (~ 300 nm) of conventional spectroscopy. To address this, we developed a straightforward fluorescence mapping technology capable of accurately locating, quantifying, and identifying Nile-Red-stained polystyrene and polyethylene terephthalate NPs down to sizes of 60 nm. Verification of the quantity and locations of dyed NPs within a scanned area was carried out by scanning electron microscopy in conjunction with fluorescence mapping analysis. The ability to successfully resolve individual NPs of different type and sizes in complex real-world samples in the presence of contaminant and chemical additive nanoparticles was demonstrated and provides the basis for low-cost rapid screening of NPs.

This study investigates the flocculation induced destabilization of particulate dispersions by oppositely charged polymer–surfactant complexes, with a particular focus on controlling interactions by modulating the charge ratio Z, (where Z = [+polymer]/[−surfactant]) via [−surfactant] at fixed Cpolymer. Cationic hydroxyethyl cellulose (cat-HEC) polymer-sodium dodecylsulfate (SDS) complexes were prepared with either excess polymer (Z > 1) or surfactant (Z < 1) charges. Anionic particulate dispersions (Ludox and polystyrene-butadiene Latex) were then exposed to the complexes, and solvent relaxation NMR was used to characterize the particle surfaces before and after exposure. In both particulate dispersions, flocculation induced destabilization was enhanced after exposure to cat-HEC-SDS complexes with Z > 1, leaving any excess particle surfaces uncoated after gentle centrifugation. However, complexes with Z < 1 showed no adsorption and destabilization in the Ludox dispersions and only slight destabilization in the Latex dispersions due to possible hydrophobic interactions. Substituting SDS for non-ionic surfactant (C12E6) showed no additional destabilization of the dispersions, but post-centrifugation relaxation rates indicated preferential adsorption of C12E6 onto the particle surfaces. Since the dominant forces are electrostatic, this study highlights the possibility of controlling the interactions between oppositely charged polymer–surfactant complexes and particle surfaces by modulating Z through [−surfactant].

Previous studies [Langmuir, 2014, 30, 21, 6057-6063, Phys. Chem. Chem. Phys., 2017,19, 23869-23877] have shown that surfactants bearing highly-methylated alkyl tails (so-called "hedgehog" groups) are able to reduce the limiting surface tension at the aqueous critical micelle concentration (CMC) to gamma(CMC)-24 mN m(-1), which is considerably lower than for common n-alkyl tail surfactants (30-40 mN m(-1)). In the quest to develop even more effective and efficient non-fluorinated surfactants, this study introduces new amphiphiles having double and triple hedgehog tails and examines relationships between surfactant structure and aqueous solution properties. Of particular interest are links between gamma(CMC), the effective hydrophobic-tail layer density (rho(layer)) and total number of carbon and silicon atoms in the hydrophobic tails (NC+Si). Interestingly, gamma(CMC) is seen to depend on rho(layer) rather than NC+Si, and rho(layer) similar to 0.63 g cm(-3) appears to be an optimal surface layer density for promoting low gamma(CMC). For a surfactant bearing trimethysilyl (TMS) chain tips, exchanging the surfactant counterions from Na+ to Mg2+ reduced gamma(CMC) from 23.8 mN m(-1) to 21.5 mN m(-1), which is very low for a hydrocarbon surfactant, and comparable to typical fluorinated surfactants. A new measure of the ability of different surfactants to lower surface tension is proposed, which is helpful for targeting low surface energy (tension) non-fluorinated surfactants. In terms of both gamma(CMC) and CMC TMS-terminal tips are shown to be key groups for promoting hydrophobicity and/or low surface tensions.

Oppositely charged polymer–surfactant complexes are frequently explored as a function of phase space defined by the charge ratio Z, (where Z = [+polymer]/[−surfactant]), commonly accessed through the surfactant concentration. Tuning the phase behaviour and related properties of these complexes is an important tool for optimising commercial formulations; hence, understanding the relationship between Z and bulk properties is pertinent. Here, within a homologous series of cationic hydroxyethyl cellulose (cat-HEC) polymers with minor perturbations in the degree of side chain charge modification, phase space is instead explored through [+polymer] at fixed Cpolymer. The nanostructures were characterised by small-angle neutron scattering (SANS) in D2O solutions and in combination with the oppositely charged surfactant sodium dodecylsulfate (h- or d-SDS). Scattering consistent with thin rods with an average radius of ∼7.7 Å and length of ∼85 Å was observed for all cat-HEC polymers and no significant interactions were shown between the neutral HEC polymer and SDS (CSDS < CMC). For the charge-modified polymers, interactions with SDS were evident and the radius of the formed complexes grew up to ∼15 Å with increasing Z. This study demonstrates a novel approach in which the Z phase space of oppositely charged polymer–surfactant complexes can be controlled at fixed concentrations.

With an aim to control the surface hydrophobicity and water adhesion, as observed on various natural surfaces, novel 3,4-propylenedioxythiophene (ProDOT) monomers having one and two 3-trimethylsilylpropyl (TMS) groups were synthesized and subjected to electropolymerization to form surface coatings. The monomer ProDOT is employed owing to its tendency to form fibrous structures by electropolymerization [T. Darmanin, F. Guittard, Mater. Chem. Phys. 146 (2014) 6–11], whereas the TMS groups generate very low surface energies comparable to short chain fluorocarbons [N. M. Kovalchuk, et al., Colloids Surfaces A 604 (2020) 125277.]. It is shown that even though these two types of monomer lead to fibrous structures, the dimensions of the fibers as well as the wetting properties are different. The monomer with only a single TMS group (ProDOTSiMe3) generates extremely long nanofibers with only low surface roughness. The resulting surfaces have extremely high apparent contact angles (θw) up to 141.7° and strong water adhesion, similar to rose petals or gecko feet. On the other hand, the analogue with two TMS groups (ProDOT(SiMe3)2) forms short nanofibers but with extremely high surface roughness. The resulting surfaces are superhydrophobic with θw > 160° and ultra-low water adhesion (hysteresis and sliding angles < 1°), similar to lotus leaves. These results point to interesting applications offering control over water adhesion whilst maintaining high hydrophobicity.

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.

The interfacial properties and water-in-CO2 (W/CO2) microemulsion (μE) formation with double- and novel triple-tail surfactants bearing trimethylsilyl (TMS) groups in the tails are investigated. Comparisons of these properties are made with those for analogous hydrocarbon (HC) and fluorocarbon (FC) tail surfactants. Surface tension measurements allowed for critical micelle concentrations (CMC) and surface tensions at the CMC (γCMC) to be determined, resulting in the following trend in surface activity FC > TMS > HC. Addition of a third surfactant tail gave rise to increased surface activity, and very low γCMC values were recorded for the double/triple-tail TMS and HC surfactants. Comparing effective tail group densities (ρlayer) of the respective surfactants allowed for an understanding of how γCMC is affected by both the number of surfactant tails and the chemistry of the tails. These results highlight the important role of tail group chemical structure on ρlayer for double-tail surfactants. For triple-tail surfactants, however, the degree to which ρlayer is affected by tail group architecture is harder to discern due to formation of highly dense layers. Stable W/CO2 μEs were formed by both the double- and the triple-tail TMS surfactants. High-pressure small-angle neutron scattering (HP-SANS) has been used to characterize the nanostructures of W/CO2 μEs formed by the double- and triple-tail surfactants, and at constant pressure and temperature, the aqueous cores of the microemulsions were found to swell with increasing water-to-surfactant ratio (W0). A maximum W0 value of 25 was recorded for the triple-tail TMS surfactant, which is very rare for nonfluorinated surfactants. These data therefore highlight important parameters required to design fluorine-free environmentally responsible surfactants for stabilizing W/CO2 μEs.

High-water-content water-in-supercritical CO2 (W/CO2) microemulsions are considered to be green, universal solvents, having both polar and nonpolar domains. Unfortunately, these systems generally require environmentally unacceptable stabilizers like long and/or multifluorocarbon-tail surfactants. Here, a series of catanionic surfactants having more environmentally friendly fluorinated C4-C6 tails have been studied in terms of interfacial properties, aggregation behavior, and solubilizing power in water and/or CO2. Surface tensions and critical micelle concentrations of these catanionic surfactants are, respectively, lowered by ∼9 mN/m and 100 times than those of the constituent single fluorocarbon-tail surfactants. Disklike micelles in water were observed above the respective critical micelle concentrations, implying the catanionic surfactants have a high critical packing parameter, which should be suitable for the formation of reverse micelles. Based on visual observation of phase behavior and Fourier transform infrared spectroscopic and small-angle neutron scattering studies, one of the three catanionic surfactants tested was found to form transparent single-phase W/CO2 microemulsions with a water-to-surfactant molar ratio of up to ∼50. This is the first successful demonstration of the formation of W/CO2 microemulsions by synergistic ion-pairing of anionic and cationic single-tail surfactants. This indicates that catanionic surfactants offer a promising approach to generate high-water-content W/CO2 microemulsions.

Previous work (M. Sagisaka, etal. Langmuir 31 (2015)7479-7487), showed the most effective fluorocarbon (FC) and hydrocarbon (HC) chain lengths in the hybrid surfactants FCm-HCn (sodium 1-oxo-1-[4-(perfluoroalkyl)phenyl]alkane-2-sulfonates, where m = FC length and n = HC length) were m and n = 6 and 4 for water solubilization, whereas m 6 and n 6, or m 6 and n 5, were optimal chain lengths for reversed micelle elongation in supercritical CO2. To clarify why this difference of only a few methylene chain units is so effective at tuning the solubilizing power and reversed micelle morphology, nanostructures of water-in-CO2(W/CO2) microemulsions were investigated by high-pressure small-angle neutron scattering (SANS) measurements at different water-to-surfactant molar ratios (W-0) and surfactant concentrations. By modelling SANS profiles with cylindrical and ellipsoidal form factors, the FC6-HCn/W/CO2 microemulsions were found to increase in size with increasing W-0 and surfactant concentration: Ellipsoidal cross-sectional radii of the FC6-HC4/W/CO2 microemulsion droplets increased linearly with Wo, and finally reached similar to 39 angstrom and similar to 78 angstrom at W-0 = 85 (close to the upper limit of solubilizing power). These systems appear to be the largest W/CO2 microemulsion droplets ever reported. The aqueous domains of FC6-HC6 rod-like reversed micelles increased in size by 3.5 times on increasing surfactant concentration from 35 mM to 50 mM: at 35 mM, FC6-HC5 formed rod-like reversed micelles 5.3 times larger than FC6-HC6. Interestingly, these results suggest that hybrid HC-chains partition into the microemulsion aqueous cores with the sulfonate headgroups, or at the W/CO2 interfaces, and so play important roles' for tuning the W/CO2 interfacial curvature. The super-efficient W/CO2-type solubilizer FC6-HC4, and the rod-like reversed micelle forming surfactant FC6-HC5, represent the most successful cases of low fluorine content additives. These surfactants facilitate VOC-free, effective and energy-saving CO2 solvent systems for applications such as extraction, dyeing, dry cleaning, metal-plating, enhanced oil recovery and organic/inorganic or nanomaterial synthesis. (C) 2017 Elsevier B.V. All rights reserved.

Hypothesis: Reports on the colloidal and interfacial properties of fluorocarbon (FC) surfactants used in fire-fighting foam formulations are rare. This is primarily because these formulations are complex mixtures of different hydrocarbon (HC) and fluorocarbon (FC) surfactants. By developing a greater understanding of the individual properties of these commercial FC surfactants, links can be made between structure and respective surface/bulk behaviour. Improved understanding of structure property relationships of FC surfactants will therefore facilitate the design of more environmentally responsible surfactant replacements. Experiments: Surface properties of three partially fluorinated technical grade surfactants were determined using tensiometry and neutron reflection (NR), and compared with a research-grade reference surfactant (sodium perfiuorooctanoate (NaPFO)). To investigate the bulk behaviour and self-assembly in solution, small-angle neutron (SANS) scattering was used. Findings: All FC surfactants in this study generate very low surface tensions (< 20 mN m(-1)) which are comparable, and in some cases, lower than fully-fluorinated surfactant analogues. The complementary techniques (tensiometry and NR) allowed direct comparison to be made with NaPFO in terms of adsorption parameters such as surface excess and area per molecule. Surface tension data for these technical grade FC surfactants were not amenable to reliable interpretation using the Gibbs adsorption equation, however NR provided reliable results. SANS has highlighted how changes in surfactant head group structure can affect bulk properties. This work therefore provides fresh insight into the structure property relationships of some industrially relevant FC surfactants, highlighting properties which are essential for development of more environmentally friendly replacements. (C) 2018 Elsevier Inc. All rights reserved.

A facile electrochemical exfoliation method was established to efficiently prepare conducive paper containing reduced graphene oxide (RGO) with the help of single chain anionic surfactant ionic liquids (SAILs). The surfactant ionic liquids are synthesized from conventional organic surfactant anions and a 1-butyl-3-methyl-imidazolium cation. For the first time the combination of SAILs and cellulose was used to directly exfoliate graphite. The ionic liquid 1-butyl-3-methyl-imidazolium dodecylbenzenesulfonate (BMIM-DBS) was shown to have notable affinity for graphene, demonstrating improved electrical properties of the conducive cellulose paper. The presence of BMIM DBS in the system promotes five orders of magnitude enhancement of the paper electrical conductivity (2.71 x 10(-5) S cm(-1)) compared to the naive cellulose (1.97 x 10(-10) S cm(-1)). A thorough investigation using electron microscopy and Raman spectroscopy highlights the presence of uniform graphene incorporated inside the matrices. Studies into aqueous aggregation behavior using small-angle neutron scattering (SANS) point to the ability of this compound to act as a bridge between graphene and cellulose, and is responsible for the enhanced exfoliation level and stabilization of the resulting dispersion. The simple and feasible process for producing conducive paper described here is attractive for the possibility of scaling-up this technique for mass production of conducive composites containing graphene or other layered materials.

8 This article discusses different natural and man-made foams, with particular emphasis on 9 the different modes of formation and stability. Natural foams, such as those produced on 10 the sea or by numerous creatures for nests, are generally stabilised by dissolved organic 11 carbon (DOC) molecules or biological proteins. In addition to this, foam nests are 12 stabilised by multifunctional mixtures of surfactants and proteins called ranaspumins, 13 which act together to give the required physical and biochemical stability. With regards 14 to industrial foams, the article focuses on how various features of foams are exploited for 15 different industrial applications. Stability of foams will be discussed, with the main focus 16 on how the chemical nature and structure of surfactants, proteins and particles act 17 together to produce long-lived stable foams. Additionally, foam destabilisation is 18 considered, from the perspective of elucidation of the mechanisms of instability 19 determined spectroscopically or by scattering methods. 20

A random copolymer, poly(methyl methacrylate-co-2-dimethylaminoethyl methacrylate) (poly(MMA-co-DMAEMA)) is shown to form nanoscale aggregates (NAs) (∼20 nm) at copolymer concentrations ≥10% w/w, directly from the preformed surfactant-stabilized latex (∼120 nm) in aqueous solution. The copolymer is prepared by conventional emulsion polymerization. Introducing a small mole fraction of DMAEMA (∼10%) allows the copolymer hydrophilicity to be adjusted by the pH and external temperature, generating NAs with tuneable sizes and a defined weight-average aggregation number, as observed by dynamic light scattering (DLS) and small-angle neutron scattering (SANS). These NAs are different from the so-called mesoglobular systems and are insensitive to temperature at fixed pH. The relatively broad chemical composition distribution of the copolymer and lumpy (or blocky but not diblock) incorporation of DMAEMA mean that the NAs cannot be simply thought of as conventional polymer micelles. In the acidic pH regime, the amphiphilic copolymer exhibits a defined critical assembly concentration (CAC) and a minimum air-water surface tension of 45.2 mN m-1. This copolymer represents a convenient route to self-assembled NAs, which form directly in aqueous dispersions after pH and temperature triggers, rather than the typically applied (and time-consuming) water-induced micellization approach for common polymer micelles.

Hypothesis: Reports of random copolymers capable of solubilising hydrophobic oils are rare. This is primarily because random copolymers are unlikely to self-assemble into suitable aggregates (or micelles) in water. A random copolymer with a "blocky" (or lumpy) microstructure may have potential to solubilise hydrophobic oils in water. This type of polymer would have advantages over block copolymers which are more laborious and costly to synthesise.Experiments: The solubilising capacity of a blocky random copolymer, namely poly(methyl methacrylate-co-2-dimethylaminoethyl methacrylate) (PMMA-co-PDMAEMA) is assessed by UV-visible spectroscopy and compared with common reference surfactants. The relative solubilising performance of random copolymers (across a narrow range of DMAEMA mol % fraction) for aromatic and aliphatic oils was also studied. The morphology of the aggregates was monitored as a function of the solubilisation capacity by small-angle neutron scattering (SANS) and dynamic-light scattering (DLS).Findings: Similarly to well-defined block copolymers, these random copolymers have a specific preference for solubilising aromatic over aliphatic oils. Increasing hydrophobicity of the copolymer enhances the solubilisation capacity. SANS has highlighted that aggregates become swollen and more uniform/spherical with increasing concentration of aromatic solubilisate, and that the aromatic solubilisate partitions throughout the random copolymer aggregates. (C) 2017 Elsevier Inc. All rights reserved.

For equivalent micellar volume fraction (ϕ), systems containing anisotropic micelles are generally more viscous than those comprising spherical micelles. Many surfactants used in water-in-CO2 (w/c) microemulsions are fluorinated analogues of sodium bis(2-ethylhexyl) sulfosuccinate (AOT): here it is proposed that mixtures of CO2-philic surfactants with hydrotropes and cosurfactants may generate elongated micelles in w/c systems at high-pressures (e.g., 100-400 bar). A range of novel w/c microemulsions, stabilized by new custom-synthesized CO2-phillic, partially fluorinated surfactants, were formulated with hydrotropes and cosurfactant. The effects of water content (w = [water]/[surfactant]), surfactant structure, and hydrotrope tail length were all investigated. Dispersed water domains were probed using high pressure small-angle neutron scattering (HP-SANS), which provided evidence for elongated reversed micelles in supercritical CO2. These new micelles have significantly lower fluorination levels than previously reported (6-29 wt % cf. 14-52 wt %), and furthermore, they support higher water dispersion levels than other related systems (w = 15 cf. w = 5). The intrinsic viscosities of these w/c microemulsions were estimated based on micelle aspect ratio; from this value a relative viscosity value can be estimated through combination with the micellar volume fraction (ϕ). Combining these new results with those for all other reported systems, it has been possible to "map" predicted viscosity increases in CO2 arising from elongated reversed micelles, as a function of surfactant fluorination and micellar aspect ratio.

Presented here are the results for a novel class of hydrocarbon surfactants, termed trimethylsilyl hedgehogs (TMS-hedgehogs), due to the presence of silicon in the tails. By comparing the surface properties of these hybrid hedgehogs to purely hydrocarbon equivalents, links between performance and the structure are made. Namely, by controlling the molecular volume of the surfactant fragments, improvements can be made in surface coverage, generating lower surface energy monolayers. Small-angle neutron scattering (SANS) data have been collected showing that these novel surfactants aggregate to form ellipsoidal micelles which grow with increasing concentration. This study highlights the sensitive relationship between surface tension and the surfactant chain, for designing new super-efficient surfactants close to the limit of the lowest surface tensions possible.