Bicontinuous Microemulsion Phase Research Articles

Key features of nano-emulsion formation by the phase inversion temperature method

Nano-emulsion formation by the phase inversion temperature (PIT) method is reviewed. Characteristic features of low-energy emulsification are first summarized, and then, follows a description of the main characteristics of the PIT emulsification method. The main focus is on the relation between phase behavior and nano-emulsion formation. Emphasis is put on the key role of phase transitions involving equilibrium phases such as lamellar liquid crystalline and/or bicontinuous microemulsion phases to obtain nano-emulsions with minimum and controlled droplet size.

Predicting the effect of additives on wormlike micelle and liquid crystal formation and rheology with phase inversion phenomena

HypothesisSurfactant-based viscoelastic fluids are used in consumer products such as body wash, cosmetics, and in hydraulic fracturing fluids to suspend proppant, among others. The solubilization of oil within these fluids changes the curvature of the surfactant and their nanostructure and rheological properties. The curvature-based hydrophilic-lipophilic-difference + net-average-curvature (HLD-NAC) framework may be able to quantify curvature changes and predict the formulation conditions required to obtain viscoelasticity. ExperimentsPhase inversion experiments were conducted for combinations of commercial-grade C8, C10 and C12 tetrapropylene glycol ether sulfate (extended) surfactant and sodium dihexyl sulfosuccinate with oil to obtain the HLD-NAC parameters. Wormlike micelles (WLMs) and liquid crystals (LCs) were then formulated and characterized. The transition from spherical micelles to WLMs/LCs at different oil contents was identified and compared with phase transitions predicted via the HLD-NAC model. FindingsThe spherical micelle to branched WLM/LC transition in surfactant + oil systems coincided with the water-continuous (Type I) to bicontinuous (Type III) microemulsion phase transition predicted with the HLD-NAC model. Using this finding, the transition of commercial-grade sodium laureth sulfate (SLES) micelles to viscoelastic LCs containing various oils was predicted using the HLD-NAC. The HLD-NAC also predicted the presence of a secondary peak in viscosity obtained in “salt curves” experiments associated with branched WLMs and LCs.

Effect of water on the electrodeposition of copper on nickel in deep eutectic solvents

ABSTRACTMost studies of metal electrodeposition in ionic liquids dry the electrolyte thoroughly, as water is thought to be detrimental. In some cases, water has a beneficial effect on deposit morphology. The electrodeposition of copper has been studied in 1ChCl: 2EG-water mixtures. It is shown here that the presence of water increases the apparent brightness of the deposit due to changes in the electrodeposit surface feature size, up to a water content of approximately 20 wt-%. This study characterises speciation and mass transport in solution, and shows that diffusion can be controlled independently of speciation. It is shown that there is an optimal water content, which is thought to originate from formation of a bi-continuous micro-emulsion phase in DES-water mixtures. Additionally, the copper species remains in a predominantly ionic medium at low water content but moves to an aqueous environment when water is the main component.

Thin film confinement reduces compatibility in symmetric ternary block copolymer/homopolymer blends

ABSTRACTThe thin film phase behavior of ternary blends consisting of symmetric poly(styrene) (PS)‐b‐poly(dimethylsiloxane)(PDMS), PS, and PDMS was investigated using X‐ray reflectivity (XRR) and atomic force microscopy (AFM). This system is strongly segregated, and the homopolymers are approximately the same length as the corresponding blocks of the copolymer. The XRR and AFM data are used to quantify changes in domain spacing (L) and morphology evolution with increasing homopolymer content (Φ H). In 100 nm thick films, from Φ H = 0 to 0.20, the system maintains a perfect parallel lamellar structure and domains swell as predicted based on theory; however, from Φ H = 0.30 to 0.50, a morphology transition to a “dot pattern” morphology (tentatively identified as perforated lamellae) and mixed morphologies were observed before macrophase separation. In thicker films, dot patterns were observed for a broad range of Φ H before macrophase separation. The absence of the bicontinuous microemulsion phase reported for bulk blends and thin films of perpendicular lamellae and the presence of dot patterns/perforated lamellae are attributed to preferential migration of the PDMS homopolymer to the wetting layers located at the substrate and free air interfaces, which leads to an asymmetric composition within the film and morphology transition. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 1443–1451

A Novel Microemulsion Phase Transition: Toward the Elucidation of Third-Phase Formation in Spent Nuclear Fuel Reprocessing.

We present evidence that the transition between organic and third phases, which can be observed in the plutonium uranium reduction extraction (PUREX) process at high metal loading, is an unusual transition between two isotropic bicontinuous microemulsion phases. As this system contains so many components, however, we have been seeking first to investigate the properties of a simpler system, namely, the related metal-free, quaternary water/n-dodecane/nitric acid/tributyl phosphate (TBP) system. This quaternary system has been shown to exhibit, under appropriate conditions, three coexisting phases: a light organic phase, an aqueous phase, and the so-called third phase. In the current work, we focused on the coexistence of the light organic phase with the third phase. Using Gibbs ensemble Monte Carlo (GEMC) simulations, we found coexistence of a phase rich in nitric acid and dilute in n-dodecane (the third phase) with a phase more dilute in nitric acid but rich in n-dodecane (the light organic phase). The compositions and densities of these two coexisting phases determined using the simulations were in good agreement with those determined experimentally. Because such systems are generally dense and the molecules involved are not simple, the particle exchange rate in their GEMC simulations can be rather low. To test whether a system having a composition between those of the observed third and organic phases is indeed unstable with respect to phase separation, we used the Bennett acceptance ratio method to calculate the Gibbs energies of the homogeneous phase and the weighted average of the two coexisting phases, where the compositions of these phases were taken both from experimental results and from the results of the GEMC simulations. Both demixed states were determined to have statistically significant lower Gibbs energies than the uniform, mixed phase, providing confirmation that the GEMC simulations correctly predicted the phase separation. Snapshots from the simulations and a cluster analysis of the organic and third phases revealed structures akin to bicontinuous microemulsion phases, with the polar species residing within a mesh and with the surface of the mesh formed by amphiphilic TBP molecules. The nonpolar n-dodecane molecules were observed in these snapshots to be outside this mesh. The only large-scale structural differences observed between the two phases were the dimensions of the mesh. Evidence for the correctness of these structures was provided by the results of small-angle X-ray scattering (SAXS) studies, where the profiles obtained for both the organic and third phases agreed well with those calculated from simulations. Finally, we looked at the microscopic structures of the two phases. In the organic phase, the basic motif was observed to be one nitric acid molecule hydrogen-bonded to a TBP molecule. In the third phase, the most common structure was that of the hydrogen-bonded TBP-HNO3-HNO3 chain. A cluster analysis provided evidence for TBP forming an extended, connected network in both phases. Studies of the effects of metal ions on these systems will be presented elsewhere.

Observation of a structural gradient in Winsor-III microemulsion systems.

We demonstrate here for the first time via small-angle neutron scattering (SANS) that the middle, bicontinuous microemulsion (BμE) phase of Winsor-III systems undergoes a gradual change of structure and composition in the vertical direction, contrary to the commonly held belief of uniform structure and composition. A vertical stage was deployed to enable precise alignment of a custom-designed rectangular cell containing the WIII system with respect to the neutron beam, allowing for several different vertical positions to be analyzed. For the water/AOT/CK-2,13 (two-tailed alkyl ethoxylate containing a 1,3-dioxolane linkage)/heptane Winsor-III system, the quasi-periodic repeat distance (d) and correlation length (ξ), obtained from the Teubner-Strey model applied to the SANS data, decreased and the surface area per volume of the surfactant monolayer (via Porod analysis) increased in the downward direction, trends that reflect an increase of surfactant concentration, consistent with the ultralow interfacial tension that often occurs for the lower liquid-liquid interface of many WIII systems. The water/sodium dodecyl sulfate (SDS)/1-pentanol/dodecane system shared the same trend with regard to d as observed for AOT/CK-2,13. In contrast, for SDS/pentanol, ξ increased and the amphiphilicity factor (fa) decreased in the downward direction, trends consistent with a decrease of cosurfactant (pentanol) concentration in the downward direction. Non-uniformity in the vertical direction has implications in the transport of solutes between WIII phases during the extractive purification of proteins or the removal of heavy metals and pollutants from wastewater, or the deposition of BμEs onto hydrophilic vs. hydrophobic surfaces as thin coatings.

Protein extraction into the bicontinuous microemulsion phase of a Water/SDS/pentanol/dodecane winsor-III system: Effect on nanostructure and protein conformation

Bicontinuous microemulsions (BμEs), consisting of water and oil nanodomains separated by surfactant monolayers of near-zero curvature, are potentially valuable systems for purification and delivery of biomolecules, for hosting multiphasic biochemical reactions, and as templating media for preparing nanomaterials. We formed Winsor-III systems by mixing aqueous protein and sodium dodecyl sulfate (SDS) solutions with dodecane and 1-pentanol (cosurfactant) to efficiently extract proteins into the middle (BμE) phase. Bovine serum albumin (BSA) and cytochrome c partitioned to the BμE phase at 64% and 81% efficiency, respectively, producing highly concentrated protein solutions (32 and 44gL−1, respectively), through release of water and oil from the BμEs. Circular dichroism spectroscopic analysis demonstrated that BSA underwent minor secondary structural changes upon incorporation into BμEs, while the secondary structure of cytochrome c and pepsin underwent major changes. Small-angle x-ray scattering (SAXS) results show that proteins promoted an increase of the interfacial fluidity and surface area per volume for the BμE surfactant monolayers, and that each protein uniquely altered self-assembly in the Winsor-III systems. Cytochrome c partitioned via electrostatic attractions between SDS and the protein’s positively-charged groups, residing near the surfactant head groups of BμE monolayers, where it decreased surfactant packing efficiency. BSA partitioned through formation of SDS-BSA complexes via hydrophobic and electrostatic attractive interactions. As the BSA-SDS ratio increased, complexes’ partitioning favored BμEs over the oil excess phase due to the increased hydrophilicity of the complexes. This study demonstrates the potential utility of BμEs to purify proteins and prepare nanostructured fluids possessing high protein concentration.

Field-Theoretic Simulations of Fluctuation-Stabilized Aperiodic “Bricks-and-Mortar” Mesophase in Miktoarm Star Block Copolymer/Homopolymer Blends

A new class of thermoplastic elastomers possessing unusual mechanical properties has recently been discovered in binary blends of A-b-(B-b-A′)n miktoarm star block copolymers and A homopolymers that spontaneously form an unusual, thermodynamically stable, aperiodic “bricks-and-mortar” (B&M) mesophase morphology. The B&M mesophase is believed to be stabilized by thermal fluctuations as in the well-known case of the bicontinuous microemulsion phase. Here, two-dimensional field-theoretic simulations are used to study the equilibrium self-assembly of such miktoarm polymer binary blends. As expected, the B&M mesophase is not present in the mean-field phase diagram obtained with self-consistent field theory, but complex Langevin (CL) simulations, which fully incorporate thermal fluctuation effects, reveal dramatic changes to the phase diagram. A region of strong fluctuations results in the emergent stabilization of the B&M mesophase in a broad composition channel positioned between microphase separation and mac...

Temperature-induced three-phase equilibrium of medium-chain-length poly-3-hydroxyalkanoates-incorporated emulsion system for production of polymeric nanoparticle

ABSTRACTThe study investigated the effects of temperature on the phase behavior of medium-chain-length poly-3-hydroxyalkanoates (mcl-PHA)-incorporated emulsion system. It is suggested that the three-phase equilibrium consisting of lamellar liquid crystalline (La), bi-continuous microemulsion (D), and oil-swollen micelle phases formed in the vicinity of optimal formulation when the combination of phase inversion composition (PIC) and phase inversion temperature (PIT) methods was applied. The interaction effects between two parameters, viz. temperature and mcl-PHA molecular weight, influenced the lamellar/bi-continuous microemulsion formation within the mcl-PHA-incorporated emulsion. It is suggested that the lamellar/bi-continuous microemulsion phase of mcl-PHA-incorporated emulsion can be thermally induced from multiple emulsion system proximately before EIP, and its hypothetical formation mechanism is elucidated in this study.

Segregation of Amphiphilic Polymer-Coated Nanoparticles to Bicontinuous Oil/Water Microemulsion Phases

Polymer-coated nanoparticles are interfacially active and have been shown to stabilize macroscopic emulsions of oil and water, also known as Pickering emulsions. However, prior work has not explored the phase behavior of amphiphilic nanoparticles in the presence of bicontinuous microemulsions. Here, we show that properly designed amphiphilic polymer-coated nanoparticles spontaneously and preferentially segregate to the bicontinuous microemulsion phases of oil, water, and surfactant. Mixtures of hydrophilic and hydrophobic chains are covalently grafted onto the surface of oxidized carbon black nanoparticles. By sulfating hydrophilic chains, the polymer-coated nanoparticles are stable in the aqueous phase at salinities up to 15 wt % NaCl. These amphiphilic, negatively charged polymer-coated nanoparticles segregate to the bicontinuous microemulsion phases. We analyzed the equilibrium phase behavior of the nanoparticles, measured the interfacial tension, and quantified the domain spacing in the presence of na...

Monodisperse core-shell magnetic organosilica nanoflowers with radial wrinkle for lipase immobilization

The monodisperse core-shell magnetic organosilica nanoflowers were successfully synthesized by a method based on the bicontinuous microemulsion phase of the Winsor III system. The obtained nanoflowers with magnetic core and flower-like organosilica shell possess radial-wrinkle, tunable perpendicular channels, and high magnetization (62emu/g). The nanoflowers were employed as support for Candida antarctica lipase B (CALB) covalent immobilization. The maximum amount of CALB immobilized on the nanoflowers was 93mg/gsupport, while the specific hydrolytic activity was 22,700U/gsupport. Meanwhile, the CALB@nanoflowers showed better pH stability than free CALB and CALB@MMPS, which can remain 65% of initial activity after incubated in cyclohexane at 60°C for 96h, and remain 90% of initial activity after stored in room temperature for 42days. In addition, the CALB@nanoflowers could catalyze the synthesis of alkyl levulinates through the esterification of levulinic acid alcohols with different chain length (n-butyl alcohol, n-caprylic alcohol, n-lauryl alcohol) in a solvent-free system effectively. After recycling 10 times, the CALB@nanoflowers retained more than 85% of its initial activity in catalyzing the synthesis of butyl-levulinates and more than 96% of the initial activity in catalyzing the synthesis of long chain alkyl levulinates, which was much higher than commercial N435. With these desired characteristics, the design of hydrophobic nanoflowers with tunable wrinkle channels for lipases immobilization opens up a new way to improve the catalytic activity and stability of the lipases, and may have potential applications in various lipase-based industrial processes.

Microemulsions of Record Low Amphiphile Concentrations Are Affected by the Ambient Gravitational Field.

It is shown that the ternary system heavy water-heptane-hexadecyl hexaethylene oxide (C16E6) has a stable bicontinuous microemulsion phase down to an exceptionally low concentration at the balanced temperature of 26.8 °C. It is further demonstrated that the ambient gravitational field has an influence on the observed phase equilibria for typical sample sizes (∼1 cm). Direct measurements using a nuclear magnetic resonance imaging technique demonstrate that sample compositions vary with the height in the vials. It is furthermore found that some samples show four phases at equilibrium in apparent violation of Gibbs' phase rule. It is pointed out that Gibbs' phase rule strictly applies only when effects of gravity are negligible. A further consequence of the ambient gravitational field is that, for the system studied, the microemulsion one-phase samples are not observed, when using standard size vials, that is, sample heights on the order of a centimeter. Quantitative determinations of concentration profiles can be used to determine parameters of the free-energy density for the system.

Rational Design of Thermally Stable, Bicontinuous Donor/Acceptor Morphologies with Conjugated Block Copolymer Additives.

The bicontinuous microemulsion (BμE) phase is an equilibrium morphology characterized by cocontinuous domains, high interfacial areas, and nanoscale domain dimensions. These characteristics make the BμE potentially suitable for use in organic photovoltaic applications. Here, we use a combination of simulations and experiments to investigate the equilibrium morphologies formed by a ternary blend of conjugated polymer, all-conjugated diblock copolymer, and fullerene derivative PCBM. Using coarse-grained simulations, we identify the blend compositions that are most likely to result in donor/acceptor morphologies resembling the BμE. Experimentally, we probe these compositions through transmission electron microscopy and grazing-incidence X-ray scattering measurements. We demonstrate that all-conjugated block copolymer additives can be used to produce thermally stable, cocontinuous donor/acceptor morphologies at higher additive contents and longer annealing times than previously reported. These results demonstrate that conjugated BCP compatibilizers can be used as a means to achieve equilibrium, cocontinuous morphologies in donor/acceptor blends.

Effect of protein incorporation on the nanostructure of the bicontinuous microemulsion phase of Winsor-III systems: a small-angle neutron scattering study.

Small-angle neutron scattering (SANS) analysis using the Teubner-Strey model has been employed to evaluate the effect of protein incorporation into the middle, bicontinuous microemulsion (BμE) phase of Winsor-III (WIII) systems formed by an aerosol-OT (AOT)/alkyl ethoxylate mixed surfactant system to understand better the extraction of proteins into and out of BμEs and to study the effect of proteins on a system that serves as a biomimetic analog of cell membranes. Under conditions of high salinity, the incorporation of positively charged proteins cytochrome c, lysozyme, and α-chymotrypsin, near their solubilization limit in the BμEs promoted the release of water and oil from the BμEs, a decrease in the quasi-periodic repeat distance (d), an increase in ordering (a decrease in the amphiphilicity factor, fa) for the surfactant monolayers, and a decrease in the surface area per surfactant headgroup, suggesting that the proteins affected the self-assembly of components in the BμE phase and produced Debye shielding of AOT's sulfonate headgroup. For WIII systems possessing lower salinity, cytochrome c reduced the efficiency of surfactant in the BμE phase, noted by increases in d and fa, suggesting that the enzyme and AOT underwent ion pairing. The results of this study demonstrate the importance of ionic strength to modulate protein-surfactant interactions, which in turn will control the release of proteins encapsulated in the BμEs, relevant to WIII-based protein extraction and controlled release from BμE delivery systems, and demonstrate the utility of BμEs as a model system to understand the effect of proteins on biomembranes.

Tunable Synthesis of Hierarchical Mesoporous Silica Nanoparticles with Radial Wrinkle Structure

We studied the formation mechanism of hierarchical mesoporous silica nanoparticles with a wrinkle structure (wrinkled silica nanoparticles, WSNs), and a method for substructure control of silica nanoparticles was proposed. We confirmed that WSNs were generated in the bicontinuous microemulsion phase of the Winsor III system. By using the phase behavior of the Winsor III system, which depends on the water-surfactant-oil mixing ratio, and by adding various cosolvents, we could precisely control the structure of silica nanoparticles from the mesoporous to the wrinkle form; furthermore, we could control the interwrinkle distance.

Water-in-oil nanostructured emulsions: towards the structural hierarchy of liquid crystalline materials

We present novel water-in-oil (W/O) emulsions with a nanostructured oil phase that resemble soft materials such as creams, pastes and spreadable materials used in cosmetics, pharma and food applications. These emulsions have a broad structural hierarchy that involves 50 to 90 volume percent of micron sized water droplets (2–50 µm) confined by a continuous hydrophobic film that itself is made of a lyotropic nanostructure. This nanostructure can be modulated into inverse bicontinuous cubic, micellar cubic, inverse hexagonal or microemulsion phases. The novelty of these W/O nanostructured emulsions lies in (i) their preparation, which does not require any emulsion stabilizer, (ii) their hierarchical structure and intrinsic properties, which can be fine-tuned by varying temperature, water content and amount of oil and (iii) their ability to be loaded with hydrophobic, amphiphilic and hydrophilic functional molecules. Here, we present a systematic study along with the principles behind these dense nanostructured emulsions prepared, for the first time, from a monoglyceride system. High interfacial area, continuous architectural motif, enhanced water storage capacity and extensive tunability of these nanostructured emulsions open up new avenues in various scientific and technological applications.

Formation and stability of nanoemulsions with mixed ionic–nonionic surfactants

A simple, low-energy two-step dilution process has been applied with binary mixtures of ionic-nonionic surfactants to prepare nanoemulsions. The systems consist of water/DDAB-C(12)E(5)/decane. Nanoemulsions were obtained by dilution of concentrates located in bicontinuous microemulsion or lamellar liquid crystal phase regions. The nanoemulsions generated were investigated both by contrast-variation small-angle neutron scattering (SANS) and dynamic light scattering (DLS). The SANS profiles show that C(12)E(5) nanodroplets suffer essentially no structural change on incorporation of the cationic DDAB surfactant, except for increased electrostatic repulsive interactions. Interestingly, SANS indicated that the preferred droplet sizes were hardly affected by the surfactant mixture composition (up to a DDAB molar ratio (m(DDAB)/(m(DDAB) + m(C(12)E(5))) of 0.40) and droplet volume fraction, phi, between 0.006 and 0.120. No notable changes in the structure or radius of nanoemulsion droplets were observed by SANS over the test period of 1 d, although the droplet number intensity decreased significantly in systems stabilized by C(12)E(5) only. However, the DLS sizing shows a marked increase with time, with higher droplet volume fractions giving rise to the largest changes. The discrepancy between apparent nanoemulsion droplet size determined by DLS and SANS data can be attributed to long-range droplet interactions occurring outside of the SANS sensitivity range. The combined SANS and DLS results suggest flocculation is the main mechanism of instability for these nanoemulsions. The flocculation rate is shown to be significantly retarded by addition of the charged DDAB, which may be due to enhanced electrostatic repulsive forces between droplets, leading to improved stability of the nanoemulsions.

A Narrow Bicontinuous Microemulsion Domain in Mixed Polymeric Silicone Systems

We have prepared a viscous bicontinuous microemulsion consisting of water / [20 wt% POE-GIS + 30 wt% PEPTME + 47.5 wt% POE/POP-PDMS + 2.5 wt% OA)] / DMPS system. A pseudoternary phase diagram was constructed for the mixture, and the bicontinuous microemulsion phase was characterized by means of rheometry and freeze-fracture transmission electron microscopy (FF-TEM).

The effect of structure of oil phase, surfactant and co-surfactant on the physicochemical and electrochemical properties of bicontinuous microemulsion

Efforts were made to prepare bicontinuous microemulsions with ten different oil phases involving aliphatic, linear, and aromatic hydrocarbons as oil phases, two co-surfactants ( n-butanol and n-pentanol) and two surfactants: cationic (CTAB) and anionic (SDS). Different weight percentages were employed for the preparation of cationic and anionic surfactant based microemulsions as reported in the literature. Out of the 40 compositions (10 oil phases × 2 co-surfactants × 2 surfactants) thus selected only 28 systems showed stable bicontinuous microemulsion phase. This behavior is explained on the basis of the structures of various constituents present in the microemulsions. Viscosity variations of stable bicontinuous microemulsions are found to depend mainly on the nature of co-surfactant. Conductivity behavior on the other hand depends mainly on the weight percentage and composition of aqueous phase. The solubility of pyrene in the oil phase determines the excimer formation and fluorescence behavior in microemulsions. The electron transfer property of both the water-soluble and the oil-soluble redox systems does not depend on the oil phase and the co-surfactant. The significance and importance of characterizing well defined bicontinuous microemulsions is thus highlighted.

Condensed Exponential Correlation Functions in Multicomponent Polymer Blends Measured by X-ray Photon Correlation Spectroscopy

X-ray photon correlation spectroscopy experiments were conducted on bicontinuous microemulsion and lamellar phases in polystyrene/polyisoprene/poly(styrene-b-isoprene) blends. Regardless of the microstructure, the scattering intensity autocorrelation function at low temperatures in the vicinity of the primary X-ray scattering peak, g2(q,t) (q is the scattering vector), was found to be a condensed exponential, i.e., g2(q,t) ∼ exp{−[t/τ(q)]α}with α > 1. This is in direct contrast to previous observations of exponential and stretched exponential correlation functions (α ≤ 1) in microstructured materials comprising polymers as well as small molecules. At higher temperatures, more conventional stretched exponential correlation functions are recovered. We suggest that condensed exponential relaxation functions may be related to the spontaneous breakup of microsctructure.