Further studies on the effect of degassing on the dispersion and stability of surfactant-free emulsions

Recently reported results indicate that the formation of surfactant-free, oil-in-water emulsions can be significantly enhanced by the almost complete removal of dissolved gases and that the reintroduction of dissolved gases does not immediately destabilize the already-formed emulsions. These initial experiments have been repeated and extended to include a wider range of organic liquids and the application of light scattering to determine droplet size and distribution. The earlier observations have been confirmed. In addition, a systematic trend was found between the solubility of the oil in water and the stability (lifetime) of the degassed oil droplets in water. The lower the solubility, the more stable the emulsion, and for oils that are sparingly soluble in water such as squalane, the small droplets remain stable for several weeks, with buoyancy separation being the main cause of instability of the large droplets with time. The addition of electrolytes, up to molar concentrations, substantially reduces the enhancement of the dispersions on degassing but appears to have little effect on the stability of the already-formed emulsions. The reduction of pH to about 2 significantly reduces both the enhancement of the dispersions on degassing and the stability of the already-formed emulsions. In contrast, the increase of pH to about 11 hardly affects the enhancement of the dispersions on degassing or the stability of the already-formed emulsions. We have confirmed the importance of dissolved gas and its association with the electrostatic effects, but we still cannot provide a complete explanation for the effect of degassing on the hydrophobic dispersions.     

Removal of induced nanobubbles from water/graphite interfaces by partial degassing

Nanobubbles at an interface between a hydrophobic solid and water have a wide range of implications, but the evidence for their existence is still being debated. Here we artificially induced nanobubbles on freshly cleaved HOPG substrates in water using the protocol developed previously and subjected the system to moderate levels of degassing (approximately 0.1 atm for 0.5 to 3 h). The AFM images after the partial degassing revealed that some nanobubbles had coalesced and detached from the substrate because of buoyancy, whereas others apparently remained unaffected. The size and spatial distributions of the nanobubbles after the partial degassing suggest that there is a critical size for a nanobubble above which it may grow. The contact angle of water next to nanobubbles (approximately 160 degrees) is much larger than the advancing contact angle of a macroscopic water droplet on the same substrate (approximately 80 degrees) both before and after the partial degassing and concomitant growth and shrinkage of the nanobubbles. The contact angle of a nanobubble also remained unchanged as the nanobubble was moved along the substrate by the AFM tip. The apparent lack of contact angle hysteresis in the nanobubble systems may suggest that the very large contact angle may correspond to a local minimum of the free-energy landscape.     

Surface modification of cellulose with plant triglycerides for hydrophobicity

Hydrophobic cotton was achieved by surface modification of the cellulose with triglycerides from several plant oils including soybean, rapeseed, olive and coconut oils. These oils were delivered to the cellulose substrates in homogeneous solutions of ethanol or acetone as well as aqueous emulsions. Surface modification was facilitated by solvent evaporation followed by heating between 110 and 120 °C for 60 min. All oils, except for coconut, produced hydrophobic and less water-absorbing cotton, supporting the desirable role of higher unsaturation in the fatty acids to achieve crosslinked network. The most hydrophobic surfaces were obtained by the reaction with 1% soybean oil in acetone. On both bleached and scoured cotton, a water contact angle of 80° and water absorption value of 0.82 μL/mg were achieved. The acquired hydrophobicity was not only retained after water washing but also improved with subsequent exposures to elevated temperatures. The surface tension of scoured cotton cellulose was lowered from 63.81 mJ/m² to 25.74 mJ/m² when modified by soybean oil delivered in acetone, which is lower than that of poly(ethylene terephthalate). An aqueous emulsion of soybean oil also rendered the scoured cotton hydrophobic, which shows promise for a green chemistry and bio-based approach to achieve water repellency on cellulosic materials.     

A study of de-gassed oil in water dispersions as potential drug delivery systems

The natural hydrophobicity of many drugs makes it very difficult to use them for water-based intravenous injection. This lack of water solubility also hinders the development and testing of new drugs. Clinical tests are often refused if the drug can only be dissolved in water-insoluble oils and therefore cannot be administered safely or easily. However, we have discovered that de-gassing a mixture of a typical hydrophobic drug carrier oil and water produces, on vigorous shaking, a uniform fine dispersion of oil droplets, which are of suitable size for intravenous injection. These dispersions are stable and yet do not require the use of added stabilizing agents, such as surfactants and polymers, which can lead to harmful side effects. This novel process has been used to enhance the dispersion of the commonly used drug delivery oils, soybean oil and perfluorooctyl bromide (PFOB). This process can also be applied to other drug delivery oils, which are immiscible with water. For example, the dispersion of perfluorohexane in water is greatly improved by de-gassing. Over time, the dispersions phase separate but are easily re-generated simply by shaking, when stored under de-gassed conditions in sealed vials. The process has also been successfully applied to hydrophobic drugs, both liquid and solid, where dispersion was obtained without the use of either carrier oil or added dispersants. These dispersions offer safer drug delivery systems and also might be used in facilitating the development or testing of new experimental, water-insoluble drugs.     

The dispersion of natural oils in de-gassed water

Recent studies have demonstrated that pure hydrocarbon oils can be dispersed in water as fine droplets without the use of additives. The high interfacial tension between hydrocarbons and water is expected to cause cavitation between oil droplets during separation. This cavitation is aided by dissolved atmospheric gases present in both the oil and water. Their removal allows oil droplets to be readily dispersed in water. In this paper we report on the effect of the de-gassing process on the dispersion of several natural, water immiscible oils. These natural, mixed oils are eucalyptus, lavender and tea tree oil. Although these oils are mixtures and in some cases not as hydrophobic as those used in the earlier studies, the effect of de-gassing substantially enhances their dispersion, producing micron-sized droplets without the need for additives. Dispersions of these natural oils in pure water have a wide range of uses where purity is an advantage, for example, in skin cleaning products and oral sprays.     

A membrane method for degassing nonaqueous liquids

Degassing of nonaqueous solvents is useful for their applications in chemical synthesis and in maintaining purity (against oxidative degradation) during long term storage. In addition, degassed solvents have been found to be of value in the production of oil and water emulsions. Currently, there are three main methods for degassing solvents. These are the freeze-pump-thaw process, partial degassing using sonication under slight vacuum and purging, where one active gas (usually oxygen) is replaced with an inert gas (e.g., nitrogen). In this work we have demonstrated the potential application of hollow-fibre membranes to efficiently degas water-immiscible, hydrophobic liquids. Mixtures of dodecane and water, separately degassed using membranes, show an enhanced dispersion of dodecane, similar to that previously reported for freeze-thaw degassed mixtures.     

De-gassed water is a better cleaning agent

It is demonstrated that de-gassed water is more effective at dispersing hydrophobic "dirt", such as liquid hydrocarbons or oils. This effect appears to be due to the reduction of natural cavitation, which would otherwise oppose the dispersion of hydrophobic liquid droplets into water. De-gassing of the oil enhances this effect still further, and this has led to a proposal for a novel cleaning process, based on using a combination of a de-gassed (hydrophobic) solvent followed by rinsing in de-gassed water. This method might be useful as an effective, detergent-free cleaning process. Also reported are some initial studies which suggest that the effect of "inert" dissolved gases on the electrical conductivity of water may need to be reconsidered.     

Preparation and characterization of fragrance by extracting the essential oils from different raw materials

The extraction is a simple process and it is widely used to extract the fragrances in fragrance industries from essential oils. There are number of compounds (i.e. flowers, oils, leaves etc.) from which we can prepare the fragrance by extracting the essential oils from them. In this work, we have prepared the fragrance from the essential oils by the liquid-liquid extraction process, where the essential oil presented as the concentrated hydrophobic liquid containing volatile aroma compounds. We used the combination of Gas chromatography and Mass spectrometry (GC/MS) characterization techniques to make our product more useful, convenient and compitative with the other fragrance available in the market. This study would be helpful to understand the preparation of the fragrance from the concentrated hydrophobic liquid type essential oils which contains volatile aroma compounds by using a significant liquid-liquid extraction process.     

Linker molecules in surfactant mixtures

Linker molecules are amphiphiles that segregate near the microemulsion membrane either near the surfactant tail (lipophilic linkers) or the surfactant head group (hydrophilic linkers). The idea of the lipophilic linkers was introduced a decade ago as a way to increase the surfactant–oil interaction and the oil solubilization capacity. Long chain (>9 tail carbons) alcohols were first used as lipophilic linkers. Later it was found that the solubilization enhancement plateaus (saturates) above a certain lipophilic linker concentration. Hydrophilic linkers have been recently introduced as a way to compensate for the saturation effect observed for lipophilic linkers. Hydrophilic linkers are surfactant-like molecules with 6–9 tail carbons that coadsorb with the surfactant at the oil/water interface, thereby increasing the surfactant–water interaction, but have a poor interaction with the oil phase due to their short tail. A special synergism emerges when combining hydrophilic and lipophilic linkers, which further increases the solubilization enhancement over lipophilic linkers alone. We will discuss the profound impact of linker molecules on interfacial properties such as characteristic length, interfacial rigidity and dynamics (coalescence, solubilization and relaxation experiments) of the interface. We also demonstrate how these properties affect the performance of cleaning formulations designed around linker molecules. We describe linker-based formulations for a wide range of oils, including highly hydrophobic oils (e.g. hexadecane) that have proven very hard to clean. We also report on the use of ‘extended’ surfactants as an alternative to self-assembled linker systems.     

Modeling solubilization of oil mixtures in anionic microemulsions II. Mixtures of polar and non-polar oils

Polar/amphiphilic oils, called lipophilic linkers, are sometimes added to oil-water-ionic surfactant microemulsions in order to increase the solubilization of hydrophobic oils. The solubilization increase has been well documented for a number of systems. However, mathematical models to calculate the solubilization increase have been proposed only for optimum microemulsions (i.e., middle phase microemulsions solubilizing equal volumes of oil and water). In this paper we propose a model, which predicts solubilization enhancement for non-optimum microemulsion systems as well. The model is an extension of the net-average curvature model of microemulsion. The net-average curvature model is combined with a surface activity model to account for the increased palisade layer solubilization due to the presence of the polar/amphiphilic oil component. New non-linear mixing rules are also incorporated to account for the optimum salinity and the characteristic length variation of the anionic surfactant microemulsion as a function of the lipophilic linker concentration. The model predicts the effect of the lipophilic linker and the electrolyte concentration on the oil solubilization in accordance with the experimental results.     

A membrane-based, high-efficiency, microfluidic debubbler

In many lab-on-chip applications, it is necessary to remove bubbles from the flow stream. Existing bubble removal strategies have various drawbacks such as low degassing efficiency, long degassing time, large dead volumes, sensitivity to surfactants, and the need for an external vacuum or pressure source. We report on a novel, simple, robust, passive, nozzle-type, membrane-based debubbler that can be readily incorporated into microfluidic devices for rapid degassing. The debubbler is particularly suitable to operate with microfluidic systems made with plastic. The debubbler consists of a hydrophobic, porous membrane that resembles a normally closed valve, which is forced open by the working fluid's pressure. To illustrate the operation of the debubbler, we describe its use in the context of a chip containing a bead array for immunoassays. Our debubbler was able to completely filter gas bubbles out of a segmented flow at rates up to 60 μl s(-1) mm(-2) of membrane area.     

A Phytic Acid Induced Super‐Amphiphilic Multifunctional 3D Graphene‐Based Foam

Surfaces with super‐amphiphilicity have attracted tremendous interest for fundamental and applied research owing to their special affinity to both oil and water. It is generally believed that 3D graphenes are monoliths with strongly hydrophobic surfaces. Herein, we demonstrate the preparation of a 3D super‐amphiphilic (that is, highly hydrophilic and oleophilic) graphene‐based assembly in a single‐step using phytic acid acting as both a gelator and as a dopant. The product shows both hydrophilic and oleophilic intelligence, and this overcomes the drawbacks of presently known hydrophobic 3D graphene assemblies. It can absorb water and oils alike. The utility of the new material was demonstrated by designing a heterogeneous catalytic system through incorporation of a zeolite into its amphiphilic 3D scaffold. The resulting bulk network was shown to enable efficient epoxidation of alkenes without prior addition of a co‐solvent or stirring. This catalyst also can be recovered and re‐used, thereby providing a clean catalytic process with simplified work‐up.     

NEW SURFACTANTS FOB SOLUBLE EXTREME PRESSURE CUTTING OILS

The use of nonionic and anionic surfactants is common in soluble cutting oils to facilitate spontaneous emulsification and to keep the formulation stable. Various additives are also introduced in order to achieve high pressure stability, better resistance to high sheers, minimum corrosion and other related properties. Tailor-made surfactants into which specific functional groups are introduced into the hydrophobic chain are of special interest mainlv if extreme pressure (EP) properties can be improved. Those surfactants will help to replace part of the additives and will reduce the cost of the formulation. Incorporation of halogens (chlorine, bromine) to the hydrophobic tail of ethoxylated nonylphenols; sorbitan esters of fatty acids, ethoxylated oleyl alcohols and polyglycerol esters has been carried out. The new surfactants have high specific gravities and therefore can minimize creaming of the emulsion and will improve the EP properties of the soluble cutting oils. Functionalization of the surfactants did not retained the emulsion stability, yet reduced the creaming and the cost of the formulation. It has been also shown that the lubrication properties e.g. the resistance to load and torque have been improved.     

Simple, reversible emulsion system switched by pH on the basis of chitosan without any hydrophobic modification

Chitosan without hydrophobic modification is not a good emulsifier itself. However, it has a pH-tunable sol-gel transition due to free amino groups along its backbone. In the present work, a simple reversible Pickering emulsion system based on the pH-tunable sol-gel transition of chitosan was developed. At pH > 6.0, as adjusted by NaOH, chitosan was insoluble in water. Chitosan nanoparticles or micrometer-sized floccular precipitates were formed in situ. These chitosan aggregates could adsorb at the interface of oil and water to stabilize the o/w emulsions, so-called Pickering emulsions. At pH < 6.0, as adjusted by HCl, chitosan was soluble in water. Demulsification happened. Four organic solvents (liquid paraffin, n-hexane, toluene, and dichloromethane) were chosen as the oil phase. Reversible emulsions were formed for all four oils. Chitosan-based Pickering emulsions could undergo five cycles of emulsification-demulsification with only a slight increase in the emulsion droplet size. They also had good long-term stability for more than 2 months. Herein, we give an example of chitosan without any hydrophobic modification to act as an effective emulsifier for various oil-water systems. From the results, we have determined that natural polymers with a stimulus-responsive sol-gel transition should be a good particulate emulsifier. The method for in situ formation of pH-responsive Pickering emulsions based on chitosan will open up a new route to the preparation of a wide range of reversible emulsions.     

Photochemically Produced Superhydrophobic Silane@polystyrene-Coated Polypropylene Fibrous Network for Oil/Water Separation

Cost-effective separation of oil and immiscible organic contaminants from water has become an urgent challenge to protect aquatic and human life from devastating effects. Therefore, it has become imperative to develop super-selective materials for efficiently separating oil from water. In this work, a superhydrophobic surface has been formed that consists of a silane@polystyrene-coated polypropylene fibrous network (silane@PS-PPF) for efficient separation of accidentally spilled oil from water. The superhydrophobic PPFs were designed by a simple, cost-effective two-step process that includes photochemically controlled polymerization of styrene and subsequent dip coating in octadecyltrichlorosilane solution. The hydrophobic surface (CA=129°±4°) of the PS coated PPF after treating with silane was turned into a superhydrophobic body (CA=161°±2°). The achieved silane@PS-PPF fibrous network selectively allowed the fast permeation of the oils and non-polar organic liquids by altogether rejecting water during operation. The separation efficiency for various oils from the contaminated water was 96 to 99%, with a high flux in the range of 7606±312 L m⁻²h⁻¹ to 9870±151 L m⁻²h⁻¹. Apart from being used as a filter, the silane@PS-PPF was also used as an oil absorber and has shown an absorption capacity in the range of 1185 to 1535% for various oils. We anticipate that the developed silane@PS-PPF, due to its facile synthetic route, cost-effectiveness, and high performance, can be effectively used in oily wastewater treatment and clean-up of large oil spills from water.     

Evaluation of Hydrophobic Polyurethane Foam as Sorbent Material for Oil Spill Recovery

In this work, hydrophobic polyurethane foam was prepared using hy-drosilicone oil-grafted polybutadiene as soft segment via foaming technology. It was found that the hydrophobic polyurethane foams exhibited good hydrophobic capability and were regenerated easily. Of great interest, the hydrophobic polyurethane foams expand in contact with the oils. This indicates that the process of sorption by the hydrophobic polyurethane foams involves both the filling of the pores with oils and the absorption of oils by the polymer regions (polyurethane elastomer skeleton), and the adsorption capacity of the hydrophobic polyurethane foams can be enhanced by the swelling of the polyurethane elastomer skeleton. We can use this finding to improve the adsorption capacity of the hydrophobic polyurethane foams without merely changing the porosity. The effect of the swelling property of the hydrophobic polyurethane foams on the sorption capacity was further investigated. The results suggest that the hydrophobic polyurethane foams are promising in the application of oil spill recovery.     

Wettability of tri-block copolymer coated hydrophobic surfaces Predictions and measurements

Hydrophobic surfaces with adsorbed tri-block copolymers are wetted by oil in spite of the hydrophilic buoy groups of the block copolymer that are present near the surface. The effect of the buoy group length of the adsorbed molecules on the wettability of hydrophobic surfaces is studied by contact angle measurements and by computer modelling.

The computer model predicts an increase in interfacial free energy with increasing buoy group length for equilibrium adsorption of block copolymer from water. Molecules with large buoy groups occupy more lateral space; therefore the “bare” surface gets more exposed and the anchor groups contribute less to the interfacial free energy which thus increases with the buoy group length.

The calculations showed that the variation of the interaction parameter between solvent and buoy group hardly influences the interfacial free energy. In contrast the interaction parameter between solvent and surface influences the interfacial free energy to a large extent because the oil/surface interactions have a lower energetic value as compared to water/surface interactions and therefore the interfacial free energy is lower than in water. The interfacial free energy varies slightly with increasing buoy group length, depending on the value chosen for the solvent/surface interaction parameter.

Advancing and receding contact angles of hexadecane, sunflower oil and hydrolysate (partly hydrolysed sunflower oil) were measured on hydrophobic surfaces. All oil/water contact angles were small, indicating a hydrophobic apolar surface character. It was found that, for oils with a “good” interaction with the surface (hexadecane and sunflower oil), the contact angle has a minimum value at a certain buoy group length. For hydrolysate (less-strong interaction with the surface) the contact angle decreases monotonically with increasing buoy group length. The results for hexadecane, sunflower oil and hydrolysate are in reasonable agreement with the model predictions. The effect of increasing buoy group length is weak; both decreasing and increasing angles are found, depending on the type of oil used.     

SURFACE ENTHALPY AND ENTROPY AND THE PHYSICO-CHEMICAL NATURE OF HYDROPHOBIC AND HYDROPHILIC INTERACTIONS

The attractive Interactions between typically hydrophobic molecules such as hexane or CCl₄, and the repulsive Interactions between extremely hydrophilic molecules such as poly(ethylene oxide) (PEO), when immersed in water, as well as the interactions between these molecules and water, have been examined from a surface thermodynamic viewpoint, taking the changes in surface free energy into account, as a function of temperature. It was found that attractive hydrophobic Interactions are not, as vas generally believed up to now, invariably entropic. Hydrophobic Interactions can be mainly enthalpic or mainly entropic, or more or less equal mixtures of both, depending on each individual case; however, all hydrophobic interactions are polar (in the sense of Lewis acid-base) in nature. Repulsive hydrophilic interactions are enthalpic, and also polar in nature. The interaction between hydrophobic solutes and water is mainly enthalpic, and is apolar in nature.     

Forces between extended hydrophobic solids: Is there a long-range hydrophobic force?

Thirty years ago there was considerable excitement over the first report of a long-ranged “hydrophobic force” between solids that were not wet by water (Israelachvili and Pashley, Nature 1982, 300, 341–342). Many of the subsequent measurements have been reexamined and found not to support the existence of a long-range hydrophobic force. The principal difficulty was that hydrophobic solids frequently experience other forces, which obscured or were mistaken for a hydrophobic force. In this paper, we review the surviving evidence for a long-range hydrophobic force and find that there is only supporting evidence in a total of two papers, one old and one new, where net attractive forces were measured at separations greater than about 5–6 nm. Thus the evidence is scarce. In contrast there are new experiments showing no such force, thereby arguing against the universality of a measureable hydrophobic force beyond about 6 nm. Since solvent water is common to the experiments, such evidence makes it difficult to describe a universal mechanism for a long-ranged hydrophobic force based on water structure. There are also new measurements that are consistent with a hydrophobic force with a decay length in the range 0.3–1.0 nm. In particular, attractive forces have been measured on small radius surfaces (8–50 nm) consistent with a hydrophobic force with a decay length of 0.5–0.6 nm, and a variety of net repulsive measurements are consistent with an attractive hydrophobic force that has a decay length of 0.3–1.0 nm. We also discuss some new measurements, which are consistent with cavitation, and not a surface force that acts at a distance.     

Effect of Temperature in micro-HPLC Separation of PAHs under Isocratic Conditions Using Octadecyl and Alkylamide Phases

The main difficulty in micro-HPLC separation is the manipulation with the composition of the mobile phase (degassing of solvents and a slow establishment of equilibrium) but the problem of elution can be solved by temperature optimalization. The effect of temperature in micro-HPLC separation of the 16 polycyclic aromatic hydrocarbons (PAHs) (mixture SRM 1647 of the US EPA) has been studied using conventional C₁₈ and new developed AP phase (an amide group localized in the hydrophobic ligands). All the investigations have been performed under isocratic conditions (binary hydroorganic mobile phase: acetonitrile/water). The results have shown that, in the case of AP phase, application of temperature gradient (from 298 to 303 K), enabled the attainment of complete 16 PAHs separation (especially of the first 4 solutes).