Zhenggang Cui

Multiple phase inversion of emulsions stabilized by in situ surface activation of CaCO3 nanoparticles via adsorption of fatty acids.

The in situ surface activation of raw CaCO(3) nanoparticles by interaction with a series of sodium carboxylates of chain length between 6 and 12 as well as sodium 2-ethylhexylsulfosuccinate (AOT) was studied, and the impact of this on the stabilization and phase inversion of toluene-water emulsions was assessed. By using complementary experiments including measurement of particle zeta potentials, adsorption isotherms of amphiphile, and relevant contact angles, the mechanism of this activation was revealed. The results show that hydrophilic CaCO(3) nanoparticles can be surface activated by interaction with sodium carboxylates and AOT even if they are not surface-active themselves. Both the electrostatic interaction between the positive charges on particle surfaces and the negative charges of anionic amphiphile headgroups and the chain-chain interactions of the amphiphile result in monolayer adsorption of the amphiphile at the particle-water interface. This transforms the particles from hydrophilic to partially hydrophobic such that they become surface-active and stabilize oil-in-water O/W(1) emulsions and induce O/W(1) → water-in-oil W/O phase inversion, depending on the chain length of the carboxylate molecules. At high amphiphile concentration, bilayer or hemimicelle adsorption may occur at the particle-water surface, rendering particles hydrophilic again and causing their desorption from the oil-water interface. A second phase inversion, W/O → O/W(2), may occur depending on the surface activity of the amphiphile. CaCO(3) nanoparticles can therefore be made good stabilizers of both O/W and W/O emulsions once surface activated by mixing with traces of suitable anionic amphiphile.

Switchable Pickering emulsions stabilized by silica nanoparticles hydrophobized in situ with a conventional cationic surfactant.

A stable oil-in-water Pickering emulsion stabilized by negatively charged silica nanoparticles hydrophobized in situ with a trace amount of a conventional cationic surfactant can be rendered unstable on addition of an equimolar amount of an anionic surfactant. The emulsion can be subsequently restabilized by adding a similar trace amount of cationic surfactant along with rehomogenization. This destabilization-stabilization behavior can be cycled many times, demonstrating that the Pickering emulsion is switchable. The trigger is the stronger electrostatic interaction between the oppositely charged ionic surfactants compared with that between the cationic surfactant and the (initially) negatively charged particle surfaces. The cationic surfactant prefers to form ion pairs with the added anionic surfactant and thus desorbs from particle surfaces rendering them surface-inactive. This access to switchable Pickering emulsions is easier than those employing switchable surfactants, polymers, or surface-active particles, avoiding both the complicated synthesis and the stringent switching conditions.

Responsive Aqueous Foams Stabilized by Silica Nanoparticles Hydrophobized in Situ with a Conventional Surfactant

In the recent past, switchable surfactants and switchable/stimulus-responsive surface-active particles have been of great interest. Both can be transformed between surface-active and surface-inactive states via several triggers, making them recoverable and reusable afterward. However, the synthesis of these materials is complicated. In this paper we report a facile protocol to obtain responsive surface-active nanoparticles and their use in preparing responsive particle-stabilized foams. Hydrophilic silica nanoparticles are initially hydrophobized in situ with a trace amount of a conventional cationic surfactant in water, rendering them surface-active such that they stabilize aqueous foams. The latter can then be destabilized by adding equal moles of an anionic surfactant, and restabilized by adding another trace amount of the cationic surfactant followed by shaking. The stabilization-destabilization of the foams can be cycled many times at room temperature. The trigger is the stronger electrostatic interaction between the oppositely charged surfactants than that between the cationic surfactant and the negatively charged particles. The added anionic surfactant tends to form ion pairs with the cationic surfactant, leading to desorption of the latter from particle surfaces and dehydrophobization of the particles. Upon addition of another trace amount of cationic surfactant, the particles are rehydrophobized in situ and can then stabilize foams again. This principle makes it possible to obtain responsive surface-active particles using commercially available inorganic nanoparticles and conventional surfactants.

pH-Responsive Pickering Emulsions Stabilized by Silica Nanoparticles in Combination with a Conventional Zwitterionic Surfactant

pH-responsive oil-in-water Pickering emulsions were prepared simply by using negatively charged silica nanoparticles in combination with a trace amount of a zwitterionic carboxyl betaine surfactant as stabilizer. Emulsions are stable to coalescence at pH ≤ 5 but phase separate completely at pH > 8.5. In acidic solution, the carboxyl betaine molecules become cationic, allowing them to adsorb on silica nanoparticles via electrostatic interactions, thus hydrophobizing and flocculating them and enhancing their surface activity. Upon increasing the pH, surfactant molecules are converted to zwitterionic form and significantly desorb from particles surfaces, triggering dehydrophobization and coalescence of oil droplets within the emulsion. The pH-responsive emulsion can be cycled between stable and unstable many times upon alternating the pH of the aqueous phase. The average droplet size in restabilized emulsions at low pH, however, increases gradually after four cycles due to the accumulation of NaCl. Experimental evidence including adsorption isotherms, zeta potentials, microscopy, and three-phase contact angles is given to support the postulated mechanisms.

Pickering Emulsions Responsive to CO2/N2 and Light Dual Stimuli at Ambient Temperature.

A dual stimuli-responsive n-octane-in-water Pickering emulsion with CO2/N2 and light triggers is prepared using negatively charged silica nanoparticles in combination with a trace amount of dual switchable surfactant, 4-butyl-4-(4-N,N-dimethylbutoxyamine) azobenzene bicarbonate (AZO-B4), as stabilizers. On one hand, the emulsion can be transformed between stable and unstable at ambient temperature rapidly via the N2/CO2 trigger, and on the other hand, a change in droplet size of the emulsion can occur upon light irradiation/rehomogenization cycles without changing the particle/surfactant concentration. The dual responsiveness thus allows for a precise control of emulsion properties. Compared with emulsions stabilized by specially synthesized stimuli-responsive particles or by stimuli-responsive surfactants, the method reported here is much easier and requires a relatively low concentration of surfactant (≈1/10 cmc), which is important for potential applications.

Thermoresponsive Pickering Emulsions Stabilized by Silica Nanoparticles in Combination with Alkyl Polyoxyethylene Ether Nonionic Surfactant.

We put forward a simple protocol to prepare thermoresponsive Pickering emulsions. Using hydrophilic silica nanoparticles in combination with a low concentration of alkyl polyoxyethylene monododecyl ether (C12En) nonionic surfactant as emulsifier, oil-in-water (o/w) emulsions can be obtained, which are stable at room temperature but demulsified at elevated temperature. The stabilization can be restored once the separated mixture is cooled and rehomogenized, and this stabilization-destabilization behavior can be cycled many times. It is found that the adsorption of nonionic surfactant at the silica nanoparticle-water interface via hydrogen bonding between the oxygen atoms in the polyoxyethylene headgroup and the SiOH groups on particle surfaces at low temperature is responsible for the in situ hydrophobization of the particles rendering them surface-active. Dehydrophobization can be achieved at elevated temperature due to weakening or loss of this hydrogen bonding. The time required for demulsification decreases with increasing temperature, and the temperature interval between stabilization and destabilization of the emulsions is affected by the surfactant headgroup length. Experimental evidence including microscopy, adsorption isotherms, and three-phase contact angles is provided to support the mechanism.

Photoresponsive Foams Generated by a Rigid Surfactant Derived from Dehydroabietic Acid

Innovation in the structure of surfactants is crucial to the construction of a surfactant-based system with intriguing properties. With dehydroabietic acid as a starting material, a nearly totally rigid azobenzene surfactant (R-azo-Na) was synthesized. The trans-R-azo-Na formed stable foams with half-lives of 636, 656, 976, and 872 min for 0.3, 1, 2, and 4 mmol·L-1 aqueous solutions, respectively. Under UV light irradiation, a fast collapse of the foams was observed, showing an in situ response. The excellent foam stability of trans-R-azo-Na leads to the extremely high photoresponsive efficiency. As revealed by dynamic surface tension and pulsed-field gradient NMR methods, an obvious energy barrier existed in the adsorption/desorption process of trans-R-azo-Na on the air/water interface. The foams formed by trans-R-azo-Na are thus stable against coarsening processes. The results reveal the unique photoresponsive behavior of a surfactant with a rigid hydrophobic skeleton and provide new insights into the structure causing aggregation of surfactants.

Improving performances of double-chain single-head surfactants for SP flooding by combining with conventional anionic surfactants

ABSTRACT The binary surfactant mixtures of 1,3-dialkyl (diC8-diC12) glyceryl ether ethoxylates with didodecylmethylhydroxylpropyl sulfobetaine (diC12HSB) are good formulations for surfactant–polymer flooding of Daqing crude oil, China, but suffer from low aqueous solubility. By combining with α-olefin sulfonates (AOS) at small molar fractions, the aqueous solubility of the formulations can be significantly improved due to the formation of charged mixed micelles. The ternary formulations can reduce Daqing crude oil/connate water interfacial tension to ultralow at a wide range of total surfactant concentration (0.625u2009∼u200910u2009mM), have good resistance to adsorption by sandstone, and can keep sandstone surface water-wet. GRAPHICAL ABSTRACT

Synthesis of a new sulfobetaine surfactant with double long alkyl chains and its performances in surfactant-polymer flooding

ABSTRACT A new zwitterionic surfactant with double long alkyl chains, 3-((3-((1,3-bis (decyloxyl) propane-2-yl) oxy) -2-hydroxypropyl) dimethylamonio) -2-hydroxypropane-1-sulfonate (diC10GE-HSB), was synthesized, and its performances in Surfactant-Polymer (SP) flooding were studied. As a hydrophobic surfactant diC10GE-HSB solely cannot reduce Daqing crude oil/connate water IFT to ultralow, but ultralow IFT can be achieved by using binary mixtures of diC10GE-HSB with various conventional hydrophilic surfactants such as α–olefin sulfonates, dodecyl polyoxyethylene (10) ether, and cetyl dimethyl hydroxypropyl sulfobetaine, over a wide total concentration range (0.625u2009∼u200910u2009mM) at reservoir temperature. This new sulfobetaine surfactant is therefore a good candidate for SP flooding free of alkali. GRAPHICAL ABSTRACT

Regioselective Nitration of Phenols in O/W Microemulsion by NaNO3 and Dilute Sulfuric Acid

Highly regiospecific mononitration of phenol by NaNO3 and dilute sulfuric acid was carried out in a TX100 oil-in-water microemulsion. Effects of various parameters such as acid type, surfactant concentration, water content, and alcohol have been investigated. The use of inexpensive and relatively nontoxic acidic reagent is an advantage of this method.