Synthesis of mesoporous TiO2 with colloidal gas aphrons,colloidal liquid aphrons,and colloidal emulsion aphrons for dye-sensitized solar cells

High surface area mesoporous titanium dioxide (TiO₂) particles have been prepared by three different kinds of colloidal aphrons: colloidal gas aphrons, colloidal liquid aphrons, and colloidal emulsion aphrons (CEAs). The precipitate of amorphous TiO₂ was prepared by hydrolysis, condensation, and polycondensation reaction of the precursor. The reaction took place under the effect of coulombic repulsion and electrostatic layers of multilayer surfactant molecules. TiO₂ particles with various sizes were prepared with different molar ratio of titanium ion to surfactants, which were sodium lauryl sulfate (SDS), cetyltrimetyhlammonium bromide, triblock copolymer Pluronic P123, and triblock copolymer Pluronic F127. The synthesized samples were characterized by X-ray diffraction, Brunauer-Emmett-Teller analysis, N₂ adsorption/desorption, and transmission electron microscopy. The mesoporous TiO₂ prepared by CEAs method showed a high specific surface area of 224 m²/g with the total pore volume of 0.7751 cm³/g by using SDS as the membrane phase surfactant due to electrostatic attraction favors of anionic surfactant. The solar conversion efficiency of the cell made from TiO₂ increases with the combination of increased surface area and total pore volume for higher amount of dye wetting and loading.     

Aphron applications — A review of recent and current research

Colloidal aphrons are multi-layered stable bubbles (CGAs) or droplets (CLAs), surrounded by a thin surfactant film. The small size of the aphrons creates a system with a high interfacial area which can be pumped like water without collapsing. The high stability of colloidal aphrons due to a thin soapy shell surrounding the core, and high interfacial area make them of interest in many processes such as mineral processing, protein recovery, drilling fluids, separation of organic dyes from waste water, predispersed solvent extraction of dilute streams, clarification and purification of suspensions, soil remediation, material synthesis and immobilization of enzymes. This article aims to provide a comprehensive database in generation, characterization and applications of colloidal gas and liquid aphrons from more than 140 published works so far. The article also reports scale up, industrial applications, technical limitation regarding aphrons application and important future research scopes.     

Preconcentration of strontium using aphrons

Aphrons containing di-(2-ethylhexyl)phosphoric acid (DEHPA) as an active substance were used for preconcentration of strontium from acetate buffers. Conditions for preparation of reasonably stable aphrons using non-ionic and anionic detergents in n-alkane and water mixture were found. After distribution of strontium, aphrons were separated from water solution by filtration with micro-filters. The separation efficiency was compared to the results obtained in liquid-liquid extraction of strontium with DEHPA in n-alkane. The results show that the preconcentration efficiency for strontium for aphrons is as good as for liquid-liquid extraction systems.     

Surface modification of colloidal silica particles

Colloidal silica particles in organic solvents were grafted, using several reagents, in order to make them hydrophobic. The hydrophobicity of the beads could be easily varied. Quasielastic light scattering and transmission electron microscopy experiments showed that no aggregation occurs during the reaction when monofunctional agents are used. Elemental analysis and solid-state NMR measurements gave us the rate of surface modification of the silanol groups. We also studied the rheological behaviour of the grafted particles as a function of the volume fraction in solvents of various hydrophobicity. Hexamethyldisilazane-grafted particles display hard-sphere behaviour in polar solvents such as 2-propanol, but not in alkanes, whereas dimethyldodecylchlorosilane-grafted particles flocculated in polar solvents but could easily be dispersed in apolar solvents. Received: 15 March 2000 Accepted: 11 July 2000     

Stabilization and characterization of colloidal gas aphron dispersions

Colloidal gas aphrons (CGAs) are finding increasing application in water processing, bioseparation, bubble-entrained floc flotation, separation of oil from sand, etc. This article proposes an effective method of encapsulation to stabilize the CGA bubbles with silicic sol solution for their characterization. The stabilized CGA bubbles can keep shapes and sizes for at least 12 h; even the bubbles smaller than 25 mum can also be stabilized and exist for very long times. Effects of concentration and pH of silicic sol solution on CGA stabilization were studied. The optimal ranges of concentration and pH of silicic sol solution are 0.15-0.25 mol/dm(3) and 7-10, respectively. The bubble distortion behavior in disturbance and size distribution of CGAs were examined by using the stabilization method and photographic techniques.     

Synthetic-based aphrons: Correlation between properties and filtrate reduction performance

Aphrons fluids, because of their “noninvasive” characteristic, are indicated for drilling zones that have multiple intercalations of depleted formations adjacent to formations that require high-density fluids. Aphrons are colloidal dispersions containing microbubbles, with cores of gas, liquid or emulsion ranging from 10 to 100 μm in diameter, that are highly stable due to their high interfacial area and multiple surrounding surfactant layers. This paper presents results of physical–chemical properties, bubble size distribution and filtration of systems containing microbubbles. The aphrons were generated by applying a pressure differential under a high-pressure high-temperature (HPHT) filtration cell. Tests were also run with different types of surfactants, specific for generation of bubbles in an organic medium (ester). The surfactants were analyzed for their surface tension and the dispersions produced were photographed under an optical microscope at 60× magnification. The images obtained were digitized to enable determination of the bubble size distribution using an ImageJ program. The filtrate reduction performance of these fluids was determined by static filtration in synthetic porous media. There was a correlation between the filtration characteristics of the fluids, the bubble size distribution and number of bubbles produced in each base and for each surfactant tested. The results obtained served as a reference to formulate a light, non-water-based drilling fluid containing microbubbles with “noninvasive” characteristics.     

Effect of calcination temperature on the surface morphology and crystallinity of tungsten (VI) oxide nanorods prepared using colloidal gas aphrons method

The effect of calcination temperature on the surface morphology and crystallinity of tungsten (VI) oxide, WO₃ nanorods prepared using colloidal gas aphrons (CGAs) as template was studied. The synthesized WO₃ nanorods were calcined in a furnace for 4 h at four different temperatures, i.e., 400, 500, 600 and 700 °C. The morphology of the calcined WO₃ nanorods have been characterized by both transmission electron microscope (TEM) and variable pressure scanning electron microscope (SEM) equipped with energy dispersive X-ray analysis (EDAX). The results showed that the calcination temperature influenced the shape and size of the WO₃ nanorods produced. It is also found that the calcination at various temperature do not effect the composition and the purity of the WO₃ nanorods. In order to characterize the crystalinity of WO₃, X-ray diffraction (XRD) has been used. It shows that all the calcined WO₃ produced are in crystalline form compared to the as-prepared WO₃ nanorods, which is in amorphous form.     

Lecithin organogels used as bioactive compounds carriers. A microdomain properties investigation

Organogels were obtained by adding small amounts of water to a solution of lecithin in organic solvents. Either isooctane or isopropyl palmitate and isopropyl myristate were used as the continuous organic phase of the gels. EPR spectroscopy using both DSA membrane-sensitive and lipophilic spin probes was applied to define the dynamic structure of the surfactant monolayer and the continuous oil phase of lecithin organogels. It was found that by increasing the water quantity, an increase of the polar head area per lecithin molecule was induced, and as a consequence the total interface expanded. It was found that the use of esters as organic solvents induced a decrease of the size of the dispersed structures. The interconnection of the aqueous microdomains and their dynamics were monitored by both static and time-resolved fluorescence quenching spectroscopy using Ru(bipy)32+ as fluorophore and Fe(CN)63- as quencher. It was found that the rates of inter- and/or intra-micellar exchange of water molecules were very slow because they appeared quite immobilized close to the lecithin polar heads. According to the results of the dynamic studies, appropriate organogels were formulated and used to incorporate model bioactive compounds with medicinal or cosmetic interest such as caffeine and theophylline. When these systems were tested for trans-membrane diffusion, they showed a 24 h permeation of 20% and 35%, respectively.     

Stability versus phase ratios of geranyl acetate three-phase emulsions

Three-phase geranyl acetate emulsions stabilized by a non-ionic surfactant, Laureth 4, were prepared with a constant weight fraction of a lamellar liquid crystal and varied aqueous to oil phase weight ratios according to the phase diagram. The appearance and micrographs of the drop pattern versus time were recorded. As expected, emulsions with the lower values of the water to oil (W/O) ratio appeared to be of the W/O variety while the two more stable emulsions with the highest W/O ratio appeared as oil to water (O/W). Considering the surfactant exclusive solubility in the oil, this result was unexpected and the emulsions were investigated as to their structure. Unpredictably, all the emulsions were of the O/W kind; including the highest ratio of oil to water. The reason for this unanticipated outcome was the lamellar liquid crystal being dispersed into the aqueous phase at the slightest perturbation.     

Initial inter-phase transport of compounds in a model emulsion system

Three-phase geranyl acetate emulsions stabilized by a non-ionic surfactant, Laureth 4, were prepared with a constant weight fraction of a lamellar liquid crystal and varied aqueous to oil phase weight ratios according to the phase diagram. The appearance and micrographs of the drop pattern versus time were recorded. As expected, emulsions with the lower values of the water to oil (W/O) ratio appeared to be of the W/O variety while the two more stable emulsions with the highest W/O ratio appeared as oil to water (O/W). Considering the surfactant exclusive solubility in the oil, this result was unexpected and the emulsions were investigated as to their structure. Unpredictably, all the emulsions were of the O/W kind; including the highest ratio of oil to water. The reason for this unanticipated outcome was the lamellar liquid crystal being dispersed into the aqueous phase at the slightest perturbation.     

离子液体参与构筑的微乳液:离子液微乳液

微乳液一般是指两种互不相溶的液体(极性相:一般为水;非极性相:一般为有机溶剂),在表面活性剂作用下形成的均一透明的热力学稳定体系,已广泛应用于材料制备、化学合成等领域.离子液体是熔点低于100℃,完全由离子组成的一类物质,作为一种"绿色溶剂",具有诸多优异的物理化学性质,又被称为"可设计型溶剂".本文综述了离子液体作为极性相、非极性相,甚至表面活性剂,构筑的一类微乳液――离子液微乳液,重点介绍了其物理化学性质的研究进展,并展望了发展趋势.     

Characterization of Colloidal Gas Aphron-Fluids Produced from a New Plant-Based Surfactant

Colloidal gas aphrons (CGAs) are gas bubbles with diameters ranging from 10 to 100 microns, generated by intense stirring of a surfactant solution at high speed. The surface activity and aggregation behavior of the surfactant affects the size/size distribution, stability, and other physicochemical properties of generated aphrons. Therefore, selection of a suitable surfactant is important for the generation of microbubbles with the desired properties. The goal of this articleis to investigate the potential use of a new plant-derived surfactant as an aphronizer surfactant in preparation of CGA-based drilling fluids for accomplishing desirable rheological and filtration properties. For this purpose, natural surfactant obtained from leaves of special tree, namely, Zizyphusspina Christi and used for preparation of aphron-based fluids. To achieve the research objectives, laboratory tests of suspension generation, microscopic visualization, initial yield, filtration loss, and rheological characterization with varying concentrations of surfactant and polymer were performed. Experimental results demonstrate that newly proposed biosurfactant has a great potential for application in preparation of CGA-based drilling fluids for implementation in petroleum drilling industry.      

Ultrasonic characterisation of colloidal dispersions: detection of flocculation and adsorbed layers

A series of experiments to detect flocculation and the presence of adsorbed layers on polystyrene latices is presented. The system consisted of 504.1 nm diameter polystyrene latex at 4.39% w/w in the absence or presence of non-ionic surfactant, Triton (TX100) and hydroxyethylcellulose (HEC). Ultrasonic scattering calculations were performed on each system using the theory of Allegra and Hawley. Ultrasonic spectroscopy was carried out using the Institute of Food Research (IFR) discrete frequency spectrometer, accurate to 0.01% and 4% in velocity and attenuation, respectively. The instrumental precision was up to an order of magnitude better. There were marked increases in ultrasonic attenuation upon flocculation, whether by a bridging or a depletion mechanism. Small but significant increases in attenuation were observed in the presence of adsorbed layers of surfactant or HEC, compared with a model that assumed the solutes to be uniformly dispersed in the continuous phase.     

Nanostructure and amphiphile self-assembly in polar molecular solvents: amides and the "solvophobic effect"

The ability of low molecular weight amides to support amphiphile self-assembly is shown to be a general feature for this class of solvents. This report extends the number of known polar solvents which can support amphiphile self-assembly by five new amides; more than doubling the number of known amides able to serve as amphiphile self-assembly media. The formation of lyotropic liquid crystalline phases by cationic and non-ionic surfactants in these liquid amides is reported. The ability of a solvent to promote amphiphile self-assembly is governed by the "solvophobic effect" and is linked to the solvent cohesiveness. The Gordon parameter which is a measure of the solvent cohesiveness was found to provide a guide to an amides capacity to support lyotropic liquid crystalline phase diversity and thermal stability ranges of those phases. The "solvophobic effect" and steric hindrance factors were compared between amide's and protic ionic liquids possessing analogous chemical structures and also being able to promote amphiphile self-assembly.     

Degradation of kinetically-stable o/w emulsions

This article summarizes the studies on the degradation of the thermodynamically unstable o/w (nano)emulsion--a dispersion of one liquid in another, where each liquid is immiscible, or poorly miscible in the other. Emulsions are unstable exhibiting flocculation, coalescence, creaming and degradation. The physical degradation of emulsions is due to the spontaneous trend toward a minimal interfacial area between the dispersed phase and the dispersion medium. Minimizing the interfacial area is mainly achieved by two mechanisms: first coagulation possibly followed by coalescence and second by Ostwald ripening. Coalescence is often considered as the most important destabilization mechanism leading to coursing of dispersions and can be prevented by a careful choice of stabilizers. The molecular diffusion of solubilizate (Ostwald ripening), however, will continuously occur as soon as curved interfaces are present. Mass transfers in emulsion may be driven not only by differences in droplet curvatures, but also by differences in their compositions. This is observed when two or more chemically different oils are emulsified separately and the resulting emulsions are mixed. Compositional ripening involves the exchange of oil molecules between emulsion droplets with different compositions. The stability of the electrostatically- and sterically-stabilized dispersions can be controlled by the charge of the electrical double layer and the thickness of the droplet surface layer formed by non-ionic emulsifier. In spite of the similarities between electrostatically- and sterically-stabilized emulsions, there are large differences in the partitioning of molecules of ionic and non-ionic emulsifiers between the oil and water phases and the thickness of the interfacial layers at the droplet surface. The thin interfacial layer (the electrical double layer) at the surface of electrostatically stabilized droplets does not create any steric barrier for mass transfer. This may not be true for the thick interfacial layer formed by non-ionic emulsifier. The interactive sterically-stabilized oil droplets, however, can favor the transfer of materials within the intermediate agglomerates. The stability of electrosterically-stabilized emulsion is controlled by the ratio of the thickness of the non-ionic emulsifier adsorption layer (delta) to the thickness of the electrical double layer (kappa(-1)) around the oil droplets (delta/(kappa(-1))) = (deltakappa). The monomer droplet degradation can be somewhat depressed by transformation of coarse emulsions to nano-emulsion (miniemulsion) by intensive homogenization and by the addition of a surface active agent (coemulsifier) or/and a water-insoluble compound (hydrophobe). The addition of hydrophobe (hexadecane) to the dispersed phase significantly retards the rate of ripening. A long chain alcohol (coemulsifier) resulted in a marked improvement in stability, as well, which was attributed to a specific interaction between alcohol and emulsifier and to the alcohols tendency to concentrate at the o/w interface to form stronger interfacial film. The rate of ripening, according to the Lifshitz-Slyozov-Wagner (LSW) model, is directly proportional to the solubility of the dispersed phase in the dispersion medium. The increased polarity of the dispersed phase (oil) decreases the stability of the emulsion. The molar volume of solubilizate is a further parameter, which influences the stability of emulsion or the transfer of materials through the aqueous phase. The interparticle interaction is expected to favor the transfer of solubilizate located at the interfacial layer. The kinetics of solubilization of non-polar oils by ionic micelles is strongly related to the aqueous solubility of the oil phase (the diffusion approach), whilst their solubilization into non-ionic micelles can be contributed by interparticle collisions.     

胶体泡沫(CGA)排液动力学研究

分别对三种表面活性剂, 十二烷基硫酸钠(SDS)、十六烷基三甲基溴化铵(HTAB)以及吐温80 (Tween 80)形成的胶体泡沫(CGA)的排液过程动力学进行了研究. 讨论了表面活性剂种类和浓度, 体系温度等对CGA排液过程的影响. 运用非线性最小二乘法拟合, 推出了表征CGA排液过程的动力学模型: V_t＝V_maxtⁿ/(Kⁿ＋tⁿ), 式中, V_t表示时间t时的排液量(mL), t表示排液时间(s), V_max表示CGA最大排液量(mL)的模型参数, K为模型参数, 表征CGA排液过程的半衰期t_1/2, n为排液曲线反曲特征指数. 通过该模型计算出了表征CGA排液过程的速率常数k_d和半衰期t_1/2等参数. 并通过lnk_d～T^－1的线性关系, 证明了该模型符合Arrhenius方程. 最后, 通过对CGA排液速率随时间的变化分析, 解析了CGA排液过程的“两段论”机理.     

Effect of silica particles on stability of highly concentrated water-in-oil emulsions with non-ionic surfactant

Water-in-oil, high internal phase emulsion made of super-cooled aqueous solution containing a mixture of inorganic salts and stabilized with non-ionic surfactant (sorbitan monooleate) alone was investigated. It was not possible to produce a highly concentrated emulsion (with aqueous phase fraction = 94 wt %), stabilized with surface-treated silica, solely: we were able to form an emulsion with a maximal aqueous phase mass fraction of 85 wt % (emulsion inverts/breaks above this concentration). The inversion point is dependent on the silica particle concentration, presence of salt in the aqueous phase, and does not depend on the pH of the dispersed phase. All emulsions stabilized by the nanoparticles solely were unstable to shear. So, the rheological properties and stability of the emulsions containing super-cooled dispersed phase, with regards to crystallization, were determined for an emulsion stabilized by non-ionic surfactant only. The results were compared to the properties obtained for emulsions stabilized by surface treated (relatively hydrophobic) silica nanoparticles as a co-surfactant to sorbitan monooleate. The influence of the particle concentration, type of silica surface treatment, particle/surfactant ratio on emulsification and emulsion rheological properties was studied. The presence of the particles as a co-stabilizer increases the stability of all emulsions. Also, it was found that the particle/surfactant ratio is important since the most stable emulsions are those where particles dominate over the surfactant, when the surfactant’s role is to create bridging flocculation of the particles. The combination of the two types of hydrophobic silica particles as co-surfactants is: one that resides at the water/oil interface and provides a steric boundary and another that remains in the oil phase creating a 3D-network throughout the oil phase, which is even more beneficiary in terms of the emulsion stability.     

Kinetics of colloidal templating using emulsion drop consolidation

The emulsion templating of ordered colloidal microsphere assemblies by Manoharan et al. involves a consolidation process where dispersed phase fluid is transported from droplets into a continuous phase. Consolidation can be approximated as a diffusion process with moving boundaries. The kinetics of consolidation are investigated here by following droplet shrinkage with time as a prelude to understanding rate effects on assembly structure. Consolidation kinetics are influenced by liquid diffusivity, the number of colloidal particles in a droplet, and the surfactant concentration. While surfactant exhibits little effect well below its critical micelle concentration (CMC) value, it significantly slows consolidation above the CMC. For a specific continuous phase (i.e., silicone oil and fluorinated silicone oil), with proper scalings, the droplet size shrinks with time following a power law independent of droplet diameter, surfactant concentrations, and particle number concentration. The power law exponent varies from 1/2 to 2/3 with different continuous oil phases as a result of concentration and interfacial effects. This study leads to an improved understanding of colloidal microstructure development at interfaces that can be applied in novel materials synthesis and drug delivery areas.     

Preparation of clear colloidal solutions of detonation nanodiamond in organic solvents

Highly transparent colloidal solutions of detonation nanodiamonds in organic solvents such as tetrahydrofuran (THF), methyl ethyl ketone (MEK) and acetone were attained in this investigation through an easy process, in which the detonation nanodiamond powder was oxidized at 420 °C for 1.5 h and then dispersed into solvents by beads-milling with the addition of the surfactant, oleylamine (OLA). The results of both Fourier transform infrared spectroscopy and zeta potential measurements confirm that a readily apparent number of Lewis acid sites composed of mainly carboxylic acid and cyclic acid anhydrides were derived on the surface of thermally oxidized nanodiamond (T-ND). This acid sites-derived T-ND is chemically active, favoring the formation of charge-transfer complexes with the amino-containing surfactants such as OLA and octadecylamine (ODA). After being dispersed with one of the surfactants, OLA or ODA, the T-ND shows good dispersion stability in organic solvents; however, the dispersion efficiency of the saturated ODA is not as good as that of the unsaturated OLA. By using the dispersant OLA, accompanied with de-agglomeration by beads-milling, a clear colloidal solution of T-ND in solvents of THF, MEK or acetone can be easily attained and stabilized for at least 3 months.     

Cloud point preconcentration of rather polar compounds: application to the high-performance liquid chromatographic determination of priority pollutant chlorophenols

The potential of the cloud point methodology for the preconcentration of relatively polar compounds was studied using the non-ionic surfactant Triton X-114 and five EPA chlorophenols as test analytes. Analyte determination was performed using reversed-phase gradient LC with electrochemical and spectrophotometric detection. The amount of surfactant used is a critical variable in the preconcentration factor because it determines the extraction yield and the volume of surfactant-rich phase obtained. These values were determined as a function of the Triton X-114 concentration, together with the phase ratio, which allows prediction of the maximum preconcentration factor under given conditions.