Micro-emulsion method

Recently, Mark and co-workers also reported on organophilic silica formed by the combination of the sol-gel procedure and water-in-oil micro-emulsion method, in which methacryloyloxypropyltrimethoxysilane was used as one component of silica matrix [8]. The size of the silica particle was controlled by the content of water and emulsifier used. The surface of the particles was effectively covered with methacryloyl. organic groups. This organophilic silica is expected to be used as a novel component of composite materials. 

CH4 oxidation has been experienced for ceria supported on a barium hexaaluminate, an heat resistant support. Preparation by a new reverse microemulsion method leads to ceria nanoparticles deposited on support and having a BET area close to 100 mVg after calcination at 1000 0 [72]. Such ultrahigh disperse nanoparticles show exceptional thermal resistance the authors mentioned that ceria particles prepared with a size of 6 nm sinters only to 18 nm after a calcination at 1IOO°C under a water containing atmosphere. Of course excellent activity in methane combustion has been observed. According to their experimental conditions calculated specific activity expressed as mol(CH4).h. m was estimated to 6.4x10 at 500°C whereas Bozo [44J reported a value of 1.5x1 O at the same temperature both values look similar. Thus the difference in methane conversion may be related to BET area only which is spectacularly preserved using the reverse micro-emulsion method for synthesis. 

Figure 1 explains the formation mechanism of ZMP nanocontainer. ZMP nanoparticles were prepared by sonochemical irradiation method explained in figure 1. ZMP nanoparticles were functionalized by using myristic acid (C13H27COO-) with the help sonochemical micro emulsion method of to make ZMP nanoparticles hydropho-... 

The AuNPs can also be prepared by the two-phase micro-emulsion method in which, first the metal-containing reagent is transferred from an aqueous to an organic phase. After the addition of a surfactant solution to this system, a micro-emulsion, i.e., a dispersion of two imntiscible liquids, is formed. In micro-emulsion methods, alkane thiols are often added to the reaction solution, and tliese additives form dense self-assembled monolayers on the gold surface. This method was employed for the preparation of self-assembled two- and three-dimensional ensembles of AuNPs [12,13,50]. 

Spherical ultra-fine polymer particles (10-35 nm) were prepared by chemical polymerization of aniline in an inverse water-in-oil microemukion [42]. This micro emulsion method provided a denser, more uniform and compact film of higher condensation than that produced in an aqueous medium [16]. 

PtRu nanoparticles can be prepared by w/o reverse micro-emulsions of water/Triton X-lOO/propanol-2/cyclo-hexane [105]. The bimetallic nanoparticles were characterized by XPS and other techniques. The XPS analysis revealed the presence of Pt and Ru metal as well as some oxide of ruthenium. Hills et al. [169] studied preparation of Pt/Ru bimetallic nanoparticles via a seeded reductive condensation of one metal precursor onto pre-supported nanoparticles of a second metal. XPS and other analytical data indicated that the preparation method provided fully alloyed bimetallic nanoparticles instead of core/shell structure. AgAu and AuCu bimetallic nanoparticles of various compositions with diameters ca. 3 nm, prepared in chloroform, exhibited characteristic XPS spectra of alloy structures [84]. 

The shake-flask method has some drawbacks, however. One problem that occurs occasionally is the formation of micro-emulsions which remain stable for hours or days, and prevent the two solvent layers from separating. In this case it is not possible to measure the concentration of analyte in each phase. More generally, the upper and lower range of log D values is limited by problems of solution handling. For very high log D values the sample is much more soluble in octanol than in water. For example, if log D is 4 the sample is 10,000 times more soluble in octa-... 

Fluorescent silica nanoparticles, called FloDots, were created by Yao et al. (2006) by two synthetic routes. Hydrophilic particles were produced using a reverse micro-emulsion process, wherein detergent micelles formed in a water-in-oil system form discrete nanodroplets in which the silica particles are formed. The addition of water-soluble fluorescent dyes resulted in the entrapment of dye molecules in the silica nanoparticle. In an alternative method, dye molecules were entrapped in silica using the Stober process, which typically results in hydrophobic particles. Either process resulted in luminescent particles that then can be surface modified with... 

An alternative to the injection method for importing enzymes into a microemulsion is the phase transfer method. In this method, a layer of an aqueous enzyme solution is located under a mixture of surfactant and oil. Upon gentle shaking, the enzyme is transferred into the reverse micelles of the hydrocarbon phase. Finally, the excess of water is removed and the hydrophobic substrates can be added. The main advantage of this method is that it ensures thermodynamically stable micro emulsions with maximum water concentrations. However, the method is very time consuming. The method is often applied in order to purify, concentrate or renaturate enzymes in the reverse micellar extraction process [54-58]. 

In many cases, anhydrous metal oxides have been prepared by solvothermal treatments of sol-gel or micro-emulsion-based precursors. Wu and coworkers prepared anatase and rutile Ti02 by a micro-emulsion-mediated method, in which the micro-emulsion medium was further treated by hydrothermal reaction [171]. This micro-emulsion-mediated hydrothermal (MMH) method could lead to the formation of crystalline titania powders under much milder reaction conditions. 

In this communication new results are reported on developing of the template method of synthesis of the nanostructured silicates, and methods micro emulsions and micro suspensions for incorporation of metal oxides and pure metals into mesoporous silicates. 

When the appropriate precautions are taken the method appears particularly suited for measuring very low tensions 10 mN m sometimes even as low as 10 mN m ). Such ultralow tensions are for example encountered in micro-emulsion systems and in just phase-separated polymeric or micellar solutions. For phase-separated colloid-polymer systems de Hoog and Lekkerkerker ) even reported values down to a few pN m , reproducibly being obtained after implementing a number of methodical improvements. (Alternatives for low tensions are the sessile and pending (micro-) drop but these do not usually go below 10 mN m ) Commercial apparatus are nowadays available. A variant proposed by Than et al. J employs a thin rod in the axis of the cylinder, to reduce spin-up time and suppress drift. Another variant, proposed by Kokov, analyses the centrifugal field required to squeeze liquid out of an orifice" ). 

A variant is the micro-pipette method, which is also similar to the maximum bubble pressure technique. A drop of the liquid to be studied is drawn by suction into the tip of a micropipette. The inner diameter of the pipette must be smaller than the radius of the drop the minimum suction pressure needed to force the droplet into the capillary can be related to the surface tension of the liquid, using the Young-Laplace equation [1.1.212). This technique can also be used to obtain interfacial tensions, say of individual emulsion droplets. Experimental problems include accounting for the extent of wetting of the inner lumen of the capillary, rate problems because of the time-dependence of surfactant (if any) adsorption on the capillary and, for narrow capillaries accounting for the work needed to bend the interface. Indeed, this method has also been used to measure bending moduli (sec. 1.15). 

Early work by Vonnegut and Schaefer demonstrated that water could be undercooled by close to 40 degrees below the equilibrium freezing point. Wood and Walton carried out a careful series of experiments in 1970 that were interpreted as due to homogeneous nucleation and from which the surface free energy and its temperature derivative were extracted. These experiments used the droplet emulsion method with the fraction of droplets crystallized as a function of time measured with a camera through a micro-... 

In 2003, Yates and coworkers[148] explored a new method to prepare microporous AlP04-5 fibers by using micro-emulsion droplets as the templates. The surfactant cetylpyridinium chloride with the cosurfactant butanol in the ratio 1/2 forms a stable micro-emulsion in the... 

The extensive research on microemulsions was prompted by two oil crises in 1973 and 1979, respectively. To optimise oil recovery, the oil reservoirs were flooded with a water-surfactant mixture. Oil entrapped in the rock pores can thus be removed easily as a microemulsion with an ultra-low interfacial tension is formed in the pores (see Section 10.2 in Chapter 10). Obviously, this method of tertiary oil recovery requires some understanding of the phase behaviour and interfacial tensions of mixtures of water/salt, crude oil and surfactant [4]. These in-depth studies were carried out in the 1970s and 1980s, yielding very precise insights into the phase behaviour of microemulsions stabilised by non-ionic [5, 6] and ionic surfactants [7-9] and mixtures thereof [10]. The influence of additives, like hydro- and lyotropic salts [11], short- and medium-chain alcohols (co-surfactant) [12] on both non-ionic [13] and ionic microemulsions [14] was also studied in detail. The most striking and relevant property of micro emulsions in technical applications is the low or even ultra-low interfacial tension between the water excess phase and the oil excess phase in the presence of a microemulsion phase. The dependence of the interfacial tension on salt [15], the alcohol concentration [16] and temperature [17] as well as its interrelation with the phase behaviour [18, 19] can be regarded as well understood. 

Perhaps the most striking property of a microemulsion in equilibrium with an excess phase is the very low interfacial tension between the macroscopic phases. In the case where the microemulsion coexists simultaneously with a water-rich and an oil-rich excess phase, the interfacial tension between the latter two phases becomes ultra-low [70,71 ]. This striking phenomenon is related to the formation and properties of the amphiphilic film within the microemulsion. Within this internal amphiphilic film the surfactant molecules optimise the area occupied until lateral interaction and screening of the direct water-oil contact is minimised [2, 42, 72]. Needless to say that low interfacial tensions play a major role in the use of micro emulsions in technical applications [73] as, e.g. in enhanced oil recovery (see Section 10.2 in Chapter 10) and washing processes (see Section 10.3 in Chapter 10). Suitable methods to measure interfacial tensions as low as 10 3 mN m 1 are the sessile or pendent drop technique [74]. Ultra-low interfacial tensions (as low as 10 r> mN m-1) can be determined with the surface light scattering [75] and the spinning drop technique [76]. 

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