Reaction Kinetics in the Production of Pd Nanoparticles in Reverse Microemulsions. Effect on Particle Size

In the synthesis of metallic nanoparticles in microemulsions, we hypothesized that particle size is mainly controlled by the reaction rate. Thus, the changes observed on the particle sizes as reaction conditions, such as concentrations, temperature, type of surfactant used, etc., are varied should not be correlated directly to the modification of those conditions but indirectly to the changes they produce on the reaction rates. By means of time resolved UV-vis spectroscopy, we measured the reaction rates in the production of Pd nanoparticles inside microemulsions at different reactant concentrations, keeping all the other parameters constant. The measured reaction rates were then correlated with the particle sizes measured by transmission electron microscopy (TEM). We found that nanoparticle size increases linearly as the reaction rates increases, independently of the actual reactant concentrations. We proposed that the kinetics is controlled mainly by the diffusion of the reducing agent through the surfactant monolayer covering the microemulsion membrane. With this model, we predicted that particle size should depend indirectly, via the reaction kinetics, on the micelle radius (v0 ~ r^-3), the water volume (v0~vw^3) and the total microemulsion volume (v0~vT^-3), and temperature (Arrhenius). Some of these predictions were explored in this article

Microemulsion breakdown by pervaporation technique: Effect of the alkyl chain length of n-alkanol, a cosurfactant of the microemulsion

Two sets of microemulsions, cyclohexane- and water-rich ones, were prepared with the following n-alkanols as cosurfactants: n-propanol, n-butanol, n-pentanol, and n-hexanol. The results showed the influence of the alkyl chain length of the n-alkanol on the permselectivity properties of the pervaporation technique in the breakdown of the microemulsions. The variations of the total flux rate J and the enrichment factor β were in parallel with the effect of the cosurfactant on the swelling extent of the PDMS membrane

The antimicrobial activity of oil-in-water microemulsions is predicted by their position within the microemulsion stability zone

It has been shown previously that thermodynamically stable oil-in-water microemulsions have significant antimicrobial activity against planktonic cells and biofilm cells over short periods of exposure. It was the aim of this study to identify whether the position of the microemulsion within the microemulsion stability zone of the pseudo-ternary phase structure predicts the efficiency of the antimicrobial action of the microemulsion. Microemulsions were formulated at different points within the microemulsion stability zone. Experiments were performed to observe the kinetics of killing of these microemulsions against selected test microorganisms (Pseudomonas aeruginosa ATCC 9027, Candida albicans ATCC 10231, Staphylococcus aureus ATCC 6538 and Aspergillus niger ATCC 16404). The results indicated that the antimicrobial activity of the microemulsion is dependant upon its position within the zone of stability and is greater nearer the centre of that zone. The results indicate that significant antimicrobial activity can be observed at all points within the zone of microemulsion stability, but that maximal activity is to be found at the centre of that area

Self-Diffusion and Collective Diffusion of Charged colloids Studied by Dynamic Light Scattering

A microemulsion of decane droplets stabilized by a non-ionic surfactant film is progressively charged by substitution of a non-ionic surfactant molecule by a cationic surfactant. We check that the microemulsion droplets remain identical within the explored range of volume fraction (0.02 to 0.18) and of the number of charge per droplets (0 to 40) . We probe the dynamics of these microemulsions by dynamic light scattering. Despite the similar structure of the uncharged and charged microemulsions the dynamics are very different . In the neutral microemulsion the fluctuations of polarization relax, as is well known, via the collective diffusion of the droplets. In the charged microemulsions, two modes of relaxation are observed. The fast one is ascribed classically to the collective diffusion of the charged droplets coupled to the diffusion of the counterions. The slow one has, to our knowledge, not been observed previously neither in similar microemulsions nor in charged spherical colloids. We show that the slow mode is also diffusive and suggest that its possible origine is the relaxation of local charge fluctuations via local exchange of droplets bearing different number of charges . The diffusion coefficient associated with this mode is then the self diffusion coefficient of the droplets

Clean synthesis of adipic acid from cyclohexene in microemulsions with stearyl dimethyl benzyl ammonium chloride as surfactant: From the laboratory to bench scale

Adipic acid, HOOC(CH2)4COOH, is a white crystalline solid used primarily in the manufacture of nylon-6,6 polyamide. In industry, adipic acid is mainly produced by oxidation of cyclohexane with air and nitric acidfollowing a homogeneous two-step route. However, this process leads to the formation of nitrous oxide, a greenhouse gas that has to be decomposed. The aim of this study was the development of a clean technology at pilot scale in order to obtain and recover pure adipic acid, and the evaluation of its industrial practicability. Adipic acid was synthesized from cyclohexene and hydrogen peroxide in microemulsions with stearyl dimethyl benzyl ammonium chloride as surfactant. The non-polluting catalyst sodium tungstate, which contains no heavy metal, was used and the reaction conducted under mild conditions (85 C, 8 h). Yields of up to 81% were reached at the 0.14 L scale. However at the end of the reaction the catalyst and the surfactant must be separated and recycled for subsequent cycles. The reuse of the reaction media enabled the conversion to be increased up to 92% but a loss of surfactant and/or catalyst through the cycles progressively reduced the yields. Yields at the bench scale (1.4 L) increased during the two first cycles and then decreased to conversions of between 60% and 70%. Globally the yield is a little lower at bench scale. The results obtained show that the synthesis of adipic acid by a heterogeneous one-step oxidation of cyclohexene in the presence of hydrogen peroxide is an attractive route for developing a future green industrial process

Linear viscoelasticity of emulsions : II. Measurements of the linear viscoelastic behavior of emulsions in the kilohertz range

Linear viscoelasticity of emulsions in shear deformation in the kilohertz range is demonstrated experimentally. In order to avoid complications due to inertia effects, emulsions with small droplet sizes are studied. The preliminary measurements are interpreted as being the result of droplet deformations. If this interpretation is correct, measurements of the dynamic viscosity of emulsions may be used to obtain information about the mechanical properties of the interfacial layer between droplets and the continuous phase. In particular, the evaluation of the interfacial tension of emulsion droplets from bulk properties might be possible using this technique