A study of the properties of mixed nonionic surfactants microemulsions by NMR, SAXS, viscosity and conductivity

The pseudoternary phase behavior of the water/sucrose laurate/ethoxylated mono-di-glyceride/R (+)-limonene systems was investigated for different surfactants mixing ratios (w/w) at 25 °C. The microemulsion boundaries were determined and the surfactants content at the interface of water- R (+)-limonene was estimated. For surfactants mixing ratio (w/w) equals unity, the area of the one phase microemulsion region reaches its maximum. The system with the maximum microemulsion area was investigated using electrical conductivity, dynamic viscosity, small angle X-ray scattering, and nuclear magnetic resonance. Electrical conductivity increases as the water volume fraction increases and a percolation threshold was observed. Dynamic Viscosity varies as function of the water volume fraction in a non-monotonic way giving two-peaked plot. The characteristics of the domain size of the microemulsions called periodicity measured by small angle X-ray scattering increases with the increase in the water volume fraction. The correlation length of the domain size reaches a maximum when plotted against the water volume fraction in the microemulsions. Relative diffusion coefficients of water increase and those of oil decrease with increasing the water volume fractions in the microemulsions indicating structural transitions.     

Geometry of bicontinuous microemulsions as revealed by SANS and simulations

Summary Water-octane-C₁₀E₄ microemulsions in both the isotropic and lamellar phases were measured using small-angle neutron scattering. Varying the scattering length density of both the water and oil through hydrogen-deuterium substitution enabled us to isolate the scattering contributions of the surfactant monolayers and the water-surfactant and oil-surfactant interfaces. Analyses of the resulting scattering patterns allow us to directly determine the small mean curvature of the surfactant film as a function of temperature and correlate this quantity with the overall phase behavior. A simulation using a Gaussian random field yields the three-dimensional structure of the bicontinuous microemulsion having a surfactant monolayer with zero mean curvature. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Hydrodynamic effects in bicontinuous microemulsions measured by inelastic neutron scattering

The dynamical properties of bicontinuous microemulsions have been studied with neutron spin echo spectroscopy around length scales corresponding to the correlation peak q₀. Comparison of samples with different contrasts for neutrons shed light on the two modes dominated either by variation of the oil/water difference or surfactant concentration in the hydrodynamic regime. The results have been compared to theoretical predictions of the relaxation rates of bicontinuous microemulsions by Nonomura and Ohta [M. Nonomura, T. Ohta, J. Chem. Phys. 110, 7516 (1999)]. The influence of modification of the surfactant layer bending constants in the microemulsion by addition of homopolymers (polyethylenepropylene: PEP_X and polyethyleneoxide: PEO_X, X=5 kg/mol), dissolved in the oil phase and water, has been investigated.     

Preparation of AgBr Nanoparticles in Microemulsions Via Reaction of AgNO<Subscript>3</Subscript> with CTAB Counterion

Nanoparticles of AgBr were prepared by precipitating AgBr in the water pools of microemulsions consisting of CTAB, n-butanol, isooctane and water. An aqueous solution of AgNO₃ added to the microemulsion was the source of Ag⁺ ions. The formation of AgBr nanoparticles in microemulsions through direct reaction with the surfactant counterion is a novel approach aimed at decreasing the role of intermicellar nucleation on nanoparticle formation for rapid reactions. The availability of the surfactant counterion in every reverse micelle and the rapidity of the reaction with the counterion trigger nucleation within individual reverse micelles. The effect of the following variables on the particle size and size distribution was investigated: the surfactant and cosurfactant concentrations, moles of AgNO₃ added, and water to surfactant mole ratio, R. High concentration of the surfactant or cosurfactant, or high water content of the microemulsion favored intermicellar nucleation and resulted in the formation of large particles with broad size distribution, while high amounts of AgNO₃ favored nucleation within individual micelles and resulted in small nanoparticles with narrow size distribution. A blue shift in the UV absorption threshold corresponding to a decrease in the particle size was generally observed. Notably, the variation of the absorption peak size with the nanoparticle size was opposite to those reported by us in previous studies using different surfactants.     

Concentration dependences of solvent self-diffusion coefficients in solutions and heterogeneous systems

On the basis of the concepts of exchange processes the problem to interpret solvent self-diffusion coefficients measured by pulsed field gradient nuclear magnetic resonance in solutions of various nature and heterogeneous systems is discussed. The problem to choose the concentration scale for the interpretation of the concentration dependences of self-diffusion coefficients in such systems is discussed as well.     

Einsatz von deuterierten Molekülen zur Bestimmung von Selbstdiffusionskoeffizienten bei der Zweikomponentenadsorption in Zeolithen unter Anwendung der NMR-Meßtechnik

The nmr pulsed field gradient technique is an efficient tool for measuring molecular self-diffusion in sorplion systems. Applying alternatively perdeutcrated substances, in this way for the first lime the self-diffusion coefficients of the individual components at mullicomponent adsorption could be measured. Examples of self-diffusion results for mixtures of water, ammonia and liydrocarbons adsorbed on different types of zeolites are given.     

高分子溶液体系的自扩散系数的NMR测量

用核磁共振方法测量高聚物体系的自扩散系数是一种有效而直接的方法。本文报告了用核磁共振方法测量高分子在溶液中自扩散系数实验方法的研究结果,并对聚苯乙烯良溶液体系和θ溶液体系的自扩散现象进行了研究和比较,为半浓溶液范围的de-Gennes的"蠕动"理论提供了实验验证。     

微乳液技术制备纳米材料

微乳液是表面活性剂、油相和水相形成的热力学稳定的各向同性的单分散体系,其分散质点为纳量级,它为纳米材料的制备提供理想的模板和微环境,介绍微乳液制备纳米材料的方法和影响因素以及微乳液法制备催化剂、超导体、半导体及磁性等材料的研究进展。     

On the problem of field-gradient NMR measurements of intracrystalline diffusion in small crystallites--water in NaA zeolites as an example

Necessary conditions for measuring intracrystalline diffusion in small crystal size systems via field-gradient NMR are discussed. As an illustrative case self-diffusion coefficients of water adsorbed in NaA zeolites (average crystal diameter about 1 μm) have been measured by ¹H-NMR stimulated echoes in static magnetic field gradients of up to 180 T/m in the temperature range of 254–344 K. Obtaining intracrystalline diffusion coefficients necessitates a sufficiently high spatial resolution only provided by such large field gradients.     

Quantification of microemulsion systems using low-field T1-weighted imaging

Applied to Enhanced Oil Recovery, microemulsions are valuable systems for extracting the crude oil trapped by capillary forces in the porous reservoir rocks. The performances of the injected formulations are often assessed by quantifying oil composition in model systems that contain relatively high amount of surfactant/co-surfactant. Recently, the question of representativity of such systems was raised because kinetics aspects and complexity of crude were neglected in model systems and are likely to impact the process efficiency. The current quantification techniques limit the characterization of representative model systems as they are destructive, time consuming and not often applicable to dark or opaque systems. In the original aim to provide a quantitative kinetic study of such microemulsions, we propose a high resolution T₁-weighted imaging technique to have access to 1D-composition profiles of co-surfactant, oil and brine in Winsor I, Winsor III and Winsor II microemulsions. The analysis is carried out on model systems at equilibrium for proof of concept. Results are correlated with X-Ray Micro-CT experiments to provide better interpretations and assess the method accuracy. We provide conditions of validity of the developed NMR method and discuss its potential limitations. To a larger extent, the method could be of interest to other applications that use similar systems.     

Structural and dynamic properties of polyoxyethylene sorbitan monooleate micelle in water dispersion studied by pulsed field gradient NMR

The diffusion phenomenon of a nonionic surfactant, polyoxyethylene sorbitan monooleate (POE-SMO), micelle in aqueous solution was investigated by pulsed field gradient nuclear magnetic resonance (PFG NMR) with a high gradient strength of 17.4 T/m at the diffusion timet _d varied from 3 to 300 ms. This high gradient strength allowed us to measure the slow self-diffusion coefficient of POE-SMO micelle, and the short diffusion time below 10 ms showed the restricted diffusion of the micelle. At the shortt _d the self-diffusion of the micelle was restricted and the restricted sizes were 1.8, 1.5, and 0.8 μm for the POE-SMO concentration of 100, 200 and 300 mM, respectively, and 0.6 μm for the POE-SMO only. The possible reason of this restriction was assumed to be the formation of a spatial network or a micellar clustering. Furthermore, a proton exchange between water molecule and surfactant OH group on the micelle surface was proposed. With respect to this proposal, the residence time of the proton at the micelle surface and the thickness of the surface were investigated from proton self-diffusion coefficients by PFG NMR.     

NMR study of tomato pericarp tissue by spin-spin relaxation and water self-diffusion

Pericarp tissues of tomato varieties Quest and Cameron were studied by low-field nuclear magnetic resonance (NMR) at a controlled temperature of 20°C. The spin-spin relaxation times and the water diffusion coefficients were measured with Carr-Parcell-Meiboom-Gill and pulsed field gradient multi-spin-echo (PFGMSE) NMR sequences. Four relaxing components were extracted from the spin-spin relaxation. The components withT ₂=11 ms,T ₂=65 ms,T ₂=430 ms andT ₂=1500 ms were related to the nonexchangeable protons and water proton in each cell compartment (i.e., cell wall-extracellular space, cytoplasm and vacuole, respectively). In contrast to the relative intensities, theT ₂ values appeared insensitive to variety and harvest period. The difference in relative intensity was related to the size of the pericarp cell. The water self-diffusion coefficients for each cell compartment were determined simultaneously with the PFGMSE sequence. The water self-diffusion coefficients for the vacuole and cytoplasm were not affected by the harvest date or variety. However, the water self-diffusion in the cell wall-extracellular space was significantly different between the two varieties.     

Percolation phenomenon of calcium bis(2-ethylhexyl) sulfosuccinate water-in-oil microemulsions by conductivity and dielectric spectroscopy measurements

The sodium counterion (Na+) of the sodium bis(2-ethylhexyl) sulfosuccinate (AOT) surfactant was exchanged with calcium Ca2+ to investigate the counterion charge effect on the structure of water in normal decane microemulsions. Ohmic conductivity and dielectric permittivity measurements were performed on samples at constant water to surfactant mole ratio [water]/[Ca(AOT)(2)]=26.6. Increasing the volume fraction of the dispersed phase phi, a percolation phenomenon was observed at the constant temperature of 25 degrees C. The percolation threshold was found at phi approximately 15% by Ohmic conductivity and static dielectric permittivity studied as a function of phi, and by the frequency dependence of the complex permittivity. Critical exponents typical of the static percolation mechanism (formation of bicontinuous microemulsions) were found below and above threshold. The comparison of these results obtained for the two different counterions, Ca2+ and Na+, in AOT surfactant water in normal decane microemulsions allows detection of an important difference. The percolation below threshold is dynamic for the sodium-based microemulsions, accounting for the formation of clusters of droplets, whereas calcium-based microemulsions show a static percolation. For this system, the coalescence of droplets begins to occur below threshold at phi approximately 12%.     

Correlation between film thickness and zinc defect distribution along the growth direction in an isotopic multilayer ZnO thin film grown by pulsed laser deposition analyzed using the internal diffusion method

Zinc self-diffusion along the growth direction was analyzed for the isotopic multilayer ZnO thin film ((⁶⁴ZnO/⁶⁸ZnO)₆⁶⁴ZnO) deposited by pulsed laser deposition. The isotopic distribution was measured using a secondary ion mass spectrometry. The amplitude of the ⁶⁴Zn abundance in the depth profile was reduced by annealing at 993 K for several hours due to interdiffusion between the ⁶⁴ZnO and ⁶⁸ZnO layers. The diffusion profiles at the isotopic interfaces were analyzed using a periodic equation. The obtained zinc self-diffusion coefficients at several isotopic interfaces along the growth direction showed that the self-diffusion coefficients increased towards the film/substrate interface. A similar trend was also found in the lateral direction. The variation among the self-diffusion coefficients was related to the film thicknesses at the analysis positions. Since zinc self-diffusion is controlled by a vacancy-mediated mechanism, the variation in zinc diffusivity along the growth direction can be attributed to the effect of compressive biaxial stress. These findings are useful for producing high-quality ZnO devices.     

Effect of hydrostatic pressure on self-diffusion in metal nanoparticles

The thermodynamics approach has been developed to describe the self-diffusion in nano-sized solids. It has been established that identical homologous temperatures of metal nanoparticles with their fixed characteristic size give the identical coefficients of diffusion under different pressures. The dependence of the activation enthalpy of diffusion on pressure and on the characteristic size of nanoparticles is first obtained.     

Effect of hydrostatic pressure on self-diffusion in metal nanoparticles

The thermodynamics approach has been developed to describe the self-diffusion in nano-sized solids. It has been established that identical homologous temperatures of metal nanoparticles with their fixed characteristic size give the identical coefficients of diffusion under different pressures. The dependence of the activation enthalpy of diffusion on pressure and on the characteristic size of nanoparticles is first obtained.     

Ionic and molecular Self-Diffusion in Ion-Exchange materials for fuel energetics studied by pulsed field gradient NMR

Pulsed field gradient nuclear magnetic resonance technique was applied to investigate the self-diffusion mechanism of water, alcohol molecules and Li⁻ counterions in sulfocation exchangers with different structures of the polymeric matrix. It was shown that in the homogeneous perfluorinated sulfocation exchange membranes the ionic and water translation motions are controled by the hydrogen bond network forming in ionogenic channels at the high water content. At the low solvent content, the self-diffusion coefficients of methanol and ethanol are higher than the water self-diffusion coefficients. The influence of non-ion-exchange sorbed electrolyte on Li⁺ self-diffusion coefficients was observed in the heterogeneous sulfocation exchanger KU-23.     

Measurement of iron self-diffusion in hematite single crystals by secondary ion-mass spectrometry (SIMS) and comparison with cation self-diffusion in corundum-structure oxides

Iron bulk self-diffusion coefficients were measured in Fe₂O₃ single crystals using original methodology based on the utilization of ⁵⁷Fe stable isotope as iron tracer and depth profiling by secondary ion-mass spectrometry (SIMS). The iron self-diffusion coefficients were measured along and perpendicular to the c-axis, between 900 and 1100°C, in an oxygen atmosphere. Along the c-axis, the coefficients can be described by D _{∥ c} (cm²/s)?=?5.2?×?10⁶?exp[?510 (kJ/mol)/RT], and are close to reliable data, available in the literature, obtained by means of radioactive techniques. Perpendicular to the c-axis, D _⊥c (cm²/s)?= 83?exp[?430 (kJ/mol)/RT], and the coefficients are smaller than coefficients along the c-axis. The data are compared with previously results of cation bulk self-diffusion in Cr₂O₃ and Al₂O₃ single crystals.     

NMR波谱技术在两亲分子聚集体研究中的应用

通过近年来NMR技术在两亲分子聚集体研究中的应用实例,特别在弛豫时间、自扩散系数测定、谱线宽度、化学位移等方面取得的研究结果,对确定的两亲分子聚集性质、聚集体结构和聚集体性质的研究进行了较为详细的介绍.主要侧重点在于介绍1HNMR、13CNMR、19FNMR及2H四极分裂谱等技术在两亲分子聚集体结构及结构演变研究中的应用,特别在胶束、囊泡和微乳液结构确定上的应用.     

Self-diffusion measurements by a mobile single-sided NMR sensor with improved magnetic field gradient

A simple and fast method of measuring self-diffusion coefficients of protonated systems with a mobile single-sided NMR sensor is discussed. The NMR sensor uses a magnet geometry that generates a highly flat sensitive volume where a strong and highly uniform static magnetic field gradient is defined. Self-diffusion coefficients were measured by Hahn- and stimulated echoes detected in the presence of the uniform magnetic field gradient of the static field. To improve the sensitivity of these experiments, a Carr-Purcell-Meiboom-Gill pulse sequence was applied after the main diffusion-encoding period. By adding the echo train the experimental time was strongly shortened, allowing the measurement of complete diffusion curves in less than 1min. This method has been tested by measuring the self-diffusion coefficients D of various organic solvents and poly(dimethylsiloxane) samples with different molar masses. Diffusion coefficients were also measured for n-hexane absorbed at saturation in natural rubber with different cross-link densities. The results show a dependence on the concentration that is in good agreement with the theoretical prediction. Moreover, the stimulated-echo sequence was successfully used to measure the diffusion coefficient as a function of the evolution time in systems with restricted diffusion. This type of experiment proves the pore geometry and gives access to the surface-to-volume ratio. It was applied to measure the diffusion of water in sandstones and sheep Achilles tendon. Thanks to the strong static gradient G(0), all diffusion coefficients could be measured without having to account for relaxation during the pulse sequence.