A 2H NMR RELAXATION STUDY OF A MODEL MICROEMULSION

The microemulsion phases of the Winsor system consisting of 47 wt% brine, 2 wt% sodium dodecylsulphate, 4 wt% butanol and 47 wt% toluene were investigated by means of ²H NMR relaxation on the surfactant which was specifically deuterated in the α-position. The measurements were obtained at 20°C for salinities varying from 3 to 10 g NaCl / 100 ml H₂O. From a simple relaxation model the transverse relaxation rates were transformed into sizes of (spherical) droplets, which were compared with the droplet sizes obtained from the sample compositions in the Winsor I and II regions. For the Winsor III region, the transverse relaxation rates could be rationalised in terms of a structural model based on a bicontinuous cubic liquid crystalline phase. Moreover, by invoking previously obtained data, we show that the dependence on salinity of the water, oil and surfactant self-diffusion coefficients can also be explained within the same framework.     

Study of Winsor I to Winsor II transitions in a lattice model

Experiments show that with increasing temperature, microemulsion systems undergo Winsor transitions. The transitions occur from Winsor I (oil droplets in water media) to Winsor II (water droplets in oil media) via Winsor III (bicontinuous phase) with an increase in the temperature. In this paper, it has been shown, for the first time, how one can study the qualitative effects of temperature, head, tail, and oil chain lengths, on these transitions. Simple cubic lattice with excluded volume and periodic boundary conditions is used to mimic the box of the simulation as a bulk of solution. The simulations have been done using the standard traditional Metropolis algorithm in the canonical ensemble (N, V, T). Configurational bias Monte Carlo and reptation moves are used with an equal probability to relax the systems. A very simple interaction model, i.e., the repulsions of water (or heads of surfactants) with oil (or tails of surfactants), is used due to the main characteristic of oil-water mixtures or amphiphilic molecule that is the hydrophobicity. The interfacial tension between oil and water (gammaow) is related to the averaged total energy of the lattice. The model shows that the Winsor III has a minimum interfacial tension (gammaow) similar to experimental results. Changing the phase structure from Winsor III to Winsor I (or Winsor II), increases the interfacial tension which is in agreement with experiments. To relate interfacial tension with the interaction parameter, the simple theory of Bragg-Williams has been used. All of the results such as the effects of oil chain length, head and tail beads number are all similar to the experimental results. Using the Davies method for calculating hydrophilic-lypophilic Balance (HLB), similar to the experimental results, Winsor III phase is formed at HLB value nearly to 10.     

Etude de phases quaternaires Winsor IV. Diagrammes de phases et propriétés electriques

A comparative study of phase diagram features and electrical properties of Winsor IV phases (so-called microemulsions) led to define two types of quaternary systems involving water, a hydrocarbon, and an ionic surfactant/alcohol combination defined byk, the surfactant/alcohol mass ratio. Systems of the first type exhibit a Winsor IV domain consisting of two disjointed areas corresponding to water-in-oil (w/o) and oil-in-water (o/w) monophasic fluid transparent isotropic media. The w/o and o/w areas are separated by a composition zone over which exist viscous turbid long-range organized structures related to the o/w w/o phase inversion mechanism. In that case, over the w/o area, the low frequency electrical conductivity and permittivity undergo non-monotonous changes as the composition varies. From conductivity maxima and minima, it is possible to define in the general case two lines ₁ and ₂ separating three adjacent sub-areas to which can be assigned compositions representing pre-micellar entities, inverted swollen spherical micelles and micelles clusters. For systems of the second type, the w/o and o/w sub-areas merge so as to form a unique monophasic area, which implies that the w/o o/w phase inversion occurs through a progressive diffuse mechanism. In that case the conductivity exhibits much higher values than in the preceding situation, and its variations with composition allow to define two linesC _d andC _m partitioning the Winsor IV domain into three adjacent areas. AboveC _d , that is for low and medium water contents, the conductivity variations with water content follow equations derived from the Percolation and Effective Medium theories, which indicates that the w/o swollen spherical micelles are submitted to attractive interactions. Below C_m, i. e. in the water rich region, the conductivity decrease with water content results from the progressive dilution of the external aqueous phase of the o/w Winsor IV media. BetweenC _d andC _m , the Winsor IV media exhibit an anomalous conductive behaviour which suggests that they are neither w/o nor o/w systems. This region can be considered as the diffuse phase inversion zone over which the systems are in a hybrid state that could be depicted tentatively as resulting from the formation of equilibrium bicontinuous structures.

     

Middle-phase microemulsions of green surfactant alkyl polyglucosides

Microemulsions are important organized molecular assembles in surfactant solutions and are used in various fields such as tertiary oil recovery, pharmaceutics, cosmetics, nanoparticle synthe-sis and chemical engineering. The more commonly used nonionic surfactants to produce micro- emulsions are the ethylene oxide-based compounds (CiEj). In recent years alkyl polyglucosides have been received considerable attention in producing microemulsions[17]. Alkyl polyglucosides (APG), which are widely…     

THE RELATIONSHIP BETWEEN THE MOLAR PARTITION COEFFICIENT AND THE ULTRALOW INTERFACIAL TENSION MINIMUM IN A PETROLEUM SULFONATE/ HYDROCARBON/BRINE SYSTEM

The partitioning of a sodium petroleum sulfonate between heptane and brine yields surfactants with different molar absorptivity and λ_max values in the two phases, except near the point of minimum interfacial tension, e of the surfactant in the heptane phase increases sharply above the point of minimum interfacial tension between the two phases. The molar partition coefficient, M_H/M_W, for the surfactant between the heptane and brine phases is unity at surfactant concentrations in the brine phase below the point of minimum interfacial tension and drops sharply at concentrations above it. The critical micelle concentration of the surfactant in the aqueous phase equilibrated with the heptane phase is considerably below the concentration for minimum interfacial tension     

Study of the physicochemical characteristics of dispersions of n-alkanes C23H48 and C28H58 in water: zeta potential and temperatures of phase transitions

The effect of pH on the zeta potential of dispersions of individual n-alkanes C₂₃H₄₈ and C₂₈H₅₈ with particle sizes of the order of 100 nm, which were prepared by ultrasonic dispersion without the addition of surfactants, was studied. It is shown that at pH ranged from 4 to 12, the investigated n-alkanes form stable dispersions in water. They are characterized by a high zeta potential varying from ?30 to ?50 mV. The phase transition temperatures (melting point, crystallization temperature, formation of rotator phases) were determined for the dispersions using an optical method.

     

Influence of the chain length of K-soaps on the phase diagram and structural parameters of nonaqueous liquid crystals and the gel phase in K-soap/glycerol binary systems

 Analogously to the aqueous K-soap/water systems already examined, the five glycerol · (Gl)-containing systems KC _n /Gl (n = 12, 14, 16, 18, 22) also built up hexagonal (H_α), lamellar (L_α), isotropic micellar (S), gel-like (G) and crystalline phases (C). These phases were identified by texture observations with a polarizing microscope, by differential scanning calorimetry measurements and by X-ray diffraction investigations. The appertaining phase regions were plotted in the binary phase diagram. Binary Gl-containing K-soap systems have the following properties. The H_α phase is built up at low soap concentration. The L_α phase is formed at high soap concentrations. The temperature of the phase transition H_α ⇆ S runs through a maximum. Increasing the chain lengths of the soaps shifts the formation of the H_α phase to lower soap concentration. A strong correlation between the chain length of K-soaps and the d values of L_α, H_α, G and C phases is found. Based on the comparison of the X-ray diffractograms of the G phase a structural model is proposed. The G phase consists of two groups of domains with two different dimensions. Received: 9 August 1999/Accepted in revised form: 20 September 1999     

A thermodynamic study on the complexation between riboflavin and a diaminotriazine derivative mediated by triple hydrogen bonds at water/oil interfaces

The changes in Gibbs free energy (ΔG _int), enthalpy (ΔH _int) and entropy (TΔS _int) upon complexation between riboflavin (RF) and N,N-dioctadecyl-[1,3,5]triazine-2,4,6-triamine (DTT), mediated by triple hydrogen bonds at water/carbon tetrachloride, trichloroethylene and chloroform interfaces, were determined via temperature-controlled interfacial tension measurements. It was shown that hydrogen bonding interactions between RF and DTT were best characterized by large and negative ΔH _int values, unlike those predicted from either the polarity in each phase or the arithmetic average of the polarities in the two phases. Furthermore, the ΔH _int values became more positive as the dielectric constant of the oil phase was increased. These results strongly indicate that ΔH _int is governed by the dielectric properties of the oil phase. Adsorption of RF, DTT and the RF-DTT complex at the water/oil interface gave rise to restrictions on the translational and rotational motions of these species, as demonstrated by the ΔS _int values observed, which is another characteristic of interfacial complexation. The thermodynamic parameters evaluated in the present study revealed the characteristic complexation behavior that occurs at a water/oil interface, as mediated by hydrogen bonding.     

Thermodynamics of Zr<Subscript>52.5</Subscript>Cu<Subscript>17.9</Subscript>Ni<Subscript>14.6</Subscript>Al<Subscript>10</Subscript>Ti<Subscript>5</Subscript> bulk metallic glass forming alloy

Recently, multicomponent glass forming alloys have been found which exhibit extraordinary glass forming ability and cooling rates of less than 100 K/s are sufficient to suppress nucleation of crystalline phases and consequently bulk metallic glass (BMG) is formed. The undercooled melts of BMG systems have high thermal stability in the undercooled region. Therefore, it is interesting to study the thermodynamics of such materials. This article investigates the thermodynamic behavior of a BMG system namely Zr_52.5Cu_17.9Ni_14.6Al₁₀Ti₅ by estimating the Gibbs free energy difference ΔG, entropy difference ΔS, enthalpy difference ΔH between the undercooled liquid and corresponding equilibrium crystalline solid phase, in the entire temperature range from T _m to T _K. Glass forming ability (GFA) of this system has been investigated through various GFA parameters indicating the degree of ease of glass formation.     

Tailoring Spontaneous Pillar Structure Using Phase-Separating Organosiloxane Sol-Gel Systems in Micro-Fabricated Grooves

A sharp transition to pillar structure has been observed in simple sol-gel systems accompanying phase separation inside rectangular-sectioned open grooves which were fabricated on a silica glass chip. The structural variation was investigated using two contrastive systems; one with a rapid sol-gel reaction and the other with a sluggish reaction. In the slower system, transition from web-like bicontinuous structure to pillar structure, we call it as “web-to-pillar transition”, occurred when the bulk characteristic length Λ_m exceeded the width of the groove D. On the other hand, the transition did not occur in the same condition in the faster system; it occurred when Λ_m became much longer than D. A consistent formation mechanism model was also proposed using a relation between interfacial curvatures and pressure.     

High‐ and low‐temperature phases in isostructural 4‐chloro‐3‐nitroaniline and 4‐iodo‐3‐nitroaniline

The structures of 4‐chloro‐3‐nitroaniline, C₆H₅ClN₂O₂, (I), and 4‐iodo‐3‐nitroaniline, C₆H₅IN₂O₂, (II), are isomorphs and both undergo continuous (second order) phase transitions at 237 and 200 K, respectively. The structures, as well as their phase transitions, have been studied by single‐crystal X‐ray diffraction, Raman spectroscopy and difference scanning calorimetry experiments. Both high‐temperature phases (293 K) show disorder of the nitro substituents, which are inclined towards the benzene‐ring planes at two different orientations. In the low‐temperature phases (120 K), both inclination angles are well maintained, while the disorder is removed. Concomitantly, the b axis doubles with respect to the room‐temperature cell. Each of the low‐temperature phases of (I) and (II) contains two pairs of independent molecules, where the molecules in each pair are related by noncrystallographic inversion centres. The molecules within each pair have the same absolute value of the inclination angle. The Flack parameter of the low‐temperature phases is very close to 0.5, indicating inversion twinning. This can be envisaged as stacking faults in the low‐temperature phases. It seems that competition between the primary amine–nitro N—H...O hydrogen bonds which form three‐centred hydrogen bonds is the reason for the disorder of the nitro groups, as well as for the phase transition in both (I) and (II). The backbones of the structures are formed by N—H...N hydrogen bonding of moderate strength which results in the graph‐set motif C(3). This graph‐set motif forms a zigzag chain parallel to the monoclinic b axis and is maintained in both the high‐ and the low‐temperature structures. The primary amine groups are pyramidal, with similar geometric values in all four determinations. The high‐temperature phase of (II) has been described previously [Garden et al. (2004). Acta Cryst. C 60 , o328–o330].     

Phase separation in semicrystalline blends of poly(phenylene sulfide) and poly(ethylene terephthalate). II. Effect of poly(phenylene sulfide) homopolymer solubilization of PPS‐graft‐PET copolymer on morphology and crystallization behavior

The morphology and crystallization behavior of poly(phenylene sulfide) (PPS) and poly(ethylene terephthalate) (PET) blends compatibilized with graft copolymers were investigated. PPS‐blend‐PET compositions were prepared in which the viscosity of the PPS phase was varied to assess the morphological implications. The dispersed‐phase particle size was influenced by the combined effects of the ratio of dispersed‐phase viscosity to continuous‐phase viscosity and reduced interfacial tension due to the addition of PPS‐graft‐PET copolymers to the blends. In the absence of graft copolymer, the finest dispersion of PET in a continuous phase of PPS was achieved when the viscosity ratio between blend components was nearly equal. As expected, PET particle sizes increased as the viscosity ratio diverged from unity. When graft copolymers were added to the blends, fine dispersions of PET were achieved despite large differences in the viscosities of PPS and PET homopolymers. The interfacial activity of the PPS‐graft‐PET copolymer appeared to be related to the molecular weight ratio of the PPS homopolymer to the PPS segment of the graft copolymer (M_H/M_A). With increasing solubilization of the PPS graft copolymer segment by the PPS homopolymer, the particle size of the PET dispersed phase decreased. In crystallization studies, the presence of the PPS phase increased the crystallization temperature of PET. The magnitude of the increase in the PET crystallization temperature coincided with the viscosity ratio and extent of the PPS homopolymer solubilization in the graft copolymer. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 599–610, 2000     

Phase behavior and interfacial properties of symmetric polymeric ternary blends A/B/AB

In this paper, the phase behavior and interfacial properties of symmetric ternary polymeric blends A/B/AB are studied by dissipative particle dynamics (DPD) simulations. By using the structure factor and nematic order parameter, we carefully characterized the diversified phases and phase transitions, and established the phase diagram of such symmetric ternary blends. It can be generally divided into four regions: disordered phase (DIS) region at high temperature, ordered lamellar phase (LAM) region, bicontinuous microemulsion (BµE) channel and phase-separated phase (2P) region at low temperature with the increase of the total volume fractions of homopolymers Φ _H, which shows good accordance with that in previous experimental and theoretical reports. Furthermore, we calculated the elastic constants of 2P and LAM phase, and discussed the transition mechanisms from 2P and LAM to BμE phase, respectively. The results show a direct relevance between the phase transitions and the change of interfacial properties. Finally, we also demonstrate that the BμE channel becomes narrower in lower temperature caused by the temperature dependence of interfacial properties of ternary blends.     

Size‐ and Interface‐Modulated Metal–Insulator Transition in Solution‐Synthesized Nanoscale VO2‐TiO2‐VO2 Heterostructures

The M1 form of vanadium dioxide, which exhibits a reversible insulator–metal transition above room temperature, has been incorporated into nanoscale heterostructures through solution‐phase epitaxial growth on the tips of rutile TiO₂ nanorods. Four distinct classes of VO₂‐TiO₂‐VO₂ nanorod heterostructures are accessible by modulating the growth conditions. Each type of VO₂‐TiO₂‐VO₂ nanostructure has a different insulator–metal transition temperature that depends on the VO₂ domain sizes and the TiO₂‐VO₂ interfacial strain characteristics.     

Monoclinic‐to‐orthorhombic phase transition of the hexamethylenetetramine–2‐methylbenzoic acid (1/2) cocrystal with temperature‐dependent dynamic molecular disorder

As a function of temperature, the hexamethylenetetramine–2‐methylbenzoic acid (1/2) cocrystal, C₆H₁₂N₄·2C₈H₈O₂, undergoes a reversible structural phase transition. The orthorhombic high‐temperature phase in the space group Pccn has been studied in the temperature range between 165 and 300 K. At 164 K, a t₂ phase transition to the monoclinic subgroup P2₁/c space group occurs; the resulting twinned low‐temperature phase was investigated in the temperature range between 164 and 100 K. The domains in the pseudomerohedral twin are related by a twofold rotation corresponding to the matrix (100/00/00). Systematic absence violations represent a sensitive criterium for the decision about the correct space‐group assignment at each temperature. The fractional volume contributions of the minor twin domain in the low‐temperature phase increases in the order 0.259 (2) → 0.318 (2) → 0.336 (2) → 0.341 (3) as the temperature increases in the order 150 → 160 → 163 → 164 K. The transformation occurs between the nonpolar point group mmm and the nonpolar point group 2/m, and corresponds to a ferroelastic transition or to a t₂ structural phase transition. The asymmetric unit of the low‐temperature phase consists of two hexamethylenetetramine molecules and four molecules of 2‐methylbenzoic acid; it is smaller by a factor of 2 in the high‐temperature phase and contains two half molecules of hexamethylenetetramine, which sit across twofold axes, and two molecules of the organic acid. In both phases, the hexamethylenetetramine residue and two benzoic acid molecules form a three‐molecule aggregate; the low‐temperature phase contains two of these aggregates in general positions, whereas they are situated on a crystallographic twofold axis in the high‐temperature phase. In both phases, one of these three‐molecule aggregates is disordered. For this disordered unit, the ratio between the major and minor conformer increases upon cooling from 0.567 (7):0.433 (7) at 170 K via 0.674 (6):0.326 (6) and 0.808 (5):0.192 (5) at 160 K to 0.803 (6):0.197 (6) and 0.900 (4):0.100 (4) at 150 K, indicating temperature‐dependent dynamic molecular disorder. Even upon further cooling to 100 K, the disorder is retained in principle, albeit with very low site occupancies for the minor conformer.     

Phase Diagrams and Solubilization of Chlorocarbons in Chlorocarbon/Water/Anionic Surfactant/Alcohol Microemulsion Systems

The solubilization abilities of various chlorocarbons were investigated in a middle phase microemulsion system anionic surfactant sodium dodecyl sulfate (SDS) or sodium dodecyl sulfonate (AS)/n-butanol/chlorocarbon/brine with a ε-β fishlike phase diagram. The composition of the balanced interfacial layer of the microemulsion and some other parameters are calculated. The result shows that surfactant little dissolves in water and chlorocarbon phases, while alcohol mainly dissolves in water and oil phases besides in the interfacial layer. The order of the solubilization ability is dichloromethane (CH₂Cl₂) ～ carbon tetrachloride (CCl₄) > tetrachloroethylene (PCE) > o-dichloro-benzene. The solubility of the alcohol decreases with the increase in NaCl concentrations, which should be compensated by the increase in the amount of alcohol as cosolvent (Cs), so as to maintain the balanced interfacial layer. Salinity has little effect on the partition of surfactant between phases.     

Two phases of bis­(tetraethyl­ammonium) di‐μ‐chloro‐bis­[di­chloro­palladium(II)]

A phase transition was found to occur at ∼153 K in the title compound, (C₈H₂₀N)₂[PdCl₆]. The structures of the two phases are reported at 292 and 130 K. The low‐temperature phase is twinned. The phase transition is accompanied by a minor displacement of the ions. There are C—H⋯Cl interactions as short as ∼2.80 Å, indicating the existence of hydrogen bonds, and this was confirmed by vibrational spectroscopy. The [Pd₂Cl₆]²⁻ anion occupies sites of mmm and 2/m symmetry in the room‐temperature and low‐temperature phases, respectively.     

Reversible high‐temperature phase transition of a manganese(II) formate framework with imidazolium cations

A new metal–formate framework, poly[1H‐imidazol‐3‐ium [tri‐μ₂‐formato‐manganese(II)]], {(C₃H₅N₂)[Mn(HCOO)₃]}_n, was synthesized and its structural phase transition was studied by thermal analysis and variable‐temperature X‐ray diffraction analysis. The transition temperature is around 435 K. The high‐temperature phase is tetragonal and the low‐temperature phase is monoclinic, with a β angle close to 90°. The relationship of the unit cells between the two phases can be described as: a_HT = 0.5a_LT + 0.5b_LT; b_HT = −0.5a_LT + 0.5b_LT; c_HT = 0.5c_LT. In the high‐temperature phase, both the framework and the guest 1H‐imidazol‐3‐ium (HIm) cations are disordered; the HIm cations are located about 2mm sites and were modelled as fourfold disordered. The Mn and a formate C atom are located on fourfold rotary inversion axes, while another formate C atom is on a mirror plane. The low‐temperature structure is ordered and consists of two crystallographically independent HIm cations and two crystallographically independent Mn²⁺ ions. The phase transition is attributable to the order–disorder transition of the HIm cations.     

Relation between the adhesion strength and interfacial width for symmetric polystyrene bilayers

Polystyrene (PS) bilayers were prepared and were adhered at a temperature between the surface and bulk glass-transition temperatures for a given time. Then, the interfacial adhesion strength (G_L) was examined with a conventional lap-shear measurement. G_L first increased with increasing adhesion time and then reached a constant value. This result implied that the segments moved across the interface, to a certain depth, even at a temperature below the bulk glass-transition temperature. To confirm this, the interfacial evolution for the PS/deuterated PS bilayers was examined with dynamic secondary-ion mass spectrometry. The G_L value was linearly proportional to the thickness of the interfacial adhesion layer. Finally, we propose a strategy for regulating the adhesion strength based on the chain-end chemistry. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3598–3604, 2006     

Theory of a helicoidal cholesteric phase induced by an external field

We present a mean field theory to describe a helicoidal cholesteric phase for mixtures of a chiral nematic liquid crystal (LC) and a polymer chain as well as for pure chiral nematic LC molecules in the presence of a longitudinal external field parallel to the pitch axis of a cholesteric (Ch) phase. The free energy of the helicoidal Ch phase (Ch_H) is derived as a function of a usual orientational order parameter and an order parameter of the Ch_H phase. On increasing the strength of the external field, we find that the Ch phase changes to the nematic (N) phase through the Ch_H phase. Depending on the temperature and the strength of the external field, we find the second-order N–Ch_H and Ch_H–Ch phase transitions and the first-order paranematic (pN)–N, pN–Ch_H and pN–Ch phase transitions. We also predict phase diagrams in mixtures of a flexible polymer and a Ch LC molecule under the external field.