Salting-out effect induced by temperature cycling on a water/nonionic surfactant/oil system

This paper presents original effects induced by temperature cycling on the transitional phase inversion of emulsions, stabilized by a nonionic polyethoxylated C18E6 surfactant model. The phase inversion follow-up is performed by electrical conductivity measurements, which involves focusing the study on the shape and location of the emulsion inversion region. In that way, new observations are brought out as a gradual evolution of the emulsion inversion along the cycling process. Two alternative approaches are considered for tackling these results: (i) first, a molecular approach regarding the particular organization and rearrangement of water clusters surrounding the surfactant polymer polar head, and (ii) second, a thermodynamic approach only considering the whole Gibbs free energy of the system. The volumic approaches are transposed, here, to the water/oil interface, and disclose that the phase inversion zone is included in a metastable region, able to stabilize for a given temperature, either metastable O/W emulsions or stable W/O ones. In that way, this study proposes novel and complementary insights into the phenomena governing the emulsion phase inversion.     

Effect of heating rate on thermo-induced aggregation of poly(ethylene oxide)-b-poly(N-isopropylacrylamide) in aqueous solutions

<正>The effects of heating rate on the aggregate behavior of poly(ethylene oxide)-b-poly(N-isopropylacrylamide) in aqueous solutions were investigated in detail by laser light scattering and TEM.By employing two separate heating protocols,step-by-step heating at5 K/step and one-step jump,to heat the sample from 15℃to the selected temperature, we found that the heating rate only showed significant effect on the aggregates above the cloud point.The aggregate formed by step-by-step heating exhibited a much larger size and a broader size distribution than those formed by one-step jump heating.Moreover,neither of the aggregates were ideal micellar structures as indicated by the size and the R_g/R_h values.On the contrary,at temperatures below the cloud point where the block copolymer formed core-shelled micelles,the heating rate showed negligible effect on the size and size distribution of the micelles.Since the system underwent a phase separation above the cloud point,the heating rate effect could be reasonably explained by the phase separation mechanisms:the nucleation-and-growth mechanism in the metastable region and the spinodal decomposition mechanism in the unstable region.     

Cloud point phenomena for POE-type nonionic surfactants in a model room temperature ionic liquid

The cloud point phenomenon has been investigated for the solutions of polyoxyethylene (POE)-type nonionic surfactants (C(12)E(5), C(12)E(6), C(12)E(7), C(10)E(6), and C(14)E(6)) in 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)), a typical room temperature ionic liquid (RTIL). The cloud point, T(c), increases with the elongation of the POE chain, while decreases with the increase in the hydrocarbon chain length. This demonstrates that the solvophilicity/solvophobicity of the surfactants in RTIL comes from POE chain/hydrocarbon chain. When compared with an aqueous system, the chain length dependence of T(c) is larger for the RTIL system regarding both POE and hydrocarbon chains; in particular, hydrocarbon chain length affects T(c) much more strongly in the RTIL system than in equivalent aqueous systems. In a similar fashion to the much-studied aqueous systems, the micellar growth is also observed in this RTIL solvent as the temperature approaches T(c). The cloud point curves have been analyzed using a Flory-Huggins-type model based on phase separation in polymer solutions.     

The water/n-octane/octyl-beta-D-glucoside/1-octanol system: phase diagrams and phase properties

The partial phase diagram of D2O/n-octyl-beta-D-alkyl-glucoside(C8G1)/n-octane has been determined at T=25 degrees C. The diagram contains a funnel-shaped micellar phase originating from the water corner of the phase diagram D2O/C8G1 with the stem forming a narrow three-phase region, in which the three phases in equilibrium are two microemulsions of similar composition and an excess oil phase. The microemulsions have been characterized with NMR self-diffusion measurements. At high surfactant concentration and no or low n-octane content, branched micelles exist. As the n-octane content is increased, discrete micelles are formed. Upon further addition of n-octane, the phase separation into two microemulsion phases is induced. Possible mechanisms causing the phase separation are discussed. The phase diagram of D2O/(C8G1)/1-octanol has been determined at 25 degrees C. Ten different phase regions were identified. The phases have been characterized with SAXS and deuterium heavy water NMR, and the swelling of the lamellar phase was investigated with SAXS.     

Phase separation during synthesis of polyetherimide/epoxy semi-IPNs

The phase separation behavior and the morphology of polyetherimide (PEI)-modified diglycidyl ether of bisphenol A (DGEBA) epoxy resin were studied using scanning electron microscopy and light scattering. Reaction kinetics, cloud point and onset of gelation were determined by differential scanning calorimeter, optical microscope and physica rheometer, respectively. The mixture of partially cured epoxy and PEI showed bimodal upper critical solution temperature (UCST) behavior. For PEI content smaller than 10 wt%, the blends exhibited a sea-island morphology formed via nucleation and a growth mechanism. Above 25 wt% PEI content, the phase separation proceeded via a spinodal decomposition mechanism and a nodular structure was formed. With PEI content between 15 and 20 wt%, dual phase morphology was observed. This morphology was formed via primary spinodal decomposition and secondary phase separation within the dispersed phases and the matrix phases formed by the primary phase separation. This morphology was presumed to be formed in the reaction-induced phase separation mechanism with the mixture showing bimodal UCST behavior. The curing temperature had an effect on the final morphology, and the modulus of PEI-modified epoxy was influenced by the phase separation.     

Phase transitions in solutions of polystyrene with poly(methyl methacrylate) and polybutadiene under deformation

By the cloud point and static sorption methods, phase diagrams are constructed and the concentration and temperature dependences of the Gibbs free energy of mixing and the interaction parameter are determined under static conditions and in a shear field for the poly(methyl methacrylate)-polystyrene-ethyl acetate, polystyrene-polybutadiene-toluene, polystyrene-polybutadiene, poly(methyl methacrylate)-polystyrene, poly(methyl methacrylate)-ethyl acetate, and polystyrene-ethyl acetate systems. Phase separation in the systems both under heating and cooling, as well as coexistence of three phases, is observed in the polystyrene-poly(methyl methacrylate)-ethyl acetate system. Deformation changes the phase separation temperature by 30–40 K.     

How many phases and phase transitions do exist in Gibbs adsorption layers at the air-water interface?

Four different phases and four different first-order phase transitions have been shown to exist in Gibbs adsorption layers of mixtures containing n-hexadecyl dihydrogen phosphate (n-HDP) and L-arginine (L-arg) at a molar ratio of 1:2. These conclusions have been made from surface pressure-time (pi-t) adsorption isotherms measured with a film balance and from monolayer morphology observed with a Brewster angle microscopy (BAM). The observed four phases are gas (G), liquid expanded (LE), liquid condensed (LC) and LC' phases. Three first-order phase transitions are G-LE, LE-LC and LC-LC'. However, the thermodynamically allowed G-LC phase transition in a 1.2 x 10(-4) M mixture at 2 degrees C, which is below the so-called triple point, is kinetically separated into the G-LE and LE-LC phase transitions. The most interesting observation is that the homogeneous LC phase shows a new first-order phase transition named as LC-LC' at 2 or 5 degrees C. The LE and LC phases represent circular and fractal shaped domains, respectively, whereas the LC' phase shows very bright, anisotropic and characteristic shaped domains.     

Temperature-responsive ionic liquid/water interfaces: relation between hydrophilicity of ions and dynamic phase change

Phase separation between ionic liquids (ILs) and molecular liquids is of interest physico-chemically, and also has industrial relevance. IL/water mixtures are of great interest in many fields. Unlike static phase separation between IL and water, dynamic shifts of IL/water mixtures between a homogeneous mixture and separate phases have a wide variety of applications. The miscibility of ILs with water generally increases upon heating, and a few ILs undergo a lower critical solution temperature (LCST)-type phase transition with water in which the separated biphases become miscible upon cooling. As the phase transition is controlled by changing the temperature by a few degrees, the LCST-type phase response of IL/water mixtures makes it possible to use ILs as solvents in various energy-saving processes. Since many hydrophilic ILs do not undergo phase separation with water, we aim to determine the necessary conditions under which hydrophobic ILs undergo the phase transition. Based on physico-chemical analysis of many hydrophobic ILs that undergo a phase separation after mixing with water, we find there is a particular range of "hydrophilicity" of these hydrophobic ILs within which the LCST-type phase transition is possible. Accordingly, a hydrophilicity index (HI) of ILs is proposed, in terms of the number of water molecules in the separated IL phase. The HI value proves to be a good indicator of the phase behaviour of IL/water mixtures, as well as their phase transition temperature. Potential application of the LCST-type phase change to the selective extraction of water-soluble proteins is also summarised.     

Sol-gel transition of polyacrylonitrile/propylene carbonate solution

The thermoreversible gelation of polyacrylonitrile (PAN)/propylene carbonate (PC) solution was investigated by calorimetric, thermomechanical, optical, and rheological measurements. Two endothermic signals are observed for PAN/PC gels in DSC thermograms, and the peak temperature of the higher melting endotherm coincides with the gel melting temperature determined from the TMA thermogram. SEM micrographs show that the overall structure is separated into two phases and is composed of sperical domains, which may be formed upon passing through the thermodynamically unstable or metastable state via the liquid-liquid phase separation. The gelation rate increases with the aging temperature. This is also discussed on the basis of the elasticity theory of the fishnet gel. © 1994 John Wiley & Sons, Inc.     

Effect of solute hydrophobicity on phase behaviour in solutions of thermoseparating polymers

 Two-phase systems consisting of a polymer rich phase and polymer depleted phase, where the polymer is either ethyl(hydroxy ethyl)cellulose (EHEC) or Ucon (a random copolymer of ethylene oxide and propylene oxide), have been studied. Both of these polymers can be separated from an aqueous solution by either temperature increase or addition of cosolutes. The polymers are thermoseparating and phase separate in water solutions at the cloud point temperature. Two types of EHEC have been studied: one with a cloud point at 60 °C and the other at 37 °C. The Ucon polymer used in this study has a cloud point at 50 °C. Ternary phase diagrams of polymer/water/cosolute systems have been investigated. When a strongly hydrophilic or hydrophobic cosolute is added to an EHEC- or Ucon–water solution, a phase separation occurs already at, or below, room temperature. As cosolutes, hydrophobic molecules like phenol, butyric and propionic acid, and hydrophilic molecules like glycine, ammonium acetate, sodium carboxylates (acetate to valerate), were studied. The polymer rich phase formed when mixing polymer, water and cosolute was strongly enriched or depleted with hydrophobic or hydrophilic cosolutes, respectively. The two phase region increased for propionic acid, butyric acid and phenol as a result of increased cosolute hydrophobicity. The opposite occurred in the series sodium acetate, sodium butyrate and sodium valerate. The effect of temperature on the phase behaviour has also been investigated. Model calculations based on Flory–Huggins theory of polymer solutions are presented, in form of a phase diagram, which semiquantitatively reproduce some experimental results. Received: 5 July 1996 Accepted: 4 November 1996     

Ionic liquid/water mixtures: from hostility to conciliation

Water was originally inimical to ionic liquids (ILs) especially in the analysis of their detailed properties. Various data on the properties of ILs indicate that there are two ways to design functions of ionic liquids. The first is to change the structure of component ions, to provide "task-specific ILs". The second is to mix ILs with other components, such as other ILs, organic solvents or water. Mixing makes it easy to control the properties of the solution. In this strategy, water is now a very important partner. Below, we summarise our recent results on the properties of IL/water mixtures. Stable phase separation is an effective method in some separation processes. Conversely, a dynamic phase change between a homogeneous mixture and separation of phases is important in many fields. Analysis of the relation between phase behaviour and the hydration state of the component ions indicates that the pattern of phase separation is governed by the hydrophilicity of the ions. Sufficiently hydrophilic ions yielded ILs that are miscible with water, and hydrophobic ions gave stable phase separation with water. ILs composed of hydrophobic but hydrated ions undergo a dynamic phase change between a homogeneous mixture and separate phases according to temperature. ILs having more than seven water molecules per ion pair undergo this phase transition. These dynamic phase changes are considered, with some examples, and application is made to the separation of water-soluble proteins.     

聚甲基丙烯酸甲酯/聚(苯乙烯-马来酸酐)共混体系相分离的流变学行为

采用动态流变学方法, 对聚甲基丙烯酸甲酯(PMMA)/聚(苯乙烯-马来酸酐)(PSMA)共混体系的相行为进行了研究. 相分离温度由动态储能模量对温度曲线斜率的转折点确定. 结果表明， 表观相分离温度有很大的频率依赖性, 因此， 动态流变学方法应用于相分离温度测定时要外推到频率为零.     

Phase behaviour of poly(vinyl methyl ether)-cross-polystyrene semi-interpenetrating networks

Semi-interpenetrating polymer networks of varying composition are prepared by crosslinking polystyrene containing a small number of maleic anhydride groups (4.8 mol% of MA units) with hexamethylene-diamine (HMDA) in the presence of linear poly(vinyl methyl ether) (PVME). Lightly crosslinked samples are homogeneous at room temperature and show a phase behaviour similar to uncrosslinked blends, i.e. lower critical solution temperature (LCST) behaviour. The influence of crosslinking on the phase behaviour has been studied by small angle light scattering (SALS) and turbidity measurements. The cloud point strongly depends on the heating rate. The presence of the network reduces the stable single phase region in agreement to theory. In systems showing spinodal decomposition, it is expected that some concentration fluctuations will grow more rapidly than others resulting in a separated phase system which shows high degree of connectivity with characteristic dimensions. Using temperature jump experiments, SALS can be used to estimate parameters of the phase separation kinetics and the characteristic dimensions of the phases. In temperature jump experiments into the spinodal region a maximum in the scattered light intensity is observed with time at a certain scattering vector. However, the semi-IPN's develop no scattering maximum. This is explained by a damping of the thermodynamical dominant wavelength in spinodal decomposition in the network.     

Self-assembly in mixed dialkyl chain cationic-nonionic surfactant mixtures: dihexadecyldimethyl ammonium bromide-monododecyl hexaethylene glycol (monododecyl dodecaethylene glycol) mixtures

The self-assembly of dialkyl chain cationic surfactant dihexadecyldimethyl ammonium bromide, DHDAB, and nonionic surfactants monododecyl hexaethylene glycol, C(12)E(6), and monododecyl dodecaethylene glycol, C(12)E(12), mixtures has been studied using predominantly small-angle neutron scattering, SANS. The scattering data have been used to produce a detailed phase diagram for the two surfactant mixtures and to quantify the microstructure in the different regions of the phase diagram. For cationic-surfactant-rich compositions, the microstructure is in the form of bilamellar, blv, or multilamellar, mlv, vesicles at low surfactant concentrations and is in an L(beta) lamellar phase at higher surfactant concentrations. For nonionic-rich compositions, the microstructure is predominantly in the form of relatively small globular mixed surfactant micelles, L(1). At intermediate compositions, there is an extensive mixed (blv/mlv) L(beta)/L(1) region. Although broadly similar, in detail there are significant differences in the phase behavior of DHDAB/C(12)E(6) and DHDAB/C(12)E(12) as a result of the increasing curvature associated with C(12)E(12) aggregates compared to that of C 12E 6 aggregates. For the DHDAB/C(12)E(12) mixture, the mixed (blv/mlv) L(beta)/L(1) phase region is more extensive. Furthermore, C(12)E(12) has a greater impact upon the rigidity of the bilayer in the blv, mlv, and L(beta) regions than is the case for C(12)E(6). The general features of the phase behavior are also reminiscent of that observed in phospholipid/surfactant mixtures and other related systems.     

Thermotropic and barotropic phase transitions of dialkyldimethylammonium bromide bilayer membranes: effect of chain length

The bilayer phase transitions of dialkyldimethylammonium bromides (2C(n)Br; n = 12, 14, 16) were observed by differential scanning calorimetry and high-pressure light-transmittance measurements. Under atmospheric pressure, the 2C(12)Br bilayer membrane underwent the stable transition from the lamellar crystal (L(c)) phase to the liquid crystalline (L(α)) phase. The 2C(14)Br bilayer underwent the main transition from the metastable lamellar gel (L(β)) phase to the metastable L(α) phase in addition to the stable L(c)/L(α) transition. For the 2C(16)Br bilayer, moreover, three kinds of phase transitions were observed: the metastable main transition, the metastable transition from the metastable lamellar crystal (L(c(2))) phase to the metastable L(α) phase, and the stable lamellar crystal (L(c(1)))/L(α) transition. The temperatures of all the phase transitions elevated almost linearly with increasing pressure. The temperature (T)-pressure (p) phase diagrams of the 2C(12)Br and 2C(14)Br bilayers were simple, but that of the 2C(16)Br bilayer was complex; that is, the T-p curves for the metastable main transition and the L(c(2))/L(α) transition intersect at ca. 25 MPa, which means the inversion of the relative phase stability between the metastable phases of L(β) and L(c(2)) above and below the pressure. Moreover, the T-p curve of the L(c(2))/L(α) transition was separated into two curves under high pressure, and as a result, the pressure-induced L(c(2P)) phase appeared in between. Thermodynamic quantities for phase transitions of the 2C(n)Br bilayers increased with an increase in alkyl-chain length. The chain-length dependence of the phase-transition temperature for all kinds of transitions observed suggests that the stable L(c(1))/L(α) transition incorporates the metastable L(c(2))/L(α) transition in the bilayers of 2C(n)Br with shorter alkyl chains, and the main-transition of the 2C(12)Br bilayer would occur at a temperature below 0 °C.     

Benzene under high pressure: a story of molecular crystals transforming to saturated networks, with a possible intermediate metallic phase

In a theoretical study, benzene is compressed up to 300 GPa. The transformations found between molecular phases generally match the experimental findings in the moderate pressure regime (<20 GPa): phase I (Pbca) is found to be stable up to 4 GPa, while phase II (P4(3)2(1)2) is preferred in a narrow pressure range of 4-7 GPa. Phase III (P2(1)/c) is at lowest enthalpy at higher pressures. Above 50 GPa, phase V (P2(1) at 0 GPa; P2(1)/c at high pressure) comes into play, slightly more stable than phase III in the range of 50-80 GP, but unstable to rearrangement to a saturated, four-coordinate (at C), one-dimensional polymer. Actually, throughout the entire pressure range, crystals of graphane possess lower enthalpy than molecular benzene structures; a simple thermochemical argument is given for why this is so. In several of the benzene phases there nevertheless are substantial barriers to rearranging the molecules to a saturated polymer, especially at low temperatures. Even at room temperature these barriers should allow one to study the effect of pressure on the metastable molecular phases. Molecular phase III (P2(1)/c) is one such; it remains metastable to higher pressures up to ～200 GPa, at which point it too rearranges spontaneously to a saturated, tetracoordinate CH polymer. At 300 K the isomerization transition occurs at a lower pressure. Nevertheless, there may be a narrow region of pressure, between P = 180 and 200 GPa, where one could find a metallic, molecular benzene state. We explore several lower dimensional models for such a metallic benzene. We also probe the possible first steps in a localized, nucleated benzene polymerization by studying the dimerization of benzene molecules. Several new (C(6)H(6))(2) dimers are predicted.     

Nonionic surfactant and temperature effects on the viscosity of hydrophobically modified hydroxyethyl cellulose solutions

Nonionic surfactant and temperature effects on the viscosity of hydrophobically modified hydroxyethyl cellulose (HMHEC) solutions are investigated experimentally. Weak shear thickening at intermediate shear rates takes place for HMHEC at moderate concentrations and becomes more significant at lower temperatures. While this amphiphilic polymer in surfactant-free solution does not turn turbid by heating to 95 degrees C, its mixture with nonionic surfactant shows a lower cloud point temperature than does a pure surfactant solution. For some mixture cases, phase separation takes place at temperatures as low as 2 degrees C. The drop of cloud point temperature is attributed to an additional attractive interaction between mixed micelles via chain bridging. With increasing temperature, the viscosity of an HMHEC-surfactant mixture in aqueous solution first decreases but then rises considerably until around the cloud point. The observed viscosity increase can be explained by the interchain association because of micellar aggregation.     

Driving forces for self-organized coadsorption: C6H6/2O and C6H6/2CO on Ni[111

The self-organized (2log3 x 2log3) coadsorbed phases of C(6)H(6) with O and with CO are investigated within first-principles density functional theory. The main driving force for formation of the C(6)H(6)/2O phase is found to be the reduction of O adatom repulsive interactions, while for the C(6)H(6)/2CO phase it is the interspecies attractive interactions and benzene-benzene repulsive interactions which are most important.     

温控配体与液／液两相催化

 以作者近年的研究工作为主，对液／液两相催化研究领域取得的进展做一综述．着重介绍了以温控配体为基础的新型液／液两相催化过程温控相转移催化（thermoregulatedphasetransfercatalysis，TRPTC）和温控相分离催化（thermoregulatedphase－separablecatalysis，TPSC）的基本原理及其在高碳烯烃氢甲酰化、芳香硝基化合物的CO选择性还原及烯烃加氢等反应中的应用．基于温控配体在水中的“浊点”特性而提出的温控相转移催化概念，为从根本上解决水／有机两相催化 的适用范围受底物水溶性限制的问题提供了一条新途径．而利用温控配体在某些有机溶剂中存在临界溶解温度（CST）的特性而实现的温控相分离催化，则使在高于临界溶解温度的反应温度时为均相的反应体系，在低温（＜CST）时则分成两相，催化剂自成一相，形成一种具有“均相反应、两相分离”特色的液／液两相催化新体系．