Making polyurethane foams from microemulsions

A remarkable correlation exists between the degree of expansion of polyurethane foams and the structure of the reacting premixes. Polyurethane foams obtained from reacting premixes containing microemulsions are highly expanded. The expansion rate is proportional to the volume fraction of microemulsion in the premix. The stability of premixes with and without microemulsion is completely different suggesting distinct creaming mechanisms. We apply this idea to synthesize polyurethane foams from microemulsions successfully. This approach can be used to rationalize the design of polyurethane formulations leading to highly expanded foams.     

苯乙烯/丙烯酸丁酯微乳液共聚物链段分布的研究

以苯乙烯/丙烯酸丁酯(St/BA)为共聚单体,进行了微乳液聚合反应,测定了共聚物组成和共聚单体的竞聚率。由竞聚率计算了共聚物分子的链段分布,分析了共聚物分子的微观结构。     

微乳液法制备纳米材料的研究进展

微乳液法制备纳米材料可以控制纳米粒子的大小和形状。本文综述了影响纳米粒子的主要因素和微乳液法制备纳米材料的最新研究进展。     

Formation and Phase Behavior of Winsor Type III <Emphasis Type="Italic">Jatropha curcas</Emphasis>-Based Microemulsion Systems

The formation and phase behavior of Jatropha curcas-based microemulsion systems, which could potentially be used in enhanced oil recovery applications, has been investigated. Winsor type III microemulsions were obtained by adding n-octane to Winsor type I microemulsion systems prepared using various concentrations of alkyl polyglucoside (APG). To optimize the formulation of type III microemulsion systems, five different types of co-surfactants, i.e. normal butyl alcohol (NBA), isobutyl alcohol, isopropyl alcohol, fatty acid alcohol C8 (FAC8) and fatty acid alcohol C8/C10 (FAC8/C10) were used. The microemulsion phase behavior was determined along with particle size distributions by dynamic light scattering measurements. Results show that the optimum Winston type III system can be achieved by mixing 3 wt% of NBA, 1 wt% APG and 3 wt% NaCl. At the optimum formulation, the IFT reached a minimum value (0.016 mN/m) and formed very small emulsion droplets with a narrow particle size distribution.     

Partition of <Emphasis Type="Italic">n</Emphasis>-Butanol Among Phases and Solubilization Ability of Winsor type III Microemulsions

The partition of n-butanol in Winsor type III (W-III) microemulsions was investigated in this work. Three kinds of anionic surfactants (sodium dodecyl sulfate (SDS), sodium dodecyl sulfonate (DSS), and sodium dodecyl benzene sulfonate (SDBS)) and two kinds of anionic/cationic surfactant mixtures (SDS/octadecyl trimethyl ammonium chloride (OTAC) mixtures and DSS/OTAC mixtures) were studied. Internal standard gas chromatography was employed in n-butanol content analysis. The results showed that no water exists in the excess oil (EO) phase and no oil exists in the excess water (EW) phase. For the W-III microemulsions obtained by salinity scanning, relatively constant n-butanol content in the EO (11–12 v%) and EW (1–4 v%) was found under different salinities. Accurate measurement of n-butanol content in each phase is important for those systems having low solubilization ability. For the W-III microemulsions prepared using SDS/OTAC surfactant mixture, the percentage of n-butanol distributed into the interfacial layer decreased while the fraction of n-butanol in the interfacial layer first increased sharply and then tended to be stable with the addition of n-butanol. For the different optimum W-III microemulsion systems tested, most of the surfactant-to-alcohol molar ratio data are near 1:3, but obvious deviation could be observed for some data. On the basis of the accurate measurement of n-butanol content in the EO and EW phases, the standard free energy, ΔG _o→in ^* (T = 298.15 K) of n-butanol transferring from the EO phase to the interfacial region was calculated. The results show negative ΔG _o→in ^* values. For microemulsions with the same components, n-butanol content is an important factor influencing the ΔG _o→in ^* value, and a high absolute value of ΔG _o→in ^* leads to high solubilization ability.     

Cation Effect on the Binary and Ternary Phase Behaviors of Double-Tailed Methanesulfonate Amphiphiles

A series of symmetrical dialkyl methanesulfonate amphiphiles [DiC _n CHSO ₃ ] _m M (n = 6, 7, 8) with different counter cations (M^m+ = H⁺, Li⁺, Na⁺, K⁺, Cu²⁺, Zn²⁺, Mg²⁺, Ca²⁺, Sc³⁺) were synthesized in five steps. Their solubility and critical micelle concentration (CMC) in water were determined highlighting a huge effect of the chain length and the nature of the cation. The hydrophilic–lipophilic balance of the surfactants were assessed with the phase inversion temperature (PIT)-slope method based on the deviation from the PIT of the reference C₁₀E₄/n-octane/0.01 M NaCl_(aq) emulsion through addition of increasing amounts of the dialkyl methanesulfonates. The hydrophilicity of the surfactants was thus ranked in terms of dPIT/dx_sulfonate. A “cation” scan with the [DiC ₆ CHSO ₃ ] _m M /benzene/water systems at f_w = 0.5 was finally performed confirming the hydrophilicity ranking obtained with the PIT-slope method. It revealed that the [DiC ₆ CHSO ₃ ] ₂ Mg behaves as a “Balanced Surfactant” able to form spontaneously a three-phase microemulsion system (Winsor III) just in the presence of water and oil, in the same way as the catalytic surfactant dimethyldioctylammonium molybdate, which has the same PIT-slope.     

火工药剂细化技术评价与展望

论述了国内外火工药剂细化技术的研究概况 ,针对敏感起爆药的特殊性 ,借鉴其他领域超细材料制备方法 ,提出用微乳液合成法制备超细敏感起爆药。     

萃取体系反向胶束和W／O微乳液的形成

本文评述了国内外学者在萃取体系反向胶束和微乳液领域的研究成果。探讨了胺类萃取和协同萃取体系中反向胶束的形成对萃取分配比的影响，以及某些萃取体系第三相与ＷｉｎｓｏｒⅢ微乳液的关系，并从形成反向胶束或微乳液的角度对萃取规律作了概括。     

Microemulsion synthesis of ms/tz-BiVO4 composites: The effect of pH on crystal structure and photocatalytic performance

In this work, BiVO₄ composites, containing the tetragonal zircon phase (tz-BiVO₄), and monoclinic scheelite phase (ms-BiVO₄), were synthesized using the microemulsion method. The effect of pH on phase composition and photocatalytic activity were investigated. Based on X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), a ms/tz-BiVO₄ composite forms at pH = 1.0 and pure ms-BiVO₄ is obtained in the pH range 4.0–10.0. The three primary steps in preparing BiVO₄ were monitored by optical microscopy and the role played by the microemulsion on the phase composition of BiVO₄ is explained. Photoluminescence spectroscopy (PL), UV–visible diffuse reflectance spectroscopy (UV-DRS), Brunauer-Emmett-Teller (BET), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) were employed to characterize the physical and chemical properties of BiVO₄ composites. The composite formed at pH = 1 exhibited the lowest hole-electron (h⁺-e^-) recombination rate, resulting in the highest photocatalytic activity towards microcystin-LR (MC-LR), with near 100% removal of MC-LR in 5 h. ESR and trapping experiments indicated that MC-LR degradation was mediated primarily by hydroxyl radicals (•OH), superoxide radicals (O₂^•−) and photogenerated holes (h⁺).     

How the Influence of Different Salts on Interfacial Properties of Surfactant–Oil–Water Systems at Optimum Formulation Matches the Hofmeister Series Ranking

In this work, we present the effects of salts on sodium dodecyl benzene sulfonate micellization and on the interfacial performance of a sodium dodecyl benzene sulfonate–heptane–brine system at optimum formulation, i.e., hydrophilic–lipophilic deviation (HLD) = 0. In order to do that, interfacial tension and dilational interfacial rheology properties of surfactant–heptane–water systems at optimum formulation are measured using an interfacial spinning drop tensiometer with an oscillating velocity, which can accurately measure interfacial rheology properties at both low and ultralow interfacial tensions. The brines used contain one of the following salts: MgCl₂, CaCl₂, NaCl, NH₄Cl, NaNO₃, CH₃COONa, or Na₂SO₄. We performed a one-dimensional salinity scan with each of these salts to achieve an optimum formulation. In relation to the Hofmeister series, we found that, at optimum formulation, systems with chaotropic ions (NH₄⁺, NO₃⁻) present interfaces with ultralow interfacial tensions, very low dilational modulus, and a low phase angle, whereas kosmotropic ions (Mg²⁺, Ca²⁺, SO₄⁻²) generate high interfacial tension and high rigidity monolayers. Intermediate ions in the Hofmeister series (Na⁺, CH₃COO⁻, Cl⁻) present interfaces with intermediate properties. Furthermore, according to the Hofmeister series, interfaces can be respectively ordered from higher to lower rigidity for surfactant counterions Mg²⁺ > Ca²⁺ > Na⁺ > NH₄⁺ and coions SO₄²⁻ > CH₃COO^– > Cl⁻ > NO₃⁻, which correspond to a salting-out (highest rigidity) and salting-in (lowest rigidity) effect. We observed that counterions have a more significant effect on surfactant–oil–water system properties than those that act as coions.