- The Aggregation Behavior of Mixture of Alkylmethylaminoxides with Their Protonated Analogues in Aqueous Solution (2005)
- The C12C8MAO aqueous solution at 100 mM consisted of two phases which were optically isotropic and low viscous. Addition of chloric acid induced a phase transition, and the following lamellar (L-alpha) phase was formed in the range of low protonation degree, X = 0.007 – 0.35. When the surfactant was protonated further (X > 0.35), the single L-alpha phase separated again into two isotropic phases. The abnormal phase sequence could be interpreted by the result that mixtures of protonated and non-protonated C12C8MAO were more surface active than each component. The surface and interfacial measurements showed synergism of mixing two components. This synergistic effect arised from the peculiar interaction of hydrogen bonding between protonated and non-protonated head groups. This short-range interaction would cause the C12C8MAO molecules to be more lipophilic with protonation, resulting in the phase separation at high protonation degree. The SAXS measurements in the L-alpha phase also showed the synergistic effect between the head groups. The rheological measurements and microscope observations demonstrated that the morphologies of L-alpha phase could be controlled by preparation routes. It was found that the vesicles were transformed into the classical lamellar phase by the simple process of heating and cooling through the phase transition (L-alpha <-> L-alpha;/L1) temperature. Furthermore, the classical, planar lamellar morphology could be prepared by means of kinetic protonation of the C12C8MAO molecules using hydrolysis reaction. Any classical L phase was modified to the vesicle form under shearing, and its transformation was irreversible in terms of shear force. Various acids were treated as protonation agent in 100mM C14DMAO aqueous solution, and their contributions to the viscosity of solution were examined ranging X = 0 to 1. It was elucidated that the aggregate structure remarkably depended on the ion-pair (counte-ion) thermodynamics. For the Cl-, HCOO-, and H2PO4- ions, no remarkable structural change took place with increasing protonation. For the Br-, NO3-, Oxalate, Tartarate, Tartronate, and SO42- ions, the small micelles of C14DMAO grew up with protonation. For the ClO4-, SCN-, and Salicylate ions, the L-alpha phase was formed with protonation. The interfacial curvature thus followed mostly the sequence of Hofmeister series, while the sulfuric ion was completely excluded from the series because of its divalency. The viscosity change was interpreted quantitatively by the hydration free energy (Delta-Ghyd) of counter-ion. However the divalent counter-ions did not arrange in the same order as the monovalent ones, that could be considered to arise from (1) depressing pKa of C14DMAO with increasing amount of acid and (2) electrostatic force within the diffuse double layer. For different counter-ions, the characteristic scaling laws of viscosity evolution against X were observed. The scaling laws also obeyed Delta-Ghyd. Sulfate, however, could not be manipulated by Delta-Ghyd: regardless of its strong hydrophilicity (high Delta-Ghyd), the excess amount of SO42- caused the micelles to grow up. The micelle growth therefore would be attributed by counter-ion condensation onto the micelles rather than hydrophilicity itself. Comprehensively it was proved that Delta-Ghyd and the ionic valency (electrostatic force) of counter-ion played strikingly significant roles in the structural properties. Trifluoro acetic acid CF3COOH behaved as hydrophobic acid, however, the viscosity trend could stand in neither the sequence of Delta-Ghyd nor the Hofmeister series. The interfacial tension measurments suggested that the CF3COO- ion was incorporated into the micelle, behaving like co-surfactant. Synergism on mixing was also observed in the CF3COOH system, by which the minimal CMC was obtained. The interaction parameter beta indicated that CF3COOH caused the stronger synergistic effect than HNO3. However, some experiments showed the successively hydrophobic C14DMAO with protonation. This would be due to the orientation of hydrophobic trifluoro group in the palisade layer of micelle. The increasing volume fraction of hydrophobic moiety in the surfactant molecule (OleylDMAO) built up the bilayer structure even using the strongly hydrated acids. The L-alpha formation was referred to synergism because the isotropic micellar phase was present on both the sides of high and low protonation degrees. The L-alpha phase melted on elevating temperature, and the subsequent L1 phase was highly viscoelastic. The L-alpha - L1 transition temperatures for different acids were almost correlated by the enthalpy of hydration (DeltaHhyd). And the viscoelastic properties of the L-alpha phases were dependent on the Hofmeister series.