New solvents for surfactant self-assembly : molten hydrated salts and concentrated aqueous electrolyte solutions

Dağ, Ömer
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Bilkent University
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Lyotropic liquid crystalline (LLC) mesophases are formed by at least two components: a surfactant and a solvent. Common solvents in the surfactant self-assembly include water, organic liquids, and ionic liquids. In this work, we show that molten hydrated salts of the type M(H2O)mn (where, M is a transiton metal cation and X is a suitable anion such as NO3

, Cl- , and ClO4

), which have melting points close to room temperature (RT), can organize surfactant molecules into LLC mesophases. As an example, we have focused on the Zn(H2O)62-C12EO10 system (where, C12EO10 is decaethylene monododecyl ether; H3C-(CH2)11-(OCH2CH2)10-OH). A binary phase diagram was constructed between -190oC and 110oC using differential scanning calorimetry (DSC), polarized optical microscopy (POM), X-ray diffractometry (XRD), fourier transform infrared spectroscopy (FT-IR), and raman spectroscopy. The phase diagram closely resembles the phase diagram of H2O-CmEOn systems, exhibiting typical phases such as spherical cubic, hexagonal, and bicontinuous cubic. It is also observed that the phase transitions are dictated by the critical packing parameter (CPP) as the solvent concentration is changed. The mesophases are unusually stable at low temperatures, where a LLC to mesostructured solid transformation has been observed with a glass transiton at - 52oC. The mesostructured solid phase is also stable at -190oC. The confinement of the salt species in the LLC domains prevents the crystallization of the salt at low temperatures. In the second part, from the analogy between M(H2O)mn type salts and concentrated electrolyte solutions of alkali metal salts, the mixtures of concentrated aqueous solutions of some Li+ salts (LiCl, LiBr, LiI, LiNO3 and LiClO4) with C12EO10 surfactant, were investigated. The mixtures exhibited LLC mesophases in a broad range of compositions. A ternary phase diagram was constructed for the LiNO3-H2O-C12EO10 system at room temperature using XRD and POM tecniques. In the LLC mesophases formed with the Li+ salts, the water remains as hydrated under ambient conditions and open atmosphere. In addition, the effect of anions on the phase behaviour follows a Hofmeister series except for the ClO4

ion. Ionic conductivty of the LiX-H2O-C12EO10 (where X is Cland


) mesophases has been determined in a broad range of the salt concentrations (5 to 7 salt/surfactant mole ratio) and temperature (-13 to 100oC). The LiCl-H2OC12EO10 LLC samples have also been used as a gel-electrolyte to run a polymer electrochromic device. The mesophase shows excellent performance in this device. The investigations were further extended to include some of the Ca2+ salts, namely CaCl2 and Ca(NO3)2. The concentrated aqueous solutions of both salts with C12EO10 and water exhibited LLC mesophases similar to the molten hydrated salts and concentrated solutions of Li+ salts. In the CaCl2.xH2O-C12EO10 system, an LLC to mesocrystalline phase transformation was observed, for the first time, where the salt, water and surfactant species freezes to a mesocrystalline phase at RT. Lastly, many other salt.xH2O-surfactant LLC mesophases were investigated using the following salts: NaCl, NaBr, NaI, CH3COONa, NaSCN, NaClO4, NaNO3, KNO3, KCl, KSCN, KI, MgCl2, Mg(NO3)2 and NaOH. In addition, the LLC mesophases of concentrated H3PO4 acid and C12EO10 were also investigated. Among these compounds, H3PO4 systems exhibited air stable LLC mesophases at RT and 25% relative humdity (RH). The MgCl2 system was found to exhibit air stable LLC mesophases for a couple of hours. The NaI, KSCN and NaClO4 systems were found to be stable at low salt concentrations with little or no mesostructured order. Other salt systems were unstable and leached out salt crystals rapidly. The NaOH system is unstable because of a reaction with CO2 in the air. In summary, we have found a correlation between the deliquescent relative humidity value of the salt and its LLC mesophase formation ability under ambient conditions.

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