ABSTRACT
Aiming at the fundamental understanding of solvent effects in amphiphilic polymer systems, we considered poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers in water mixed with an ionic liquid-ethylammonium nitrate (EAN), 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6), or 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4)-and we investigated the hexagonal lyotropic liquid crystal structures by means of small-angle X-ray scattering (SAXS). At 50% polymer, the hexagonal structure (cylinders of self-assembled block copolymer) was maintained across the solvent mixing ratio. The effects of the ionic liquids were reflected in the characteristic length scales of the hexagonal structure and were interpreted in terms of the location of the ionic liquid in the self-assembled block copolymer domains. The protic ionic liquid EAN was evenly distributed within the aqueous domains and showed no affinity for the interface, whereas BMIMPF6 preferred to swell PEO and was located at the interface so as to reduce contact with water. BMIMBF4 was also interfacially active, but to a lesser extent.
ABSTRACT
Ionic liquids are promising media for self-assembling block copolymers in applications such as energy storage. A robust design of block copolymer formulations in ionic liquids requires fundamental knowledge of their self-organization at the nanoscale. To this end, here, we focus on modeling two-component systems comprising a Poly(ethylene oxide)-poly (propylene oxide)-Poly(ethylene oxide) (PEO-PPO-PEO) block copolymer (Pluronic P105: EO37PO58EO37) and room temperature ionic liquids (RTILs): protic ethylammonium nitrate (EAN), aprotic ionic liquids (1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6), or 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4). Rich structural polymorphism was exhibited, including phases of micellar (sphere) cubic, hexagonal (cylinder), bicontinuous cubic, and lamellar (bilayer) lyotropic liquid crystalline (LLC) ordered structures in addition to solution regions. The characteristic scales of the structural lengths were obtained using small-angle X-ray scattering (SAXS) data analysis. On the basis of phase behavior and structure, the effects of the ionic liquid solvent on block copolymer organization were assessed and contrasted to those of molecular solvents, such as water and formamide.
ABSTRACT
We demonstrated previously (Wu, H.; Zaccone, A.; Tsoutsoura, A.; Lattuada, M.; Morbidelli, M. Langmuir 2009, 25, 4715) that, for a colloid stabilized by charges from both polymer chain-end groups and adsorbed sulfonate surfactants, when the surfactant surface density reaches a certain critical value, the shear-induced gelation becomes unachievable at room temperature, even at an extremely large Peclet number, Pe = 4.6 x 10(4). This is due to the presence of the short-range, repulsive hydration force generated by the adsorbed surfactant. In this work, we investigate how such hydration force affects the shear-induced gelation at higher temperatures, in the range between 303 and 338 K. It is found that a colloidal system, which does not gel at room temperature in a microchannel at a fixed Pe = 3.7 x 10(4), does gel when temperature increases to a certain value. The critical initial particle volume fraction for the gelation to occur decreases as temperature increases. These results indicate that the effect of the hydration force on the gelation decreases as temperature increases. Moreover, we have observed that at the criticality only part of the primary particles is converted to the gel network and the effective particle volume fraction forming the gel network does not change significantly with temperature. The effective particle volume fraction is also independent of the surfactant surface coverage. Since the effective particle volume fraction corresponds to space filling requirement of a standing gel network, which is mainly related to the clusters structure, this result indicates that at a given shear rate the cluster structure does not change significantly with the surfactant surface coverage. On the other hand, since the cluster morphology is a strong function of the shear rate, we have observed that when the Peclet number is lowered from Pe = 3.7 x 10(4) to 1.7 x 10(4), the effective particle volume fraction reduces from 0.19 to 0.12 at 313 K.
ABSTRACT
We study shear-induced gelation in a microchannel without adding any salt, for a polymer colloid that is fully stable under stagnant conditions. The initial stability is achieved by negative charges from the polymer chain end groups. Then, sulfonate surfactants are added to the system. The surfactant adsorption is characterized by coexistence of domains of gaseous-like noninteracting molecules (G) and condensed patches of interacting molecules (K). It is found that, for a fixed, substantially high shear rate of 1x10(6) 1/s (Peclet number=4.5x10(4)), in the absence of surfactants, the shear-induced gelation of the system does occur, and when the surfactants are added, as the surfactant surface coverage on the particles increases to a certain value, the shear-induced gelation or even small extent of aggregation becomes impossible. We have estimated the Derjaguin-Landau-Verwey-Overbeek (DLVO) interaction energy barrier from the measured zeta-potentials and found that in all the cases the corresponding shear-induced collision energy is orders of magnitude larger than the required energy to overcome the barrier. Thus, one would expect occurrence of gelation for all the systems. This clearly indicates presence of additional non-DLVO interactions, which under very low ionic strength are related to the adsorbed surfactant patches that generate strongly repulsive, short-range hydration force. Moreover, when no gelation but only aggregation occurs after passing through the microchannel, the cluster size distribution exhibits distinct bimodality. The structure of the obtained gels also depends on the surfactant surface coverage.
