title: Hierarchical microstructures formed by bidisperse colloidal suspensions within colloid-in-liquid crystal gels.
abstract: Past studies have reported that colloids of a single size dispersed in the isotropic phase of a mesogenic solvent can form colloid-rich networks (and gels) upon thermal quenching of the system across the isotropic-nematic phase boundary of the mesogens. Herein we report the observation and characterization of complex hierarchical microstructures that form when bidisperse colloidal suspensions of nanoparticles (NPs; iron oxide with diameters of 188 ± 20 nm or poly(methyl methacrylate) with diameters of 150 ± 15 nm) and microparticles (MPs; polystyrene with diameters of 2.77 ± 0.20 μm) are dispersed in the isotropic phase of 4-pentyl-4'-cyanobiphenyl (5CB) and thermally quenched. Specifically, we document microstructuring that results from three sequential phase separation processes that occur at distinct temperatures during stepwise cooling of the ternary mixture from its miscibility region. The first phase transition demixes the system into coexisting MP-rich and NP-rich phases; the second promotes formation of a particle network within the MP-rich phase; and the third, which coincides with the isotropic-to-nematic phase transition of 5CB, produces a second colloidal network within the NP-rich phase. We quantified the dynamics of each demixing process by using optical microscopy and Fourier transform image analysis to establish that the phase transitions occur through (i) surface-directed spinodal decomposition, (ii) spinodal decomposition, and (iii) nucleation and growth, respectively. Significantly, the observed series of phase transitions leads to a hierarchical organization of cellular microstructures not observed in colloid-in-liquid crystal gels formed from monodisperse colloids. The results of this study suggest new routes to the synthesis of colloidal materials with hierarchical microstructures that combine large surface areas and organized porosity with potential applications in catalysis, separations, chemical sensing, or tissue engineering.
authors.affiliation: †Department of Chemical Engineering, University of Puerto Rico-Mayagüez, Mayagüez 00681, Puerto Rico.
authors.forename: Heberth
authors.initials: H
authors.lastname: Diestra-Cruz
authors.affiliation: ‡Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States.
authors.forename: Emre
authors.initials: E
authors.lastname: Bukusoglu
authors.affiliation: ‡Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States.
authors.forename: Nicholas L
authors.initials: NL
authors.lastname: Abbott
authors.affiliation: †Department of Chemical Engineering, University of Puerto Rico-Mayagüez, Mayagüez 00681, Puerto Rico.
authors.forename: Aldo
authors.initials: A
authors.lastname: Acevedo
mesh_terms: D003460:Crystallization / Q000379:methods; D005782:Gels / Q000737:chemistry*; D050866:Liquid Crystals / Q000737:chemistry*; D058185:Magnetite Nanoparticles / Q000737:chemistry* / Q000648:ultrastructure; D008422:Materials Testing; D044367:Phase Transition; D019904:Polymethyl Methacrylate / Q000737:chemistry*; D013535:Suspensions / Q000737:chemistry*
chemical_list: D005782:Gels; D058185:Magnetite Nanoparticles; D013535:Suspensions; D019904:Polymethyl Methacrylate
keywords: bidisperse suspensions; colloid-in-liquid crystal gels; hierarchical microstructure; microparticles; nanoparticles; rheology; spinodal decomposition