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Abstract There is a considerable body of work that describes the scaling of diblock copolymer micelle dimensions in dilute and semi‐dilute solution based upon block degrees of polymerization and copolymer concentration. However, there is a lack of analogous information for semi‐dilute ABA triblock copolymer gels, which consist of ABA triblock copolymer dissolved in midblock‐selective (B‐selective) solvent. The present study uses small angle X‐ray scattering to extract micelle dimensions for numerous triblock copolymer gels that vary in copolymer identity (and hence block lengths) and copolymer concentration, as well as gels that contain various ratios of two unique triblock copolymers. Analysis of micelle structural data subsequently translates to universal scaling expressions for the micelle core radius –r_A≈N_A^0.53N_B^−0.14ϕ_ABA^0.16whereN_AandN_Bare the endblock and midblock degrees of polymerization, respectively, andϕ_ABAis the volume fraction of triblock copolymer in the gel – and for the intermicelle spacing –l_AA≈N_A^0.09N_B^0.29ϕ_ABA^−0.35. Each scaling expression describes the full collection of experimental data very well. Additionally, these scaling expressions are partially in line with expectations from semi‐dilute diblock copolymer solution theory. 

Abstract Establishing the independent tunability of transport and mechanical properties in polymer gels would significantly contribute to their implementation as transdermal drug delivery media, among other things. The work conducted herein uses facile changes in the formulation of physically crosslinked styrenic ABA/AB block copolymer organogels to alter their mechanical properties independently from the mass transport of an internally‐loaded nanocarrier. Such independent tunability is made possible by altering the relative amounts of ABA triblock and AB diblock copolymers while holding total copolymer concentration fixed. Specifically, three series of gels each with a fixed total copolymer concentration (10, 20, or 30 wt%) comprised of varying triblock copolymer concentration are studied. Small angle x‐ray scattering confirms that, at the nanoscale, only gel network connectivity changes within each series, while mechanical and release experiments show that increasing network connectivity leads to significant growth of gel moduli, but little change in nanocarrier release rate. 

Abstract Organogels possess characteristics that make them promising materials for enhancing our understanding of nanostructure‐diffusion relationships in gels and for use in diffusion‐centered applications including drug delivery and nanoreactor media. Unlike hydrogels, however, there are no well‐recognized techniques for measuring the fundamental diffusion parameter of diffusivity,D, in organogels. The present work establishes a technique for measuringDbased upon Fourier‐transform infrared spectroscopy. Physically crosslinked gels composed of poly[styrene‐b‐(ethylene‐butylene)‐b‐styrene] and aliphatic mineral oil are used to showcase the new technique's capability. Diffusivity of unimers—oleic acid—and reverse micelles—sodium dioctyl sulfosuccinate (AOT)—within as‐prepared and preswollen gels is quantified and resultant values are commensurate with studies of unimer and micelle diffusion in hydrogels. The case of AOT diffusion is further validated through small‐angle X‐ray scattering analysis, which is in close agreement (<20% difference). 

Organogels have recently been considered as materials for transdermal drug delivery media, wherein their transport and mechanical properties are among the most important considerations. Transport through organogels has only recently been investigated and findings highlight an inextricable link between gels’ transport and mechanical properties based upon the formulated polymer concentration. Here, organogels composed of styrenic triblock copolymer and different aliphatic mineral oils, each with a unique dynamic viscosity, are characterized in terms of their quasi-static uniaxial mechanical behavior and the internal diffusion of two unique solute penetrants. Mechanical testing results indicate that variation of mineral oil viscosity does not affect gel mechanical behavior. This likely stems from negligible changes in the interactions between mineral oils and the block copolymer, which leads to consistent crosslinked network structure and chain entanglement (at a fixed polymer concentration). Conversely, results from diffusion experiments highlight that two penetrants—oleic acid (OA) and aggregated aerosol-OT (AOT)—diffuse through gels at a rate inversely proportional to mineral oil viscosity. The inverse dependence is theoretically supported by the hydrodynamic model of solute diffusion through gels. Collectively, our results show that organogel solvent variation can be used as a design parameter to tailor solute transport through gels while maintaining fixed mechanical properties.