Effect of nanoparticle loading and magnetic field application on the thermodynamic, optical, and rheological behavior of thermoresponsive polymer solutions.

Although processing via external stimuli is a promising technique to tune the structure and properties of polymeric materials, the impact of magnetic fields on phase transitions in thermoresponsive polymer solutions is not well-understood. As nanoparticle (NP) addition is also known to impact these thermodynamic and optical properties, synergistic effects from combining magnetic fields with NP incorporation provide a novel route for tuning material properties. Here, the thermodynamic, optical, and rheological properties of aqueous poly(N-isopropyl acrylamide) (PNIPAM) solutions are examined in the presence of hydrophilic silica NPs and magnetic fields, individually and jointly, via Fourier-transform infrared spectroscopy (FTIR), magneto-turbidimetry, differential scanning calorimetry (DSC), and magneto-rheology. While NPs and magnetic fields both reduce the phase separation energy barrier and lower optical transition temperatures by altering hydrogen bonding (H-bonding), infrared spectra demonstrate that the mechanism by which these changes occur is distinct. Magnetic fields primarily alter solvent polarization while NPs provide PNIPAM-NP H-bonding sites. Combining NP addition with field application uniquely alters the solution environment and results in field-dependent rheological behavior that is unseen in polymer-only solutions. These investigations provide fundamental understanding on the interplay of magnetic fields and NP addition on PNIPAM thermoresponsivity which can be harnessed for increasingly complex stimuli-responsive materials.

Formation of Pixelated Elastic Films via Capillary Suction of Curable Elastomers in Templated Hele-Shaw Cells.

Natural materials are highly organized, frequently possessing intricate and sophisticated hierarchical structures from which superior properties emerge. In the wake of biomimicry, there is a growing interest in designing architected materials in the laboratory as such structures could enable myriad functionalities in engineering. Yet, their fabrication remains challenging despite recent progress in additive manufacturing. In particular, soft materials are typically poorly suited to form the requisite structures consisting of regular geometries. Here, a new frugal methodology is reported to fabricate pixelated soft materials. This approach is conceptually analogous to the watershed transform used in image analysis and allows the passive assembly of complex geometries through the capillary-mediated flow of curable elastomers in confined geometries. Emerging from sources distributed across a Hele-Shaw cell consisting of two parallel flat plates separated by an infinitesimally small gap, these flows eventually meet at the "dividing lines" thereby forming Voronoi tesselations. After curing is complete, these structures turn into composite elastic sheets. Rationalizing the fluid mechanics at play allows the structural geometry of the newly formed sheets to be tailored and thereby their local material properties to be tuned.