An elastomeric, healable, supramolecular polymer blend comprising a chain-folding polyimide and a telechelic polyurethane with pyrenyl end groups is compatibilized by aromatic pi-pi stacking between the pi-electron-deficient diimide groups and the pi-electron-rich pyrenyl units. This interpolymer interaction is the key to forming a tough, healable, elastomeric material. Variable-temperature FTIR analysis of the bulk material also conclusively demonstrates the presence of hydrogen bonding, which complements the pi-pi stacking interactions. Variable-temperature SAXS analysis shows that the healable polymeric blend has a nanophase-separated morphology and that the X-ray contrast between the two types of domain increases with increasing temperature, a feature that is repeatable over several heating and cooling cycles. A fractured sample of this material reproducibly regains more than 95% of the tensile modulus, 91% of the elongation to break, and 77% of the modulus of toughness of the pristine material.

Material extrusion (ME)2 is a layer-by-layer additive manufacturing process that is now used in personal and commercial production where prototyping and customization are required. However, parts produced from ME frequently exhibit poor mechanical performance relative to those from traditional means; moreover, fundamental knowledge of the factors leading to development of inter-layer strength in this highly non-isothermal process is limited. In this work, we seek to understand the development of inter-layer weld strength from the perspective of polymer interdiffusion under conditions of rapidly changing mobility. Our framework centers around three interrelated components: in-situ thermal measurements (via infrared imaging), temperature dependent molecular processes (via rheology), and mechanical testing (via mode III fracture). We develop the concept of an equivalent isothermal weld time and test its relationship to fracture energy. For the printing conditions studied the equivalent isothermal weld time for Tref = 230 °C ranged from 0.1 ms to 100 ms. The results of these analysis provide a basis for optimizing inter-layer strength, the limitations of the ME process, and guide development of new materials.

In common thermoplastic additive manufacturing (AM) processes, a solid polymer filament is melted, extruded though a rastering nozzle, welded onto neighboring layers and solidified. The temperature of the polymer at each of these stages is the key parameter governing these non-equilibrium processes, but due to its strong spatial and temporal variations, it is difficult to measure accurately. Here we utilize infrared (IR) imaging - in conjunction with necessary reflection corrections and calibration procedures - to measure these temperature profiles of a model polymer during 3D printing. From the temperature profiles of the printed layer (road) and sublayers, the temporal profile of the crucially important weld temperatures can be obtained. Under typical printing conditions, the weld temperature decreases at a rate of approximately 100 °C/s and remains above the glass transition temperature for approximately 1 s. These measurement methods are a first step in the development of strategies to control and model the printing processes and in the ability to develop models that correlate critical part strength with material and processing parameters.

The solution self-assembly of macromolecular amphiphiles offers an efficient, bottom-up strategy for producing well--defined nanocarriers, with applications ranging from drug delivery to nanoreactors. Typically, the generation of uniform nanocarrier architecturesis controlled by processing methods that rely upon cosolvent mixtures. These preparation strategies hinge on the assumption that macromolecular solution nanostructures are kinetically stable following transfer from an organic/aqueous cosolvent into aqueous solution. Herein we demonstrate that unequivocal step-change shifts in micelle populations occur over several weeks following transfer into a highly selective solvent. The unexpected micelle growth evolves through a distinct bimodal distribution separated by multiple fusion events and critically depends on solution agitation. Notably, these results underscore fundamental similarities between assembly processes in amphiphilic polymer, small molecule, and protein systems. Moreover, the non-equilibrium micelle size increase can have a major impact on the assumed stability of solution assemblies, for which performance is dictated by nanocarrier size and structure.

As more manufacturing processes and research institutions adopt customized manufacturing as a key element in their design strategies and finished products, the resulting mechanical properties of parts produced through additive manufacturing (AM) must be characterized and understood. In material extrusion (MatEx), the most recently extruded polymer filament must bond to the previously extruded filament via polymer diffusion to form a “weld”. The strength of the weld limits the performance of the manufactured part and is controlled through processing conditions. Under-standing the role of processing conditions, specifically extruder velocity and extruder temperature, on the overall strength of the weld will allow optimization of MatEx-AM parts. Here, the fracture toughness of a single weld is determined through a facile “trouser tear” Mode III fracture experiment. The actual weld thickness is observed directly by optical microscopy characterization of cross sections of MatEx-AM samples. Representative data of weld strength as a function of printing parameters on a commercial 3D printer demonstrates the robustness of the method.

We present a spatially resolved approach for the solvent vapor annealing (SVA) of block copolymer thin films that permits the facile and relatively rapid manipulation of nanoscale ordering and nanostructure orientation. In our method, a localized (point) SVA zone is created through the use of a vapor delivery nozzle. This point annealing zone can be rastered across the thin film using a motorized stage to control the local nanoscale structure and orientation in a cylinder-forming ABA triblock copolymer thin film. At moderate rastering speeds (∼100 μm/s) (i.e., relatively modest annealing time at a given point), the film displayed ordered cylindrical nanostructures with the cylinders oriented parallel to the substrate surface. As the rastering speed was decreased (∼10 μm/s), the morphology transformed into a surface nanostructure indicative of cylinders oriented perpendicular to the substrate surface. These perpendicular cylinder orientations also were created by rastering multiple times over the same region, and this effect was found when rastering in either retrace (overlapping) or crossed-path (orthogonal) geometries. Similar trends in nanostructure orientation and ordering were obtained from various nozzle diameters by accounting for differences in solvent flux and annealing time, illustrating the universality of this approach. Finally, we note that our "stylus-based" raster solvent vapor annealing technique allows a given point to be solvent annealed approximately 2 orders of magnitude faster than conventional "bell jar" solvent vapor annealing.

A polyacrylamide hydrogel system that can be liquefied by remote activation using UV irradiation is investigated as a degradable adhesive. The linear polyacrylamide copolymer, formed by conventional free-radical polymerization, contains biomimetic catechol−iron-mediated crosslinkers that are sensitive to pH changes. Hydrogel films and bulk gels are prepared by basic titration of a polymer solution doped with a photoacid generator, diphenyliodonium chloride, generating an ionic cross-linked network via the catechol pendant groups. Irradiation of these hydrogels with UV light affords a viscous liquid solution, demonstrating a gel−sol transition with a subsequent decrease in the adhesive strength of the material. These gels may be prepared in high throughput and require few synthetic steps with commercially available precursors.

Controlling the nanostructure of self-assembled block copolymer thin films is critical for applications in nanotemplate design, nanoporous membranes, and organic optoelectronics. In this study, we employed a gradient approach to examine the effects of substrate surface chemistry and film thickness on the self-assembly of cylinder-forming poly(styrene-b-isoprene-b-styrene) (SIS) thin films. Using gradients in film thickness from 85 to 120 nm (3.1d to 4.4d), we found that the thin films contained parallel cylinders on both bare silicon substrates and benzyldimethylchlorosilane (benzyl silane)-modified substrates regardless of film thickness, while thin films contained surface patterns of hexagonally arranged dots on n-butyldimethylchlorosilane (n-butyl silane)-modified substrates. These surface patterns were further investigated using film etching, cross-sectional transmission electron microscopy (TEM), and grazing-incidence small-angle X-ray scattering (GISAXS) techniques. We determined that the nanostructures represented a hexagonally perforated lamellar (HPL) morphology in which the parallel cylinder layering was preserved during the phase transformation to HPL. Additionally, controlled vapor deposition was used to generate a nearly linear substrate surface chemistry gradient from benzyl silane to n-butyl silane. Examination of SIS thin films on this surface gradient revealed a morphological transformation from parallel cylinders to HPL with changing substrate surface composition. Thus, we demonstrated the combined usage of film thickness and monolayer substrate surface chemistry gradients to manipulate the nanostructure of block copolymer films, such as SIS, that possess moderate differences in surface energy between individual blocks. Our gradients represent a high-throughput and versatile screening tool that facilitates the examination of new materials and furthers the understanding of block copolymer thin film self-assembly.