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The ability to print soft materials into predefined architectures with programmable nanostructures and mechanical properties is a necessary requirement for creating synthetic biomaterials that mimic living tissues. However, the low viscosity of common materials and lack of required mechanical properties in the final product present an obstacle to the use of traditional additive manufacturing approaches. Here, a new liquid‐in‐liquid 3D printing approach is used to successfully fabricate constructs with internal nanostructures using in situ self‐assembly during the extrusion of an aqueous solution containing surfactant and photocurable polymer into a stabilizing polar oil bath. Subsequent photopolymerization preserves the nanostructures created due to surfactant self‐assembly at the immiscible liquid–liquid interface, which is confirmed by small‐angle X‐ray scattering. Mechanical properties of the photopolymerized prints are shown to be tunable based on constituent components of the aqueous solution. The reported 3D printing approach expands the range of low‐viscosity materials that can be used in 3D printing, and enables robust constructs production with internal nanostructures and spatially defined features. The reported approach has broad applications in regenerative medicine by providing a platform to print self‐assembling biomaterials into complex tissue mimics where internal supramolecular structures and their functionality control biological processes, similar to natural extracellular matrices.

 

The tunable properties of thermoplastic elastomers (TPEs), through polymer chemistry manipulations, enable these technologically critical materials to be employed in a broad range of applications. The need to “dial-in” the mechanical properties and responses of TPEs generally requires the design and synthesis of new macromolecules. In these designs, TPEs with nonlinear macromolecular architectures outperform the mechanical properties of their linear copolymer counterparts, but the differences in deformation mechanism providing enhanced performance are unknown. Here, in situ small-angle X-ray scattering (SAXS) measurements during uniaxial extension reveal distinct deformation mechanisms between a commercially available linear poly(styrene)-poly(butadiene)-poly(styrene) (SBS) triblock copolymer and the grafted SBS version containing grafted poly(styrene) (PS) chains from the poly(butadiene) (PBD) mid-block. The neat SBS (φSBS = 100%) sample deforms congruently with the macroscopic dimensions with the domain spacing between spheres increasing and decreasing along and traverse to the stretch direction, respectively. At high extensions, end segment pullout from the PS-rich domains is detected, which is indicated by a disordering of SBS. Conversely, the PS-grafted SBS that is 30 vol% SBS and 70% styrene (φSBS = 30%) exhibits a lamellar morphology and in situ SAXS measurements reveal an unexpected deformation mechanism. During deformation there are two simultaneous processes: significant lamellar domain rearrangement to preferentially orient the lamellae planes parallel to the stretch direction and crazing. The samples whiten at high strains as expected for crazing, which corresponds with the emergence of features in the two-dimensional SAXS pattern during stretching consistent with fibril-like structures that bridge the voids in crazes. The significant domain rearrangement in the grafted copolymers is attributed to the new junctions formed across multiple PS domains by the grafts of a single chain. The in situ SAXS measurements provide insights into the enhanced mechanical properties of grafted copolymers that arise through improved physical crosslinking that leads to nanostructured domain reorientation for self-reinforcement and craze formation where fibrils help to strengthen the polymer. 

Living systems are composed of a select number of biopolymers and minerals yet exhibit an immense diversity in materials properties. The wide-ranging characteristics, such as enhanced mechanical properties of skin and bone, or responsive optical properties derived from structural coloration, are a result of the multiscale, hierarchical structure of the materials. The fields of materials and polymer chemistry have leveraged equilibrium concepts in an effort to mimic the structure complex materials seen in nature. However, realizing the remarkable properties in natural systems requires moving beyond an equilibrium perspective. An alternative method to create materials with multiscale structures is to approach the issue from a kinetic perspective and utilize chemical processes to drive phase transitions. This Account features an active area of research in our group, reaction-induced phase transitions (RIPT), which uses chemical reactions such as polymerizations to induce structural changes in soft material systems. Depending on the type of phase transition (e.g., microphase versus macrophase separation), the resulting change in state will occur at different length scales (e.g., nm – μm), thus dictating the structure of the material. For example, the in situ formation of either a block copolymer or a homopolymer initially in a monomer mixture during a polymerization will drive nanoscale or macroscale transitions, respectively. Specifically, three different examples utilizing reaction-driven phase changes will be discussed: 1) in situ polymer grafting from block copolymers, 2) multiscale polymer nanocomposites, and 3) Lewis adduct-driven phase transitions. All three areas highlight how chemical changes via polymerizations or specific chemical binding result in phase transitions that lead to nanostructural and multiscale changes. Harnessing kinetic chemical processes to promote and control material structure, as opposed to organizing pre-synthesized molecules, polymers, or nanoparticles within a thermodynamic framework, is a growing area of interest. Trapping nonequilibrium states in polymer materials has been primarily focused from a polymer chain conformation viewpoint in which synthesized polymers are subjected to different thermal and processing conditions. The impact of reaction kinetics and polymerization rate on final polymer material structure is starting to be recognized as a new way to access different morphologies not available through thermodynamic means. Furthermore, kinetic control of polymer material structure is not specific to polymerizations and encompasses any chemical reaction that induce morphology transitions. Kinetically driven processes to dictate material structure directly impact a broad range of areas including separation membranes, biomolecular condensates, cell mobility, and the self-assembly of polymers and colloids. Advancing polymer material syntheses using kinetic principles such as RIPT opens new possibilities for dictating material structure and properties beyond what is currently available with traditional self-assembly techniques. 

Associative surfactants systems involving polar oils have recently been shown to stabilize immiscible liquids by forming nanostructures at the liquid interface and have been used to print soft materials. Although these associating surfactant systems show great promise for creating nanostructured soft materials, a fundamental understanding of the self-assembly process is still unknown. In this study, a ternary phase diagram for a system of cationic surfactant cetylpyridinium chloride monohydrate (CPCl), a polar oil (oleic acid), and water is established using experiment and simulation, to study the equilibrium phase behavior. A combination of visual inspection, small-angle X-ray scattering (SAXS), and rheological measurements was employed to establish the phase behavior and properties of the self-assembled materials. Dissipative particle dynamics (DPD) is used to simulate the formation of the morphologies in this system and support the experimental results. The ternary phase diagram obtained from the simulations agrees with the experimental results, indicating the robustness of the computational simulation as a supplement to the mesoscale experimental systems. We observe that morphological transitions ( e.g. , micelle-to-bilayer and vesicle-to-lamellar) are in agreement between experiments and simulations across the ternary diagram. DPD simulations correctly predict that associative surfactant systems form new nanoscale phases due to the co-assembly of the components. The established ternary phase diagram and the DPD model pave the way towards predicting and controlling the formation of different mesostructures like lamellar or vesicles, opening new avenues to tailor and synthesize desired morphologies for applications related to liquid-in-liquid 3D printing. 

Thermoplastic elastomers based on ABA triblock copolymers are typically limited in modulus and strength due to crack propagation within the brittle regions when the hard end-block composition favors morphologies that exhibit connected domains. Increasing the threshold end-block composition to achieve enhanced mechanical performance is possible by increasing the number of junctions or bridging points per chain, but these copolymer characteristics also tend to increase the complexity of the synthesis. Here, we report an in situ polymerization method to successfully increase the number of effective junctions per chain through grafting of poly(styrene) (PS) to a commercial thermoplastic elastomer, poly(styrene)–poly(butadiene)–poly(styrene) (SBS). The strategy described here transforms a linear SBS triblock copolymer–styrene mixture into a linear-comb-linear architecture in which poly(styrene) (PS) grafts from the mid-poly(butadiene) (PBD) block during the polymerization of styrene. Through systematic variation in the initial SBS/styrene content, nanostructural transitions from disordered spheres to lamellar through reaction-induced phase transitions (RIPT) were identified as the styrene content increased. Surprisingly, maximum mechanical performance (Young's modulus, tensile strength, and elongation at break) was obtained with samples exhibiting lamellar nanostructures, corresponding to overall PS contents of 61–77 wt% PS (including the original PS in SBS). The PS grafting from the PBD block increases the modulus and the strength of the thermoplastic elastomer while preventing brittle fracture due to the greater number of junctions afforded by the PS grafts. The work presented here demonstrates the use of RIPT to transform standard SBS materials into polymer systems with enhanced mechanical properties.