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Herman, Jeremy A.

Publications and source records attributed to Herman, Jeremy A..

Digital Light Process 3D Printing of Magnetically Aligned Liquid Crystalline Elastomer Free–forms

Liquid crystalline elastomers (LCEs) are anisotropic soft materials capable of large dimensional changes when subjected to a stimulus. The magnitude and directionality of the stimuli-induced thermomechanical response is associated with the alignment of the LCE. Recent reports detail the preparation of LCEs by additive manufacturing (AM) techniques, predominately using direct ink write printing. Another AM technique, digital light process (DLP) 3D printing, has generated significant interest as it affords LCE free-forms with high fidelity and resolution. However, one challenge of printing LCEs using vat polymerization methods such as DLP is enforcing alignment. Here, we document the preparation of aligned, main-chain LCEs via DLP 3D printing using a 100 mT magnetic field. Systematic examination isolates the contribution of magnetic field strength, alignment time, and build layer thickness on the degree of orientation in 3D printed LCEs. Informed by this fundamental understanding, DLP is used to print complex LCE free-forms with through-thickness variation in both spatial orientations. Further, the hierarchical variation in spatial orientation within LCE free-forms is used to produce objects that exhibit mechanical instabilities upon heating. DLP printing of aligned LCEs opens new opportunities to fabricate stimuli-responsive materials in form factors optimized for functional use in soft robotics and energy absorption.

36 MATERIALS SCIENCE↗

Millimeter-Thick Liquid Crystalline Elastomer Actuators Prepared by-Surface-Enforced Alignment

Here, liquid crystalline elastomers (LCE) are thermally cyclable, compliant actuators with compelling mechanical properties. The large and programmable deformation of LCE has led to numerous functional examinations spanning optics, medical devices, and robotics. A well-established method to prepare complex LCE actuators is to utilize surface-enforced photoalignment. Herein, a facile and scalable approach is reported to circumvent the physical limits of surface-enforced alignment (e.g., samples that are 50 µm or less) to amplify the achievable force output in LCE. Applying an approach termed direct layering, the thermomechanical response of LCE elements prepared with +1 disclination patterns in a range of compositions and thicknesses is contrasted. The design and preparation of +1 disclination patterns and arrays is explored to assess the contribution of sample geometry and overlap to deformation and force output. The methodology detailed in this contribution allows for the preparation of elements ≈1 mm in thickness that are capable of actuating large objects. Furthermore, the fabrication of these elements uniquely enables the realization of mechanical instabilities to hasten the actuation rate in response to thermal change and to enable leaping.

36 MATERIALS SCIENCE↗

Selectively Depolymerizable Polyurethanes from Unsaturated Polyols Cleavable by Olefin Metathesis

This communication describes a novel series of linear and crosslinked polyurethanes (PUs) and their selective depolymerization under mild conditions. Two unique polyols are synthesized bearing unsaturated units in a configuration designed to favor ring-closing metathesis (RCM) to five- and six-membered cycloalkenes. These polyols are co-polymerized with toluene diisocyanate to generate linear PUs and trifunctional hexamethylene- and diphenylmethane-based isocyanates to generate crosslinked PUs. The polyol design is such that the RCM reaction cleaves the backbone of the polymer chain. Upon exposure to dilute solutions of Grubbs’ catalyst under ambient conditions, the PUs are rapidly depolymerized to low molecular weight, soluble products bearing vinyl and cycloalkene functionalities. These functionalities enable further re-polymerization by traditional strategies for polymerization of double bonds. We anticipate that this general approach can be expanded to develop a range of chemically recyclable condensation polymers that are readily depolymerized by orthogonal metathesis chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗