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Abstract 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. 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. 

Abstract Liquid crystalline elastomers (LCEs) that retain the cholesteric phase (CLCEs) are soft, polymeric materials that retain periodic structure and exhibit a selective reflection. While prior studies have examined thermochromism in CLCEs, the association of temperature change and reflection wavelength shift has been limited to 1.4 nm °C⁻¹. Here, CLCEs with intra‐mesogenic supramolecular bonds are prepared to enhance tunability as well triple the rate (e.g., 4.8 nm °C⁻¹). Specifically, these materials incorporate liquid crystalline monomers based on dimerized oxy‐benzoic acid (OBA) derivatives. Increasing the concentration of the OBA comonomers increases the magnitude of red‐shifting thermochromism of the selective reflection. At and above a threshold concentration, the selective reflection in the CLCEs can disappear upon heating, analogous to on‐off “switching.” Further, the introduction of the supramolecular bonds within the CLCE enable mechanical programming and enhanced one‐time tunable thermochromism via a one‐way shape memory process. Accordingly, this research could enable functional use in low temperature sensitive optical elements, fail‐safe thermal indicators for food packaging, and smart window coatings. 

Abstract Liquid crystalline elastomers (LCEs) are stimuli‐responsive materials capable of undergoing large deformations. The thermomechanical response of LCEs is attributable to the coupling of polymer network properties and disruption of order between liquid crystalline mesogens. Complex deformations have been realized in LCEs by either programming the nematic director via surface‐enforced alignment or localized mechanical deformation in materials incorporating dynamic covalent chemistries. Here, the preparation of LCEs via thiol‐Michael addition reaction is reported that are amenable to surface‐enforced alignment. Afforded by the thiol‐Michael addition reaction, dynamic covalent bonds are uniquely incorporated in chemistries subject to surface‐enforce alignment. Accordingly, LCEs prepared with complex director profiles are able to be programmed and reprogrammed by (re)activating the dynamic covalent chemistry to realize distinctive shape transformations. 

Abstract A mechanochromic, programmable, cholesteric liquid crystalline elastomer (CLCE) is fabricated, and after straining, resulting in a blue shift through the visible spectrum, is returned to its initial shape and color upon heating through its isotropic phase transition. Light initiated, radical‐mediated, addition fragmentation chain transfer (AFT), facilitate permanent programming or erasure of thermoreversible shape and color by relaxing stress imparted on the strained network through reversible bond exchange. Thermoreversible strain is coupled with reversible color change and can be made permanent at any desired strain by light exposure and corresponding AFT activation, temporarily restoring nearly initial shape and color upon heating. The optical characteristics and photonic structure, inherently linked to the network, are measured as a function of strain, to confirm the reflection notch narrowing indicating that prepolymerization alignment via shearing is poor thereby causing a broad spectrum of reflected light that narrows when the material is stretched. Beyond programming a new shape and color, the reflection notch is erased and separately, photopatterned to achieve dynamic color schemes that are toggled with heating and cooling, similar to that of a chameleon's camouflaging technique that has the ability to manipulate multiple colors in a single material, also with use for strain mapping.