skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


This content will become publicly available on August 4, 2026

Title: Inverse Elastocaloric Output in Supramolecular Liquid Crystalline Elastomers
NoElastocaloric cooling is a promising solid-state alternative to vapor-compression refrigeration. In conventional systems, such as natural rubber, deformation induces entropy change accompanied by temperature release. Unloading the material restores the entropic state and is accompanied by cooling. Inverse elastocaloric effects have been detailed in shape memory alloys, where deformation induces loss of order and cooling. Here, we report on a distinctive inverse elastocaloric effect in liquid crystalline elastomers (LCEs) containing supramolecular hydrogen bonds. Upon deformation, the supramolecular LCE exhibits initial organization but then disorganizes as the intramesogenic hydrogen bonds are broken. Due to the liquid crystalline nature of the dimeric supramolecular bonds, the mechanochemical bond breakage manifests in a disruption in order. By disrupting the extent of liquid crystallinity in the system, we hypothesize that the network disorganizes to the deformation (e.g., entropy increases) and produces an inverse elastocaloric output.t Available  more » « less
Award ID(s):
2105369
PAR ID:
10642799
Author(s) / Creator(s):
; ; ; ;
Publisher / Repository:
American Chemical Society
Date Published:
Journal Name:
ACS Materials Letters
Volume:
7
Issue:
8
ISSN:
2639-4979
Page Range / eLocation ID:
2688 to 2694
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Liquid crystalline elastomers (LCEs) are soft materials that associate order and deformation. Upon deformation, mechanically induced changes order affect entropy and can produce a caloric output (elastocaloric). Elastocaloric effects in materials continue to be considered for functional use as solid state refrigerants. Prior elastocaloric investigations of LCEs and related materials have measured ≈2 °C temperature changes upon deformation (100% strain). Here, the elastocaloric response of LCEs is explored that are prepared with a subambient nematic to isotropic transition temperature. These materials are referred as “isotropic” liquid crystalline elastomers. The LCEs are prepared by a two‐step thiol‐Michael/thiol‐ene reaction. This polymer network chemistry enhances elastic recovery and reduces hysteresis compared to acrylate‐based chemistries. The LCEs exhibit appreciable elastocaloric temperature changes upon deformation and recovery (> ± 3 °C, total ΔTof 6 °C) to deformation driven by minimal force (<< 1 MPa). Notably, the strong association of deformation and order and the resulting temperature change attained at low force achieves a responsivity of 14 °C MPa−1which is seven times greater than natural rubber. 
    more » « less
  2. Abstract Shape‐switching behavior, where a transient stimulus induces an indefinitely stable deformation that can be recovered on exposure to another transient stimulus, is critical to building smart structures from responsive polymers as continue power is not needed to maintain deformations. Herein, we 4D‐print shape‐switching liquid crystalline elastomers (LCEs) functionalized with supramolecular crosslinks, dynamic covalent crosslinks, and azobenzene. The salient property of shape‐switching LCEs is that light induces long‐lived, deformation that can be recovered on‐demand by heating. UV‐light isomerizes azobenzene fromtranstocis, and temporarily breaks the supramolecular crosslinks, resulting in a programmed deformation. After UV, the shape‐switching LCEs fix more than 90 % of the deformation over 3 days by the reformed supramolecular crosslinks. Using the shape‐switching properties, we print Braille‐like actuators that can be photoswitched to display different letters. This new class of photoswitchable actuators may impact applications such as deployable devices where continuous application of power is impractical. 
    more » « less
  3. Liquid crystalline elastomers (LCEs) are soft materials which disorder upon heating through the isotropic transition temperature. The order-disorder phase transition of LCEs results in a contraction of up to ∼50% along the aligned axis. Motivated by this distinctive stimuli-response, LCEs are increasingly considered as low-density actuators. Generally, LCEs are composed entirely of covalent bonds. Recently, we have prepared LCEs with intramesogenic supramolecular bonds from dimerized oxybenzoic acid derivatives and documented distinctive thermomechanical response in these supramolecular LCEs. Here, we report a detailed investigation of phase transitions in supramolecular LCEs by systematically varying the composition to affect the strength of the intermolecular interactions in the polymer network. The order-disorder phase transition is shown to be influenced by the conformation and dissociation of supramolecular dimers. Distinctly, this report isolates and details an LCE composition which undergoes an intermediate transition to an incommensurate phase at lower temperatures than the order-disorder transition. 
    more » « less
  4. Punzo, Francesco (Ed.)
    To enhance the solubility of orally administered pharmaceuticals, liquid capsules or amorphous tablets are often preferred over crystalline drug products. However, little is known regarding the variation in bonding mechanisms between pharmaceutical molecules in their different disordered forms. In this study, liquid and melt-quenched glassy carbamazepine have been studied using high energy X-ray diffraction and modeled using Empirical Potential Structure Refinement. The results show significant structural differences between the liquid and glassy states. The liquid shows a wide range of structures; from isolated molecules, to aromatic ring correlations and NH-O hydrogen bonding. Upon quenching from the liquid to the glass the number of hydrogen bonds per molecule increases by ~50% at the expense of a ~30% decrease in the close contact (non-bonded) carbon-carbon interactions between aromatic rings. During the cooling process, there is an increase in both singly and doubly hydrogen-bonded adjacent molecules. Although hydrogen-bonded dimers found in the crystalline states persist in the glassy state, the absence of a crystalline lattice also allows small, hydrogen-bonded NH-O trimers and tetramers to form. This proposed model for the structure of glassy carbamazepine is consistent with the results from vibrational spectroscopy and nuclear magnetic resonance. 
    more » « less
  5. The directional deformation of liquid crystalline elastomers (LCEs) is predicated on alignment, enforced by various processing techniques. Specifically, surface-aligned LCEs can exhibit higher temperature thermomechanical responses and weakened strain−temperature coupling in comparison to LCEs subjected to mechanical or rheological alignment. Recently, we reported enhanced stimuli response of mechanically aligned LCEs containing supramolecular liquid crystals. Here, we prepare supramolecular LCEs via surface-enforced alignment to study the impact of the supramolecular bond strength and intermolecular forces. This was evaluated using oxybenzoic acid (OBA) derivatives with and without pendant methyl groups as well as via oxybenzoic acid-pyridine complexes. Increased incorporation of supramolecular mesogens reduces the isotropic transition temperature and generally increases the strain−temperature coupling. The number of elastically active strands per unit volume, hydrogen bond conformations, and network morphology are affected by the supramolecular mesogens and influence the observed stimuli response. Overall, reduced intermolecular interactions correlate with more desirable actuation properties, demonstrating the influence of the supramolecular mesogen’s structure. 
    more » « less