4D Printing of Hygroscopic Liquid Crystal Elastomer Actuators.

Liquid crystal elastomers (LCEs) are broadly recognized as programmable actuating materials that are responsive to external stimuli, typically heat or light. Yet, soft LCEs that respond to changes in environmental humidity are not reported, except a few examples based on rigid liquid crystal networks with limited processing. Herein, a new class of highly deformable hygroscopic LCE actuators that can be prepared by versatile processing methods, including surface alignment as well as 3D printing is presented. The dimethylamino-functionalized LCE is prepared by the aza-Michael addition reaction between a reactive LC monomer and N,N'-dimethylethylenediamine as a chain extender, followed by photopolymerization. The humidity-responsive properties are introduced by activating one of the LCE surfaces with an acidic solution, which generates cations on the surface and provides asymmetric hydrophilicity to the LCE. The resulting humidity-responsive LCE undergoes programmed and reversible hygroscopic actuation, and its shape transformation can be directed by the cut angle with respect to a nematic director or by localizing activation regions in the LCE. Most importantly, various hygroscopic LCE actuators, including (porous) bilayers, a flower, a concentric square array, and a soft gripper, are successfully fabricated by using LC inks in UV-assisted direct-ink-writing-based 3D printing.

Distinguishing between Linear and Star Polystyrenes with Unentangled Arms by Dynamic Oscillatory Shear Tests.

Linear and nonlinear viscoelastic properties of star polystyrene (PS) melts with unentangled arms were measured by using small-amplitude and medium-amplitude oscillatory shear (SAOS and MAOS) tests. For comparison purposes, such tests were also conducted on entangled linear and star PS melts. Interestingly, the linear viscoelastic properties of unentangled star PS were quantitatively described using the Lihktman-McLeish model for entangled linear chains, indicating that unentangled stars were indistinguishable from linear chains by using relaxation spectra. By contrast, the relative intrinsic nonlinearity (Q0), one of the MAOS material functions, exhibited a difference between unentangled star and linear PS. When the maximum Q0 value (Q0,max) was plotted against the entanglement number of span molecules (Zs), unentangled star PS exhibited larger Q0,max values than linear PS, which was quantitatively predicted via the multimode K-BKZ model. Therefore, in the unentangled regime, star PS was concluded to be characterized by intrinsically higher relative nonlinearity than linear PS.

Linear and nonlinear oscillatory rheology of chemically pretreated and non-pretreated cellulose nanofiber suspensions.

Linear and nonlinear rheological properties of cellulose nanofiber (CNF) suspensions were measured under small and large amplitude oscillatory shear (SAOS and LAOS) flow. Four different CNFs were produced, two by only mechanical disintegration and two with chemical pretreatments. Linear viscoelastic properties distinguished chemically treated CNFs from two untreated fibers via a different scaling exponent of the elastic modulus. However, different mechanical fibrillation degree was not characterized via linear viscoelastic properties. In contrast, nonlinear viscoelastic properties reflected both effects of chemical pretreatments and mechanical fibrillation. More fibrillated CNFs exhibited nonlinear rheological phenomena at larger deformations. In addition, chemically treated CNFs exhibited greater network stiffness and higher network recovery rates due to the presence of charged functional groups on the fiber surfaces. A material-property co-plot showed that network stiffness and recovery rate were in a trade-off relationship.

Small and Medium Amplitude Oscillatory Shear Rheology of Model Branched Polystyrene (PS) Melts.

：Linear and nonlinear rheological properties of model comb polystyrenes (PS) with loosely to densely grafted architectures were measured under small and medium amplitude oscillatory shear (SAOS and MAOS) flow. This comb PS set had the same length of backbone and branches but varied in the number of branches from 3 to 120 branches. Linear viscoelastic properties of the comb PS were compared with the hierarchical model predictions. The model underpredicted zero-shear viscosity and backbone plateau modulus of densely branched comb with 60 or 120 branches because the model does not include the effect of side chain crowding. First- and third-harmonic nonlinearities reflected the hierarchy in the relaxation motion of comb structures. Notably, the low-frequency plateau values of first-harmonic MAOS moduli scaled with Mw-2 (total molecular weight), reflecting dynamic tube dilution (DTD) by relaxed branches. Relative intrinsic nonlinearity Q0 exhibited the difference between comb and bottlebrush via no low-frequency Q0 peak of bottlebrush corresponding to backbone relaxation, which is probably related to the stretched backbone conformation in bottlebrush.