The glass transition is a long-standing unsolved problem in materials science. For polymers, our understanding of glass formation is particularly poor because of the added complexity of chain connectivity and flexibility; structural relaxation of polymers thus involves a complex interplay between intramolecular and intermolecular cooperativity. Here, we study how the glass-transition temperature $T_g$ varies with molecular weight $M$ for different polymer chemistries and chain flexibilities. We find that $T_g(M)$ is controlled by the average mass (or volume) per conformational degree of freedom and that a “local” molecular relaxation (involving a few conformers) controls the larger-scale cooperative $\alpha$ relaxation responsible for $T_g$. We propose that dynamic facilitation where a local relaxation facilitates adjacent relaxations, leading to hierarchical dynamics, can explain our observations, including logarithmic $T_g(M)$ dependences. Our study provides a new understanding of molecular relaxations and the glass transition in polymers, which paves the way for predictive design of polymers based on monomer-scale metrics.

Auxetic materials exhibit a negative Poisson’s ratio, i.e., they become thicker rather than thinner in at least one dimension when strained. Recently, a nematic liquid crystal elastomer (LCE) was shown to be the first synthetic auxetic material at a molecular level. Understanding the mechanism of the auxetic response in LCEs is clearly important, and it has been suggested through detailed Raman scattering studies that it is related to the reduction of uniaxial order and emergence of biaxial order on strain. In this paper, we demonstrate direct observation of the biaxial order in an auxetic LCE under strain. We fabricated ~100 μm thick LCE strips with complementary geometries, exhibiting either planar or homeotropic alignment, in which the auxetic response is seen in the thickness or width of the sample, respectively. Polarized Raman scattering measurements on the planar sample show directly the reduction in the uniaxial order parameters on strain and suggest the emergence of biaxial order to mediate the auxetic response in the sample thickness. The homeotropic sample is studied via conoscopy, allowing direct observation of both the auxetic response in the width of the sample and increasing biaxiality in the LCE as it is strained. We verified that the mechanism of the auxetic response in auxetic LCEs is due to the emergence of the biaxial order and conclude such materials can be added to the small number of biaxial nematic systems that have been observed. Importantly, we also show that the mechanical Frèedericksz transition seen in some LCEs is consistent with a strain-induced transition from an optically positive to an optically negative biaxial system under strain, rather than a director rotation in a uniaxial system.

Determining the tunability of the optical coefficients, order parameter, and transition temperatures in optically transparent auxetic liquid crystal elastomers (LCEs) is vital for applications, including impact-resistant glass laminates. Here, we report measurements of the refractive indices, order parameters, and transition temperatures in a family of acrylate-based LCEs in which the mesogenic content varies from ∼50 to ∼85%. Modifications in the precursor mixture allow the order parameter, ⟨P₂⟩, of the LCE to be adjusted from 0.46 to 0.73. The extraordinary refractive index changes most significantly with composition, from ∼1.66 to ∼1.69, in moving from a low to high mesogenic content. We demonstrate that all LCE refractive indices decrease with increasing temperature, with temperature coefficients of ∼10^-4 K^-1, comparable to optical plastics. In these LCEs, the average refractive index and the refractive index anisotropy are tunable via both chemical composition and order parameter control; we report design rules for both.

Liquid Crystal Elastomers (LCEs) combine the anisotropic ordering of liquid crystals with the elastic properties of elastomers, providing unique physical properties, such as stimuli responsiveness and a recently discovered molecular auxetic response. Here, we determine how the molecular relaxation dynamics in an acrylate LCE are affected by its phase using broadband dielectric relaxation spectroscopy, calorimetry and rheology. Our LCE is an excellent model system since it exhibits a molecular auxetic response in its nematic state, and chemically identical nematic or isotropic samples can be prepared by cross-linking. We find that the glass transition temperatures ($T_{\mathrm{g}}$) and dynamic fragilities are similar in both phases, and the $T$-dependence of the $\alpha$ relaxation shows a crossover at the same $T^{*}$ for both phases. However, for $T>T^{*}$, the behavior becomes Arrhenius for the nematic LCE, but only more Arrhenius-like for the isotropic sample. We provide evidence that the latter behavior is related to the existence of pre-transitional nematic fluctuations in the isotropic LCE, which are locked in by polymerization. The role of applied strain on the relaxation dynamics and mechanical response of the LCE is investigated; this is particularly important since the molecular auxetic response is linked to a mechanical Fréedericksz transition that is not fully understood. We demonstrate that the complex Young’s modulus and the $\alpha$ relaxation time remain relatively unchanged for small deformations, whereas for strains for which the auxetic response is achieved, significant increases are observed. We suggest that the observed molecular auxetic response is coupled to the strain-induced out-of-plane rotation of the mesogen units, in turn driven by the increasing constraints on polymer configurations, as reflected in increasing elastic moduli and $\alpha$ relaxation times; this is consistent with our recent results showing that the auxetic response coincides with the emergence of biaxial order.

Liquid crystal elastomers (LCEs) are polymeric materials that are proposed for a range of applications. However, to reach their full potential, it is desirable to have as much flexibility as possible in terms of the sample dimensions, while maintaining well-defined alignment. In this work, photoinduced electron/energy transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization is applied to the synthesis of LCEs for the first time. An initial LCE layer (∼100 μm thickness) is partially cured before a second layer of the precursor mixture is added. The curing reaction is then resumed and is observed by FTIR to complete within 15 min of irradiation, yielding samples of increased thickness. Monodomain samples that exhibit an auxetic response and are of thickness 250-300 μm are consistently achieved. All samples are characterized thermally, mechanically, and in terms of their order parameters. The LCEs have physical properties comparable to those of analogous LCEs produced via free-radical polymerization.

A series of chemically similar liquid crystal elastomers which show an auxetic response at high cross-link densities and a semi-soft elastic response at low cross-link densities is presented. We suggest that these are extrema of continuum behaviour.