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Unlike inorganic nanoparticles, organic nanoparticles (oNPs) offer the advantage of “interior tailorability,” thereby enabling the controlled variation of physicochemical characteristics and functionalities, for example, by incorporation of diverse functional small molecules. In this study, a unique inimer-based microemulsion approach is presented to realize oNPs with enhanced control of chemical and mechanical properties by deliberate variation of the degree of hyperbranching or cross-linking. The use of anionic cosurfactants led to oNPs with superior uniformity. Benefitting from the high initiator concentration from inimer and preserved chain-end functionality during atom transfer radical polymerization (ATRP), the capability of oNPs as a multifunctional macroinitiator for the subsequent surface-initiated ATRP was demonstrated. This facilitated the synthesis of densely tethered poly(methyl methacrylate) brush oNPs. Detailed analysis revealed that exceptionally high grafting densities (~1 nm⁻²) were attributable to multilayer surface grafting from oNPs due to the hyperbranched macromolecular architecture. The ability to control functional attributes along with elastic properties renders this “bottom-up” synthetic strategy of macroinitiator-type oNPs a unique platform for realizing functional materials with a broad spectrum of applications. 

Abstract Brillouin light scattering and elastodynamic theory are concurrently used to determine and interpret the hypersonic phonon dispersion relations in brush particle solids as a function of the grafting density with perspectives in optomechanics, heat management, and materials metrology. In the limit of sparse grafting density, the phonon dispersion relations bear similarity to polymer‐embedded colloidal assembly structures in which phonon dispersion can be rationalized on the basis of perfect boundary conditions, i.e., isotropic stiffness transitions across the particle interface. In contrast, for dense brush assemblies, more complex dispersion characteristics are observed that imply anisotropic stiffness transition across the particle/polymer interface. This provides direct experimental validation of phonon propagation changes associated with chain conformational transitions in dense particle brush materials. A scaling relation between interface tangential stiffness and crowding of polymer tethers is derived that provides a guideline for chemists to design brush particle materials with tailored phononic dispersion characteristics. The results emphasize the role of interfaces in composite materials systems. Given the fundamental relevance of phonon dispersion to material properties such as thermal transport or mechanical properties, it is also envisioned that the results will spur the development of novel functional hybrid materials. 

Abstract Liquid crystal elastomers that offer exceptional load-deformation response at low frequencies often require consideration of the mechanical anisotropy only along the two symmetry directions. However, emerging applications operating at high frequencies require all five true elastic constants. Here, we utilize Brillouin light spectroscopy to obtain the engineering moduli and probe the strain dependence of the elasticity anisotropy at gigahertz frequencies. The Young’s modulus anisotropy, E || / E ⊥ ~2.6, is unexpectedly lower than that measured by tensile testing, suggesting disparity between the local mesogenic orientation and the larger scale orientation of the network strands. Unprecedented is the robustness of E || / E ⊥ to uniaxial load that it does not comply with continuously transformable director orientation observed in the tensile testing. Likewise, the heat conductivity is directional, κ || / κ ⊥ ~3.0 with κ ⊥ = 0.16 Wm −1 K −1 . Conceptually, this work reveals the different length scales involved in the thermoelastic anisotropy and provides insights for programming liquid crystal elastomers on-demand for high-frequency applications. 

Abstract Glasses are generally assumed to be isotropic and there are no literature reports of elastic anisotropy for molecular glasses. However, as glasses formed by physical vapor deposition can be structurally anisotropic, it is of interest to investigate the elastic anisotropy in these materials. Micro‐Brillouin light spectroscopy is used in several experimental geometries to determine the elastic stiffness tensors of three glass films of itraconazole vapor‐deposited at substrate temperatures (T_sub) of 330, 315, and 290 K, respectively. Significant elastic anisotropy is observed and, in these glasses, the elastic anisotropy shows a strong correlation with the molecular orientation. The out‐of‐plane and in‐plane Young's moduli of the highT_sub(330 K) sample, which features a predominantly vertical molecular orientation, exhibit a high anisotropy ratio of 2.2. The observed elastic anisotropy is much larger than those previously observed in liquid crystals and even many crystalline solids. 

Abstract Photothermal energy conversion is of fundamental importance to applications ranging from drug delivery to microfluidics and from ablation to fabrication. It typically originates from absorptive processes in materials that—when coupled with non‐radiative dissipative processes—allow the conversion of radiative energy into heat. Microstructure design provides versatile strategies for controlling light–matter interactions. In particular, the deliberate engineering of the band structure in photonic materials is known to be an effective approach to amplify absorption in materials. However, photonic amplification is generally tied to high optical contrast materials which limit the applicability of the concept to metamaterials such as microfabricated metal–air hybrids. This contribution describes the first observation of pronounced amplification of absorption in low contrast opals formed by the self‐assembly of polymer‐tethered particles. The dependence of the amplification factor on the length scale and degree of order of materials as well as the angle of incidence reveal that it is related to the slow photon effect. A remarkable amplification factor of 16 is shown to facilitate the rapid “melting” of opal films even in the absence of “visible” absorption. The results point to novel opportunities for tailoring light–matter interactions in hybrid materials that can benefit the manipulation and fabrication of functional materials.