Shell Architecture Strongly Influences the Glass Transition, Surface Mobility, and Elasticity of Polymer Core-Shell Nanoparticles.

Despite the growing application of nanostructured polymeric materials, there still remains a large gap in our understanding of polymer mechanics and thermal stability under confinement and near polymer-polymer interfaces. In particular, the knowledge of polymer nanoparticle thermal stability and mechanics is of great importance for their application in drug delivery, phononics, and photonics. Here, we quantified the effects of a polymer shell layer on the modulus and glass-transition temperature (T g) of polymer core-shell nanoparticles via Brillouin light spectroscopy and modulated differential scanning calorimetry, respectively. Nanoparticles consisting of a polystyrene (PS) core and shell layers of poly(n-butyl methacrylate) (PBMA) were characterized as model systems. We found that the high T g of the PS core was largely unaffected by the presence of an outer polymer shell, whereas the lower T g of the PBMA shell layer decreased with increasing PBMA thickness. The surface mobility was revealed at a temperature about 15 K lower than the T g of the PBMA shell layer. Overall, the modulus of the core-shell nanoparticles decreased with increasing PBMA shell layer thickness. These results suggest that the nanoparticle modulus and T g can be tuned independently through the control of nanoparticle composition and architecture.

Estimating the Segregation Strength of Microphase-Separated Diblock Copolymers from the Interfacial Width.

The ever-growing catalog of monomers being incorporated into block polymers affords exceptional control over phase behavior and nanoscale structure. The segregation strength, χN, is the fundamental link between the molecular-level detail and the thermodynamics. However, predicting phase behavior mandates at least one experimental measurement of χN for each pair of blocks. This typically requires access to the disordered state. We describe a method for estimating χN from small-angle X-ray scattering measurements of the interfacial width between lamellar microdomains, tx, in the microphase-separated melt. The segregation strength is determined by comparing tx to self-consistent field theory calculations of the intrinsic interfacial width, ti, as a function of the mean-field χN. The method is validated using a series of independent experimental measurements of tx and χN, measured via the order-disorder transition temperature, TODT. The average absolute relative difference between χN calculated from tx and the value calculated from TODT is a modest 11%. Corrections for nonplanarity of the interfaces are investigated but do not improve the agreement between the experiments and theory. Published 2019. This article is a U.S. Government work and is in the public domain in the USA.

Direct Measurement of the Local Glass Transition in Self-Assembled Copolymers with Nanometer Resolution.

Nanoscale compositional heterogeneity in block copolymers can impart synergistic property combinations, such as stiffness and toughness. However, until now, there has been no experimental method to locally probe the dynamics at a specific location within these structured materials. Here, this was achieved by incorporating pyrene-bearing monomers at specific locations along the polymer chain, allowing the labeled monomers' local environment to be interrogated via fluorescence. In lamellar-forming poly(butyl methacrylate-b-methyl methacrylate) diblock copolymers, a strong gradient in glass transition temperature, Tg, of the higher-Tg block, 42 K over 4 nm, was mapped with nanometer resolution. These measurements also revealed a strongly asymmetric influence of the domain interface on Tg, with a much smaller dynamic gradient being observed for the lower-Tg block.

Role of Chain Connectivity across an Interface on the Dynamics of a Nanostructured Block Copolymer.

Fluorescence labeling enables component- and location-specific measurements of the glass transition temperature (T_{g}) in complex polymer systems. Here we characterize the T_{g} of fluorescently labeled poly(methyl methacrylate) homopolymers (PMMA-py) blended at low concentrations into an unlabeled lamellar poly(n-butyl methacrylate-b-methyl methacrylate) diblock copolymer (PBMA-PMMA). In this system, the PMMA-py homopolymer is sequestered within the PMMA domains of the diblock copolymer and subject to soft confinement by the domains of the lower-T_{g} PBMA block, which lowers the homopolymer T_{g} by ∼5 K beyond the contribution of segmental mixing. In contrast to the PMMA block in the diblock copolymer, the PMMA-py homopolymer is not covalently bound to the interdomain interface. A comparison of T_{g} for the homopolymers in the blends to T_{g} for diblock copolymers with equivalent labeled segment density profiles reveals that the homopolymer's T_{g} is consistently ∼10 K higher than for diblock segments at the same location within the domain structure, highlighting the dominant contribution of a covalent bond across the interface to the perturbation of the chain dynamics in the block copolymer.

Ultrathin Shell Layers Dramatically Influence Polymer Nanoparticle Surface Mobility.

Advances in nanoparticle synthesis, self-assembly, and surface coating or patterning have enabled a diverse array of applications ranging from photonic and phononic crystal fabrication to drug delivery vehicles. One of the key obstacles restricting its potential is structural and thermal stability. The presence of a glass transition can facilitate deformation within nanoparticles, thus resulting in a significant alteration in structure and performance. Recently, we detected a glassy-state transition within individual polystyrene nanoparticles and related its origin to the presence of a surface layer with enhanced dynamics compared to the bulk. The presence of this mobile layer could have a dramatic impact on the thermal stability of polymer nanoparticles. Here, we demonstrate how the addition of a shell layer, as thin as a single polymer chain, atop the nanoparticles could completely eliminate any evidence of enhanced mobility at the surface of polystyrene nanoparticles. The ultrathin polymer shell layers were placed atop the nanoparticles via two approaches: (i) covalent bonding or (ii) electrostatic interactions. The temperature dependence of the particle vibrational spectrum, as recorded by Brillouin light scattering, was used to probe the surface mobility of nanoparticles with and without a shell layer. Beyond suppression of the surface mobility, the presence of the ultrathin polymer shell layers impacted the nanoparticle glass transition temperature and shear modulus, albeit to a lesser extent. The implication of this work is that the core-shell architecture allows for tailoring of the nanoparticle elasticity, surface softening, and glass transition temperature.