Over the past three decades, the combination of inorganic-nanoparticles and organic-polymers has led to a wide variety of advanced materials, including polymer nanocomposites (PNCs). Recently, synthetic innovations for attaching polymers to nanoparticles to create "hairy nanoparticles" (HNPs) has expanded opportunities in this field. In addition to nanoparticle compatibilization for traditional particle-matrix blending, neat-HNPs afford one-component hybrids, both in composition and properties, which avoids issues of mixing that plague traditional PNCs. Continuous improvements in purity, scalability, and theoretical foundations of structure-performance relationships are critical to achieving design control of neat-HNPs necessary for future applications, ranging from optical, energy, and sensor devices to lubricants, green-bodies, and structures.
The solution-processing of conjugated polymers, just like commodity polymers, is subject to solvent and molecular weight-dependent solubility, interactions and chain entanglements within the polymer, all of which can influence the crystallization and microstructure development in semi-crystalline polymers and consequently affect charge transport and optoelectronic properties. Disentanglement of polymer chains in marginal solvents was reported to work via ultrasonication, facilitating the formation of photophysically ordered polymer aggregates. In this contribution, we explore how a wide range of technologically relevant solvents and formulations commonly used in organic electronics influence chain entanglement and the aggregation behaviour of P3HT using a combination of rheological and spectrophotometric measurements. The specific viscosity of the solution offers an excellent indication of the degree of entanglements in the solution, which is found to be related to the solubility of P3HT in a given solvent. Moreover, deliberately disentangling the solution in the presence of solvophobic driving forces, leads consistently to formation of photophysically visible aggregates which is indicative of local and perhaps long range order in the solute. We show for a broad range of solvents and molecular weights that disentanglement ultimately leads to significant ordering of the polymer in the solid state and a commensurate increase in charge transport properties. In doing so we demonstrate a remarkable ability to tune the microstructure which has important implications for transport properties. We discuss its potential implications in the context of organic electronics and photovoltaics
Within the general field of polymer grafted or "hairy" nanoparticles, nanoscale ionic materials (NIMs), consisting of a soft polymeric canopy bound to a well-defined nanoparticle core by an ionic bond, occupy a growing niche. They are the first example of neat, self-suspended fluids of nanoparticles (i.e., in the absence of a suspending medium). As such, the perennial dispersion challenges associated with polymer nanocomposites are minimized while the dynamic nature of the ionic bonds provides opportunities for selfhealing behavior. Combining the properties of ionic liquids, charged colloid suspensions, and well-dispersed nanocomposites, this new materials platform offers remarkable versatility for current and future applications. This perspective covers techniques and current challenges in synthesis, discusses the state of understanding of the theory behind their structure and properties, and examines successes and future prospects in application in a number of areas, notably in energy-related technologies.
We report an ionic hybrid based on silica nanoparticles as the anion and amine-terminated poly(ethylene oxide) (PEO) as a cation. The charge on the nanoparticle anion is carried by the surface hydroxyls. SAXS and TEM reveal an exceptional degree of dispersion of the silica in the polymer and high degree of order in both thin film and bulk forms. In addition to better dispersion, the ionic hybrid shows improved flow characteristics compared to silica/PEO mixtures in which the ionic interactions are absent.
We report for the first time an ionic fluid based on hydroxylated fullerenes (fullerols). The ionic fluid was synthesized by neutralizing the fully protonated fullerol with an amine terminated polyethylene/polypropylene oxide oligomer (Jeffamine). The ionic fluid was compared to a control synthesized by mixing the partially protonated form (sodium form) of the fullerols with the same oligomeric amine in the same ratio as in the ionic fluids (20 wt% fullerol). In the fullerol fluid the ionic bonding significantly perturbs the thermal transitions and melting/crystallization behavior of the amine. In contrast, both the normalized heat of fusion and crystallization of the amine in the control are similar to those of the neat amine consistent with a physical mixture of the fullerols/amine with minimal interactions. In addition to differences in thermal behavior, the fullerol ionic fluid exhibits a complex viscoelastic behavior intermediate between the neat Jeffamine (liquid-like) and the control (solid-like).
Nanoscale ionic materials (NIMs) are organic–inorganic hybrids prepared from ionically functionalized nanoparticles (NP) neutralized by oligomeric polymer counterions. NIMs are designed to behave as liquids under ambient conditions in the absence of solvent and have no volatile organic content, making them useful for a number of applications. We have used nuclear magnetic resonance relaxation and pulsed-field gradient NMR to probe local and collective canopy dynamics in NIMs based on 18-nm silica NPs with a covalently bound anionic corona, neutralized by amine-terminated ethylene oxide/propylene oxide block copolymers. The NMR relaxation studies show that the nanosecond-scale canopy dynamics depend on the degree of neutralization, the canopy radius of gyration, and crowding at the ionically modified NP surface. Two canopy populations are observed in the diffusion experiments, demonstrating that one fraction of the canopy is bound to the NP surface on the time scale (milliseconds) of the diffusion experiment and is surrounded by a more mobile layer of canopy that is unable to access the surface due to molecular crowding. The introduction of electrolyte ions (Na+ or Mg2+) screens the canopy–corona electrostatic interactions, resulting in a reduced bulk viscosity and faster canopy exchange. The magnitude of the screening effect depends upon ion concentration and valence, providing a simple route for tuning the macroscopic properties of NIMs.
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