Segmental and secondary dynamics of nanoparticle-grafted oligomers.

The local segmental and secondary dynamics of tetramethylene oxide oligomer grafted to silica nanoparticles (NPs) were investigated as a function of grafting density and molecular weight. Grafting slows the segmental (α) dynamics, but gives rise to faster secondary (ß) motions. Interestingly, the magnitude of these effects decreases with the extent of grafting (i.e., surface coverage), as well as with oligomer molecular weight. The disparity in dynamical effects reflects the decoupling of the segmental and more local ß dynamics, the former is associated with stronger dynamic correlations that extend over a greater spatial range. This results in greater sensitivity to interactions, including tethering of the chains to the NP surface.

Unraveling the Mechanism of Nanoscale Mechanical Reinforcement in Glassy Polymer Nanocomposites.

The mechanical reinforcement of polymer nanocomposites (PNCs) above the glass transition temperature, Tg, has been extensively studied. However, not much is known about the origin of this effect below Tg. In this Letter, we unravel the mechanism of PNC reinforcement within the glassy state by directly probing nanoscale mechanical properties with atomic force microscopy and macroscopic properties with Brillouin light scattering. Our results unambiguously show that the "glassy" Young's modulus in the interfacial polymer layer of PNCs is two-times higher than in the bulk polymer, which results in significant reinforcement below Tg. We ascribe this phenomenon to a high stretching of the chains within the interfacial layer. Since the interfacial chain packing is essentially temperature independent, these findings provide a new insight into the mechanical reinforcement of PNCs also above Tg.

Unexpected Molecular Weight Effect in Polymer Nanocomposites.

The properties of the interfacial layer between the polymer matrix and nanoparticles largely determine the macroscopic properties of polymer nanocomposites (PNCs). Although the static thickness of the interfacial layer was found to increase with the molecular weight (MW), the influence of MW on segmental relaxation and the glass transition in this layer remains to be explored. In this Letter, we show an unexpected MW dependence of the interfacial properties in PNC with attractive polymer-nanoparticle interactions: the thickness of the interfacial layer with hindered segmental relaxation decreases as MW increases, in sharp contrast to theoretical predictions. Further analyses reveal a reduction in mass density of the interfacial layer with increasing MW, which can elucidate these unexpected dynamic effects. Our observations call for a significant revision of the current understandings of PNCs and suggest interesting ways to tailor their properties.

Communication: Influence of nanophase segregation on ion transport in room temperature ionic liquids.

We report measurements of the ionic conductivity, shear viscosity, and structural dynamics in a homologous series of quaternary ammonium ionic liquids (ILs) and a prototypical imidazolium-based IL over a wide range of temperatures down to the glass transition. We find that the ionic conductivity of these materials generally decreases, while the shear viscosity correspondingly increases, with increasing volume fraction of aliphatic side groups. Upon crossing an aliphatic volume fraction of ∼0.40, we observe a sharp, order-of-magnitude decrease in ionic conductivity and enhancement of viscosity, which coincides with the presence of long-lived, nanometer-sized alkyl aggregates. These strong changes in dynamics are not mirrored in the ionicity of these ILs, which decreases nearly linearly with aliphatic volume fraction. Our results demonstrate that nanophase segregation in neat ILs strongly reduces ionic conductivity primarily due to an aggregation-induced suppression of dynamics.

Ion transport and structural dynamics in homologous ammonium and phosphonium-based room temperature ionic liquids.

Charge transport and structural dynamics in a homologous pair of ammonium and phosphonium based room temperature ionic liquids (ILs) have been characterized over a wide temperature range using broadband dielectric spectroscopy and quasi-elastic light scattering spectroscopy. We have found that the ionic conductivity of the phosphonium based IL is significantly enhanced relative to the ammonium homolog, and this increase is primarily a result of a lower glass transition temperature and higher ion mobility. Additionally, these ILs exhibit pronounced secondary relaxations which are strongly influenced by the atomic identity of the cation charge center. While the secondary relaxation in the phosphonium IL has the expected Arrhenius temperature dependence characteristic of local beta relaxations, the corresponding relaxation process in the ammonium IL was found to exhibit a mildly non-Arrhenius temperature dependence in the measured temperature range-indicative of molecular cooperativity. These differences in both local and long-range molecular dynamics are a direct reflection of the subtly different inter-ionic interactions and mesoscale structures found in these homologous ILs.

Unraveling the Molecular Weight Dependence of Interfacial Interactions in Poly(2-vinylpyridine)/Silica Nanocomposites.

The structure and polymer-nanoparticle interactions among physically adsorbed poly(2-vinylpyridine) chains on the surface of silica nanoparticles (NPs) were systematically studied as a function of molecular weight (MW) by sum frequency generation (SFG) and X-ray photoelectron (XPS) spectroscopies. Analysis of XPS data identified hydrogen bonds between the polymer and NPs, while SFG evaluated the change in the number of free OH sites on the NP's surface. Our data revealed that the hydrogen bonds and amount of the free -OH sites have a significant dependence on the polymer's MW. These results provide clear experimental evidence that the interaction of physically adsorbed chains with nanoparticles is strongly MW dependent and aids in unraveling the microscopic mechanism responsible for the strong MW dependence of dynamics of the interfacial layer in polymer nanocomposites.

Controlling Interfacial Dynamics: Covalent Bonding versus Physical Adsorption in Polymer Nanocomposites.

It is generally believed that the strength of the polymer-nanoparticle interaction controls the modification of near-interface segmental mobility in polymer nanocomposites (PNCs). However, little is known about the effect of covalent bonding on the segmental dynamics and glass transition of matrix-free polymer-grafted nanoparticles (PGNs), especially when compared to PNCs. In this article, we directly compare the static and dynamic properties of poly(2-vinylpyridine)/silica-based nanocomposites with polymer chains either physically adsorbed (PNCs) or covalently bonded (PGNs) to identical silica nanoparticles (RNP = 12.5 nm) for three different molecular weight (MW) systems. Interestingly, when the MW of the matrix is as low as 6 kg/mol (RNP/Rg = 5.4) or as high as 140 kg/mol (RNP/Rg= 1.13), both small-angle X-ray scattering and broadband dielectric spectroscopy show similar static and dynamic properties for PNCs and PGNs. However, for the intermediate MW of 18 kg/mol (RNP/Rg = 3.16), the difference between physical adsorption and covalent bonding can be clearly identified in the static and dynamic properties of the interfacial layer. We ascribe the differences in the interfacial properties of PNCs and PGNs to changes in chain stretching, as quantified by self-consistent field theory calculations. These results demonstrate that the dynamic suppression at the interface is affected by the chain stretching; that is, it depends on the anisotropy of the segmental conformations, more so than the strength of the interaction, which suggests that the interfacial dynamics can be effectively tuned by the degree of stretching-a parameter accessible from the MW or grafting density.

Charge transport and structural dynamics in carboxylic-acid-based deep eutectic mixtures.

Charge transport and structural dynamics in the 1:2 mol ratio mixture of lidocaine and decanoic acid (LID-DA), a model deep eutectic mixture (DEM), have been characterized over a wide temperature range using broad-band dielectric spectroscopy and depolarized dynamic light scattering. Additionally, Fourier transform infrared spectroscopy measurements were performed to assess the degree of proton transfer between the neutral parent molecules. From our detailed analysis of the dielectric spectra, we have determined that this carboxylic-acid-based DEM is approximately 25% ionic at room temperature. Furthermore, we have found that the characteristic diffusion rate of mobile charge carriers is practically identical to the rate of structural relaxation at all measured temperatures, indicating that fast proton transport does not occur in LID-DA. Our results demonstrate that while LID-DA exhibits the thermal characteristics of a DEM, its charge transport properties resemble those of a protic ionic liquid.

Interplay between hydrophobic aggregation and charge transport in the ionic liquid methyltrioctylammonium bis(trifluoromethylsulfonyl)imide.

In order to understand the nature of the exceedingly low ionic conductivity of aprotic ammonium ionic liquids (ILs), we have measured the charge transport and structural dynamics of methyltrioctylammonium bis(trifluoromethylsulfonyl)imide [m3oa][ntf2] over a broad temperature range using broadband dielectric spectroscopy, depolarized dynamic light scattering (DDLS), rheology, and pulsed field gradient nuclear magnetic resonance. We demonstrate that the low level of ionic conductivity in this material is due to the combined effects of reduced ion mobility as well as reduced free ion concentration relative to other types of ILs. Furthermore, detailed analysis of the DDLS spectra reveals a slow process in addition to the structural α relaxation that we attribute to reorientational motion of alkyl aggregates. These findings indicate that hydrophobic aggregation strongly influences the charge transport mechanism of aprotic ammonium ionic liquids with long aliphatic side chains.