Effect of Oligomer Addition on Tube Dilation in Polymer Nanocomposite Melts.

This study investigates the effect of adding oligomers on the rheological properties of polymer nanocomposite melts with the goal of enhancing the processability of nanocomposites. The scaling analysis of plateau modulus (GN ) is used in understanding the complex mechanical behavior of entangled poly(methyl acrylate) (PMA) melts upon oligomer addition. Increasing the oligomer amount led to a decrease in GN and an apparent degree of entanglement (Z) in the neat polymer melt. The particle dispersion states at two particle loadings with oligomer addition are examined in transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). The dilution exponent is found unchanged at 7 and 17 vol% particle loadings for the well-dispersed PMA-SiO2 nanocomposites compared to the neat PMA solution. These findings suggest that attractive particles with strong interfacial layers do not influence the tube dilution scaling of the polymer with the oligomer. To the contrary, composites with weak polymer-particle interfaces demonstrate phase separation of particles when oligomers are introduced and its exponent for tube dilution scaling reaches 4 at a particle loading of 17 vol%, potentially indicating that network-forming clusters influence chain entanglements in this scenario.

The effect of dynamically heterogeneous interphases on the particle dynamics of polymer nanocomposites.

The entanglements of dynamically asymmetric polymer layers influence relaxations of nanoparticles in polymer nanocomposites. In this work, the dynamics of polymer-adsorbed and polymer-grafted nanoparticles in a poly(methyl acrylate) matrix polymer was investigated using X-ray photon correlation spectroscopy (XPCS) to understand the role of chain rigidity and chemical heterogeneities in particle dynamics. Locations of dynamic heterogeneities close to nanoparticles and away from particle surfaces were examined with the comparison of adsorbed and grafted nanoparticles. Our results show that the chemical heterogeneities around dispersed nanoparticles transitioned the particle dynamics from Brownian diffusion into hyperdiffusion, and moreover, the high rigidity of chains in the chemically heterogeneous interfacial layers slowed down the particle dynamics. The hyperdiffusion measured both in grafted particles and adsorbed particles was attributed to the dense interfacial mixing of dynamically heterogeneous chains.

Ion channels in sulfonated copolymer-grafted nanoparticles in ionic liquids.

The use of ionic liquids as solvents for polymers or polymer-grafted nanoparticles provides an exciting feature to explore electrolyte-polymer interactions. 1-Hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HMIm-TFSI) can have specific interactions with the polymer through ion-dipole forces or hydrogen bonding. In this work, poly(methyl methacrylate)-b-poly(styrene sulfonate) (PMMA-b-PSS) copolymer-grafted Fe3O4 nanoparticles with different sulfonation levels (∼4.9 to 10.9 mol% SS) were synthesized, and their concentration dependent ionic conductivities were reported in acetonitrile and HMIm-TFSI/acetonitrile mixtures. We found that conductivity enhancement with the particle concentration in acetonitrile was due to the aggregation of grafted particles, resulting in sulfonic domain connectivity. The ionic conductivity was found to be related to the effective hopping transfer within ionic channels. On the contrary, the conductivity decreased or remained constant with increasing particle concentration in HMIm-TFSI/acetonitrile. This result was attributed to the ion coupling between ionic liquids and copolymer domains.

Confinement Effects in Dynamics of Ionic Liquids with Polymer-Grafted Nanoparticles.

Ionic liquid mixed with poly(methyl methacrylate)-grafted Fe3 O4 nanoparticle aggregates at low particle concentrations was found to exhibit different dynamics and ionic conductivity than that of pure ionic liquid in our previous studies. In this work, we report on the quasi-elastic neutron scattering results of ionic liquid containing polymer-grafted Fe3 O4 nanoparticles at higher particle concentrations. The diffusivity of imidazolium (HMIM+ ) cations of 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HMIM-TFSI) in the presence of poly(methyl methacrylate)-grafted Fe3 O4 nanoparticles is discussed through the confinement. Analysis of the elastic incoherent structure factor revealed that the confinement radius decreased with the addition of grafted particles in HMIM-TFSI/solvent mixture. We propose the confinement that is induced by the high concentration of grafted particles shrinks the HMIM-TFSI restricted volume. We further conjecture that this enhanced diffusivity occurs as a result of the local ordering of cations within aggregates of poly(methyl methacrylate)-grafted Fe3 O4 nanoparticles.

Solvation in Ionic Liquids with Polymer-Grafted Nanoparticles.

Polymer-grafted nanoparticles stabilized in ionic liquid (IL)-solvent mixtures are investigated by using transmission electron microscopy, dynamic light scattering, and electrochemical impedance spectroscopy. The ionic conductivity of IL-solvent mixtures with the polymer-grafted nanoparticles is found to be higher than that of nanoparticles in the IL. These particles offer additional interactions between polymer and IL, which can mitigate solvation in ILs with solvents. Motivated by this, we present the conductivity data of 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HMIM-TFSI) with poly(methyl methacrylate) (PMMA)-grafted particles in good and bad solvents and further discuss how graft density influences the swelling of PMMA and solvation characteristics of HMIM-TFSI. We found that HMIM-TFSI-acetonitrile containing high grafting density particles has a higher conductivity than that of the HMIM-TFSI-methanol mixture with grafted particles. Thus, solubility of PMMA in acetonitrile and preferential interactions between PMMA-HMIM-TFSI are shown to govern the swelling, solvation, and conductive properties of IL with the polymer-grafted nanoparticles.

Dynamics of ionic liquids in the presence of polymer-grafted nanoparticles.

We incorporated polymer-grafted nanoparticles into ionic and zwitterionic liquids to explore the solvation and confinement effects on their heterogeneous dynamics using quasi-elastic neutron scattering (QENS). 1-Hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HMIM-TFSI) mixed with deuterated poly(methyl methacrylate) (d-PMMA)-grafted nanoparticles is studied to unravel how dynamic coupling between PMMA and HMIM-TFSI influence the fast and slow diffusion characteristics of the HMIM+ cations. The zwitterionic liquid, 1-butyl-3-methyl imidazole-2-ylidene borane (BMIM-BH3) is critically selected and mixed with PMMA-grafted nanoparticles for comparison in this work as its ions do not self-dissociate and it does not couple with PMMA through ion-dipole interactions as HMIM-TFSI does. We find that long-range unrestricted diffusion of HMIM+ cations is higher in well-dispersed particles than in aggregated particle systems, whereas the localized diffusion of HMIM+ is measured to be higher in close-packed particles. Translational diffusion dynamics of BMIM-BH3 is not influenced by any particle structures suggesting that zwitterions do not interact with PMMA. This difference between two ionic liquid types enables us to decouple polymer effects from the diffusion of ionic liquids, which is integral to understand the ionic transport mechanism in ionic liquids confined in polymer-grafted nanoparticle electrolytes.

Deformation of Chemically Heterogeneous Interfacial Layers of Polymer Nanocomposites.

Dynamics of entangled interfacial polymer layers around nanoparticles determine the linear rheological properties of polymer nanocomposites. In this study, the nonlinear elastic properties of nanocomposites are examined under large-amplitude oscillatory shear (LAOS) flow to reveal the effect of interfacial chemical heterogeneity on the deformation mechanism of polymer-grafted and polymer-adsorbed nanoparticle composites. Adsorbed-poly(methyl methacrylate) (PMMA) layers presented stronger interfacial stiffening and reinforcement than PMMA-grafted layers. Chemical heterogeneities of interfacial layers, provided by polymer-adsorbed and low graft density particles, deformed at smaller strains than the poly(ethylene oxide) (PEO) matrix. Interfaces of loosely bound PMMA and PEO exhibited stiffening at low strains due to the enhanced chain mixing and entanglements. These results demonstrate that chemical and dynamic heterogeneities in interfacial layers have significant importance in designing adaptive polymer nanocomposites for large shear deformation.

Chemical heterogeneity in interfacial layers of polymer nanocomposites.

It is well-known that particle-polymer interactions strongly control the adsorption and conformations of adsorbed chains. Interfacial layers around nanoparticles consisting of adsorbed and free matrix chains have been extensively studied to reveal their rheological contribution to the behavior of nanocomposites. This work focuses on how chemical heterogeneity of the interfacial layers around the particles governs the microscopic mechanical properties of polymer nanocomposites. Low glass-transition temperature composites consisting of poly(vinyl acetate) coated silica nanoparticles in poly(ethylene oxide) and poly(methyl acrylate) matrices, and of poly(methyl methacrylate) silica nanoparticles in a poly(methyl acrylate) matrix are examined using rheology and X-ray photon correlation spectroscopy. We demonstrate that miscibility between the adsorbed and matrix chains in the interfacial layers led to the observed unusual reinforcement. We suggest that packing of chains in the interfacial regions may also contribute to the reinforcement in the polymer nanocomposites. These features may be used in designing mechanically adaptive composites operating at varying temperature.

Examining lysozyme structures on polyzwitterionic brush surfaces.

Conformational structures of lysozyme at the interfaces of hydrophilic polymer poly[2-(methacryloyloxy)ethyl dimethyl-(3-sulfopropyl)ammonium hydroxide] (PMEDSAH), are examined to understand the role of protein-polymer interactions on the stability of lysozyme. This work underpins the effect of hydration layer on the structures of physically adsorbed lysozyme on PMEDSAH brushes. Hydrophilic nature and strength of hydration layers around brushes are controlled by varying the brush thickness and temperature. We measured that lysozyme is structurally less stable on 15nm thick hydrophilic PMEDSAH brushes at 75°C than at room temperature. To the contrary, 5-8nm thick brushes stretch in hydrated state by heating, hence yield higher structural stability of lysozyme. These results suggest that short polyzwitterionic brushes can facilitate improved biomaterial interactions that are essential for biosensors performing at elevated temperatures.

Confinement effect on the structure and elasticity of proteins interfacing polymers.

The ordered nanostructured surfaces provide confined environments that allow functionalization of proteins. Here, we used the nanopores of poly(methyl methacrylate) films to attach fibrinogen and lysozyme, and discussed the changes in proteins' structures and elasticity upon confinement. Fourier-transform infrared spectroscopic analysis of protein secondary structures reveals that fibrinogen undergoes less structural change and behaves less stiff when the pore size is close to the protein size. Lysozyme, on the other hand, retains its native-like structure, however, it exhibits the highest modulus in 15 nm pores due to the lower macromolecular crowding effect the protein faces compared to lysozyme within larger pores. These findings manifest the effect of confinement and crowding on the conformation and elasticity of different shaped proteins tethered on surfaces.

Microscopic Chain Motion in Polymer Nanocomposites with Dynamically Asymmetric Interphases.

Dynamics of the interphase region between matrix and bound polymers on nanoparticles is important to understand the macroscopic rheological properties of nanocomposites. Here, we present neutron scattering investigations on nanocomposites with dynamically asymmetric interphases formed by a high-glass transition temperature polymer, poly(methyl methacrylate), adsorbed on nanoparticles and a low-glass transition temperature miscible matrix, poly(ethylene oxide). By taking advantage of selective isotope labeling of the chains, we studied the role of interfacial polymer on segmental and collective dynamics of the matrix chains from subnanoseconds to 100 nanoseconds. Our results show that the Rouse relaxation remains unchanged in a weakly attractive composite system while the dynamics significantly slows down in a strongly attractive composite. More importantly, the chains disentangle with a remarkable increase of the reptation tube size when the bound polymer is vitreous. The glassy and rubbery states of the bound polymer as temperature changes underpin the macroscopic stiffening of nanocomposites.

Elastic Properties of Protein Functionalized Nanoporous Polymer Films.

Retaining the conformational structure and bioactivity of immobilized proteins is important for biosensor designs and drug delivery systems. Confined environments often lead to changes in conformation and functions of proteins. In this study, lysozyme is chemically tethered into nanopores of polystyrene thin films, and submicron pores in poly(methyl methacrylate) films are functionalized with streptavidin. Nanoindentation experiments show that stiffness of streptavidin increases with decreasing submicron pore sizes. Lysozymes in polystyrene nanopores are found to behave stiffer than the submicron pore sizes and still retain their specific bioactivity relative to the proteins on flat surfaces. Our results show that protein functionalized ordered nanoporous polystyrene/poly(methyl methacrylate) films present heterogeneous elasticity and can be used to study interactions between free proteins and designed surfaces.

Structure and Entanglement Factors on Dynamics of Polymer-Grafted Nanoparticles.

Nanoparticles functionalized with long polymer chains at low graft density are interesting systems to study structure-dynamic relationships in polymer nanocomposites since they are shown to aggregate into strings in both solution and melts and also into spheres and branched aggregates in the presence of free polymer chains. This work investigates structure and entanglement effects in composites of polystyrene-grafted iron oxide nanoparticles by measuring particle relaxations using X-ray photon correlation spectroscopy. Particles within highly ordered strings and aggregated systems experience a dynamically heterogeneous environment displaying hyperdiffusive relaxation commonly observed in jammed soft glassy systems. Furthermore, particle dynamics is diffusive for branched aggregated structures which could be caused by less penetration of long matrix chains into brushes. These results suggest that particle motion is dictated by the strong interactions of chains grafted at low density with the host matrix polymer.

Reversible Thermal Stiffening in Polymer Nanocomposites.

Miscible polymer blends with different glass transition temperatures (Tg) are known to create confined interphases between glassy and mobile chains. Here, we show that nanoparticles adsorbed with a high-Tg polymer, poly(methyl methacrylate), and dispersed in a low-Tg matrix polymer, poly(ethylene oxide), exhibit a liquid-to-solid transition at temperatures above Tg's of both polymers. The mechanical adaptivity of nanocomposites to temperature underlies the existence of dynamically asymmetric bound layers on nanoparticles and more importantly reveals their impact on macroscopic mechanical response of composites. The unusual reversible stiffening behavior sets these materials apart from conventional polymer composites that soften upon heating. The presented stiffening mechanism in polymer nanocomposites can be used in applications for flexible electronics or mechanically induced actuators responding to environmental changes like temperature or magnetic fields.

Understanding the role of grafted polystyrene chain conformation in assembly of magnetic nanoparticles.

Polystyrene-grafted iron oxide nanoparticles have been shown to phase separate into ordered morphologies of strings, well-dispersed particles, and spherical aggregates at low graft densities in polymer matrices. In this work, small-angle neutron scattering experiments are performed to reveal the role of grafted chain conformation on nanoparticle assemblies. We demonstrate that chains grafted at low densities follow Gaussian statistics at any dispersion states. These results suggest that grafted chains are not distorted but remain Gaussian when particles are aggregated into strings. Small-angle x-ray and neutron scattering results show that matrix chains do not influence the formation of strings, but have a significant impact on the size and internal structure of aggregated particles. We conclude that spherical aggregates of nanoparticles with low polymer graft densities are akin to interpenetrating networks in which free matrix chains bridge the fractals of particles and control the cluster density.

Modulating interfacial attraction of polymer-grafted nanoparticles in melts under shear.

The mechanical properties of polymer nanocomposites are significantly affected by spatial ordering of nanoparticles (NPs) which can be modified under shear flow fields. Polymer-grafted iron oxide NPs form strings, well-dispersed, and percolated anisotropic nanostructures depending on grafting density, and herein their mechanical properties under large oscillatory shear flows are reported. We show that flow-induced alignment of NPs is achieved with string-like structures at low particle loadings (5 wt%). Further, entropic surface tension between grafted and free chains decreases by facilitating the penetration of long matrix chains into the grafts with oscillatory shear flow. Consequently, the degree of entanglements at large strain amplitudes is enhanced which is reflected in elastic properties. These results indicate that the matrix polymer plays an effective role in the reinforcement of polymer-grafted NPs under large shear flow fields.

Spatial ordering of colloids in a drying aqueous polymer droplet.

We explore the role of polymer chains on deposition of colloidal particles at solid surfaces from drying aqueous drops and show that the kinetics of phase separation of colloids and polymers can be explained by spinodal decomposition of binary systems. Concentrations of polymer solutions and polymer chain lengths were varied to understand the aggregation dynamics of colloidal particles via a polymer bridging mechanism. We show that when polymer concentration in the droplet is increased, particles spatially order upon drying due to a combination of the phase separation of highly bridged particles and the Marangoni flow effect. The demonstrated effect of particle-adsorbing, water-soluble polymers on the coffee-ring formation opens up new ways of creating highly ordered, long-range patterned surfaces using a facile, template-free approach.

Programmable light-controlled shape changes in layered polymer nanocomposites.

We present soft, layered nanocomposites that exhibit controlled swelling anisotropy and spatially specific shape reconfigurations in response to light irradiation. The use of gold nanoparticles grafted with a temperature-responsive polymer (poly(N-isopropylacrylamide), PNIPAM) with layer-by-layer (LbL) assembly allowed placement of plasmonic structures within specific regions in the film, while exposure to light caused localized material deswelling by a photothermal mechanism. By layering PNIPAM-grafted gold nanoparticles in between nonresponsive polymer stacks, we have achieved zero Poisson's ratio materials that exhibit reversible, light-induced unidirectional shape changes. In addition, we report rheological properties of these LbL assemblies in their equilibrium swollen states. Moreover, incorporation of dissimilar plasmonic nanostructures (solid gold nanoparticles and nanoshells) within different material strata enabled controlled shrinkage of specific regions of hydrogels at specific excitation wavelengths. The approach is applicable to a wide range of metal nanoparticles and temperature-responsive polymers and affords many advanced build-in options useful in optically manipulated functional devices, including precise control of plasmonic layer thickness, tunability of shape variations to the excitation wavelength, and programmable spatial control of optical response.

Elastic properties of a protein-polymer-grafted surface.

Surfaces grafted with poly(methyl methacrylate) (PMMA) and streptavidin were synthesized through click chemistry to investigate the role of surface stiffness on protein adsorption as the hydrophilic and hydrophobic surface coverage of the substituents vary. Surface topographies coupled with the nanoindentation results indicated that, with the appropriate selections of polymer coverage and chain length, the extent of non-specific protein adhesion could be controlled by the hydrophobic interactions between PMMA, biotin, and streptavidin. It was shown that, when the molecular weight and stiffness of PMMA was close to that of streptavidin, patchy PMMA morphologies were obtained, which help inhibit the non-specific adsorption of streptavidin.

A Rheological Study of Biodegradable Injectable PEGMC/HA Composite Scaffolds.

Injectable biodegradable hydrogels, which can be delivered in a minimally invasive manner and formed in situ, have found a number of applications in pharmaceutical and biomedical applications, such as drug delivery and tissue engineering. We have recently developed an in situ crosslinkable citric acid-based biodegradable poly (ethylene glycol) maleate citrate (PEGMC)/hydroxyapatite (HA) composite, which shows promise for use in bone tissue engineering. In this study, the mechanical properties of the PEGMC/HA composites were studied in dynamic linear rheology experiments. Critical parameters such as monomer ratio, crosslinker, initiator, and HA concentrations were varied to reveal their effect on the extent of crosslinking as they control the mechanical properties of the resultant gels. The rheological studies, for the first time, allowed us investigating the physical interactions between HA and citric acid-based PEGMC. Understanding the viscoelastic properties of the injectable gel composites is crucial in formulating suitable injectable PEGMC/HA scaffolds for bone tissue engineering, and should also promote the other biomedical applications based on citric acid-based biodegradable polymers.