Viscosity of polyelectrolyte-grafted nanoparticle solutions.

The effect of charges and hydrogen bonding on viscosity in solutions containing polyelectrolyte-grafted nanoparticles (PENP) has been investigated using molecular dynamics (MD) simulations. The electrostatic interaction between the charged monomers on the grafted chains, which increases with the degree of ionization, causes the grafted polymers to stretch and increases the hydrodynamic size of the nanoparticles. The viscosity of the solution is partially governed by the balance between the entanglement of grafted chains and the electrostatic repulsion. Moreover, the charge-assisted hydrogen bonds between the monomers of different particles further enhance the viscosity of the solution. For shorter grafted chains, a majority of hydrogen bonds are formed within the same particle and thus show no significant enhancement in viscosity. The addition of polymer chains with hydrogen bonding sites has been shown to bridge multiple nanoparticles, creating a network structure, that increases viscosity. The chain stiffness has been shown to have a direct correlation with bridging and thus the viscosity of the solution.

Poly(3-hexylthiophene) (P3HT) and Phenyl-C61-Butyric Acid Methyl Ester (PC61BM) Based Bulk Heterojunction Solar Cells Containing Silica and Titanium Dioxide Nanorods: Molecular Dynamics Simulations.

Molecular dynamics simulations are used to demonstrate the effects of introducing anisotropicallyshaped silica (SiO2) and titanium dioxide (TiO2) nanoparticles on the morphology of poly(3-hexylthiophene) (P3HT)-phenyl-C61-butyric acid methyl ester (PC61BM) bulk heterojunction (BHJ) solar cells. The morphological compatibility and structure formation upon introduction of nanorods to the mixture of P3HT and PCBM are systematically studied by calculating several parameters that are known to influence the performance of BHJ. The anisotropically-shaped nanorods self-assemble into a variety of macroscopic structures, depending on the aspect ratio, and alter the phase morphology of PCBM. Several morphological properties such as domain size, crystallinity of the polymer phase and surface area of contact between P3HT and PCBM are found to be influenced by the presence of these nanorods. At low aspect ratios of the nanorods, the nanorod-PCBM clusters formed are kinetically-trapped and heavily branched, resulting in lower P3HT domain size and crystallinity. As the aspect ratio increases, the nanorods align parallel to each other and form two-dimensional sheet-like structures with PCBM. The P3HT crystallinity near the surface of longer nanorods were found to be higher. These changes in the morphological properties of the bulk heterojunction can be used as a benchmark to study the ternary blend solar cells with enhanced power conversion efficiency.

Viscosity and fragility of confined polymer nanocomposites: a tale of two interfaces.

Viscosity and fragility are key parameters determining the processability and thermo-mechanical stability of glassy polymers and polymer nanocomposites (PNCs). In confined polymers, these parameters are largely dominated by the long relaxation times of the polymers adsorbed at the substrate-polymer interface. On the other hand, for polymer nanocomposites, the interface layer (IL) between the nanoparticles and the surrounding matrix chains often control not only the morphology and dispersion but also various parameters like viscosity and glass transition temperature. Confined PNCs, hence, present a unique opportunity to study the interplay of these two independent interfacial effects. Here, we report the results of X-ray scattering based dynamics measurements of PNC thin films, with a two IL width, unraveling the subtle interplay of these two interfaces on the measured viscosity and fragility. Coupled with coarse-grained molecular dynamics (MD) simulations, our experimental results demonstrate that the viscosity of the PNC films increases with both the IL width and the thickness of the polymer layer adsorbed at the substrate interface. However, while both pristine PS and PNCs with a higher IL width become stronger glasses, as estimated by their fragility, the PNC with a lower IL width shows an increase in fragility with increasing confinement. Our results suggest a novel method to control thermo-mechanical properties and stability of PNC coatings by independently controlling the two interfacial effects in athermal glassy PNCs.

Unraveling the Polymer Chain-Adsorbed Constrained Interfacial Region on an Atomistically Thin Carbon Sheet.

Confinement of graphene and its functional derivatives in synthetic and biomacromolecules has been widely demonstrated recently to manifest in several multiscale phenomena in their mixtures. However, the intricate adsorbed interfacial region formed between polymer chains and a single layer of atomistically thin carbon sheet hitherto evaded an understanding of its nature and characteristics. Here, we reveal the structure of this constrained region and estimate the thickness of the adsorbed polymer layer on a single layer of an atomistically thin graphene oxide sheet using both direct experiments and molecular dynamics simulations. We use small-angle neutron scattering on a model multicomponent mixture formed by an adsorbing polymer, graphene oxide, and solvent for revealing the structure of the constrained interfacial region. We quantify the intricate adsorbed polymer layer thickness on a single layer of atomistically thin graphene oxide sheet by Euclidean approximation of the experimentally observed self-similar interfacial structure. The state of polymer chain random walk and influence of unadsorbed chains under experimental conditions are investigated and juxtaposed against the accuracy of this quantification. For long-chain polymers, the adsorbed layer thickness increases with increasing polymer molecular weight and shows a scaling relationship δ ∼ Rg0.22 with the polymer radius of gyration. For short-chain polymers, the thickness is nearly independent of molecular weight and shows a scaling relationship δ ∼ 0.6 Rg0.22. Coarse-grained molecular dynamics simulations performed on a model system similar to experiments qualitatively ratify the experimentally observed molecular weight-thickness relationship. Simulations show no discernible scaling relationship between radius of gyration and adsorbed layer thickness for low-molecular-weight polymers but show a consistent scaling δ ∼ Rg for high-molecular-weight polymers. A comparison between results from experiments and simulations indicates a discerning pathway in deciphering interface-governed multiscale phenomena in mixtures of adsorbing macromolecules with graphene and its functional derivatives.

Diffusion of polymer-grafted nanoparticles in a homopolymer matrix.

Molecular dynamics simulations are used to study the diffusion of polymer-grafted nanoparticles (PGNPs) in polymer. The diffusivity of PGNPs in the homopolymer matrix is investigated as a function of graft length and grafting density, and it is compared to that of bare nanoparticles with comparable effective size. Our results indicate that, in addition to the increase in the effective size of PGNPs due to grafting, the interpenetration of matrix polymers into the grafted layer also plays an important role in the mobility of PGNPs. In systems consisting of both PGNPs and bare particles, the spatial arrangement of the bare particles was found to be having a significant influence on the mobility of PGNPs. At low graft length and high grafting density, the matrix chains dewets the grafted layer, due to autophobic dewetting, creating a sharper interface between the matrix and the grafted layer. The bare particles then migrate to the interface creating a barrier around the PGNPs that hinders the matrix-graft interpenetration and results in the higher mobility of PGNPs. Our results emphasize the importance of polymer-particle interface on the dynamic properties of polymer nanocomposites.

Nanoparticle-polymer interfacial layer properties tune fragility and dynamic heterogeneity of athermal polymer nanocomposite films.

Enthalpic interactions at the interface between nanoparticles and matrix polymers are known to influence various properties of the resultant polymer nanocomposites (PNC). For athermal PNCs, consisting of grafted nanoparticles embedded in chemically identical polymers, the role and extent of the interface layer (IL) interactions in determining the properties of the nanocomposites are not very clear. Here, we demonstrate the influence of the interfacial layer dynamics on the fragility and dynamical heterogeneity (DH) of athermal and glassy PNCs. The IL properties are altered by changing the grafted to matrix polymer size ratio, f, which in turn changes the extent of matrix chain penetration into the grafted layer, λ. The fragility of PNCs is found to increase monotonically with increasing entropic compatibility, characterised by increasing λ. Contrary to observations in most polymers and glass formers, we observe an anti-correlation between the dependence on IL dynamics of fragility and DH, quantified by the experimentally estimated Kohlrausch-Watts-Williams parameter and the non-Gaussian parameter obtained from simulations.

Correlation between grafted nanoparticle-matrix polymer interface wettability and slip in polymer nanocomposites.

Controlling and understanding the flow properties of polymer nanocomposites (PNC) is very important in realising their potential for various applications. In this study we report molecular dynamics simulation studies of slip between a rotating polymer-grafted nanoparticle and the surrounding free linear matrix chains. By varying the interface wettability between the nanoparticle and matrix chains defined by the parameter f, the ratio of the graft to the matrix chain length, or the graft chain density, Σ, we were able to tune the interface slip, δ, significantly. Both f and Σ alter the interface wettability by changing the matrix chain penetration depth, λ, into the graft chain layer. We observed a large value of δ at smaller f or Σ which reduces with an increasing value of the respective parameters. Since interface slip is also likely to affect other properies of PNCs, like viscosity and the glass transition, we suggest that these parameters could become useful tools to control the flow and mechanical properties of PNCs made with grafted nanoparticles.

Polyimides Containing Phosphaphenanthrene Skeleton: Gas-Transport Properties and Molecular Dynamics Simulations.

A series of new semifluorinated polyimide (PI) films with phosphaphenanthrene skeleton were prepared by thermal imidization of poly(amic acid)s derived from a diamine monomer: 1,1-bis[2'-trifluoromethyl-4'-(4″-aminophenyl)phenoxy]-1-(6-oxido-6H-dibenz⟨c,e⟩⟨1,2⟩oxaphosphorin-6-yl)ethane on reaction with four structurally different aromatic dianhydrides. The chemical structures of the polymers were established by Fourier transform infrared and 1H NMR spectroscopy techniques. The polymers showed a good combination of thermal and mechanical properties (T d10 up to 416 °C under synthetic air and tensile strength up to 91 MPa), low dielectric constant (2.10-2.55 at 1 MHz), and T g values as high as 261 °C. Gas permeabilities of these films were investigated for four different gases CO2, O2, N2, and CH4. The PI films showed high gas permeability (P CO2 up to 175 and P O2 up to 64 barrer) with high permselectivity (P CO2 /P CH4 up to 51 and P O2 /P N2 up to 7.1), and the values are better than those of many other similar polymers reported earlier. For the O2/N2 gas pair, the PIs (PI A) surpassed the present upper boundary limit drawn by Robeson. A detailed molecular dynamics (MD) simulation study has been conducted to understand better the gas-transport properties. The effect of phosphaphenanthrene skeleton, its spatial arrangement, and size distribution function of the free volume were studied using molecular dynamics (MD) simulation and the results are correlated with the experimental data.

The effects of groove height and substrate stiffness on C. elegans locomotion.

The physical environment surrounding an animal has a significant impact on its behavior. The nematode Caenorhabditis elegans (C. elegans) has proved to be an excellent choice for understanding the adaptability of organisms crawling on soft surfaces. In this work, we investigate the modulation of C. elegans' behavioral kinematics in response to changes in the stiffness of the substrate and study the effect of grooves incised by the worms on their locomotion speed and efficiency. We measure the height of the grooves created by the animals on surfaces with different rigidity using confocal microscopy. Our results indicate that the kinematic properties of C. elegans, including amplitude (A), wavelength (λ) and frequency (f) of head turns depend strongly on surface properties and the height of the grooves created by them. During crawling, we observe that the animal assumes two distinct shapes depending on the stiffness of substrates. As the stiffness increases, the worm's body shape changes gradually from a 'W' shape, which is characterized by low amplitude curvature to the more common 'S' shape, which is characterized by high amplitude curvature, at intermediate values and back to 'W' on stiffer substrates. Although the efficiency is found to vary monotonically with surface stiffness, the forward velocity shows a non-monotonic behavior with the maximum on a surface, where the animal makes the 'S' shape.

Addition of P3HT-grafted Silica nanoparticles improves bulk-heterojunction morphology in P3HT-PCBM blends.

We present molecular dynamics simulations of a ternary blend of P3HT, PCBM and P3HT-grafted silica nanoparticles (SiNP) for applications in polymer-based solar cells. Using coarse-grained models, we study the effect of SiNP on the spatial arrangement of PCBM in P3HT. Our results suggest that addition of SiNP not only alters the morphology of PCBM clusters but also improves the crystallinity of P3HT. We exploit the property of grafted SiNP to self-assemble into a variety of anisotropic structures and the tendency of PCBM to preferentially adhere to SiNP surface, due to favorable interactions, to achieve morphologies with desirable characteristics for the active layer, including domain size, crystallinity of P3HT, and elimination of isolated islands of PCBM. As the concentration of SiNP increases, the number of isolated PCBM molecules decreases, which in turn improves the crystallinity of P3HT domains. We also observe that by tuning the grafting parameters of SiNP, it is possible to achieve structures ranging from cylindrical to sheets to highly interconnected network of strings. The changes brought about by addition of SiNP shows a promising potential to improve the performance of these materials when used as active layers in organic photovoltaics.

Durotaxis in Nematode Caenorhabditis elegans.

Durotaxis is a process where cells are able to sense the stiffness of substrates and preferentially migrate toward stiffer regions. Here, we show that the 1-mm-long nematode, Caenorhabditis elegans are also able to detect the rigidity of underlying substrates and always migrate to regions of higher stiffness. Our results indicate that C. elegans are able to judiciously make a decision to stay on stiffer regions. We found that the, undulation frequency, and wavelength of worms, crawling on surfaces show nonmonotonic behavior with increasing stiffness. A number of control experiments were also conducted to verify whether C. elegans are really able to detect the rigidity of substrates or whether the migration to stiffer regions is due to other factors already reported in the literature. As it is known that bacteria and other single-celled organisms exhibit durotaxis toward stiffer surfaces, we conjecture that durotaxis in C. elegans may be one of the strategies developed to improve their chances of locating food.

Controlling the Location of Bare Nanoparticles in Polymer-Nanoparticle Blend Films by Adding Polymer-Grafted Nanoparticles.

We present molecular dynamics simulations of polymer-nanoparticle blends in films containing both grafted and ungrafted nanoparticles where the particle cores are identical and grafted chains are similar to a matrix polymer. Our results indicate that it is possible to control the location of bare nanoparticles in the film by adding small amounts of polymer-grafted nanoparticles. In the presence of a substrate, bare particles are entropically pushed to the surface. We observed that the introduction of grafted particles to the blend prevents the migration of bare particles to the surface. This unusual behavior is caused by the formation of binary aspherical clusters due to the presence of grafted particles. Hence, parameters including grafting density and the length of the grafted polymer play a significant role in dictating the spatial arrangement of bare particles in the blend film. At higher values of these parameters, the grafted particle core is shielded from depletion attractions causing the density of bare particles to increase back near the surface.

Effect of temperature pre-exposure on the locomotion and chemotaxis of C. elegans.

The effect of temperature pre-exposure on locomotion and chemotaxis of the soil-dwelling nematode Caenorhabditis elegans has been extensively studied. The behavior of C. elegans was quantified using a simple harmonic curvature-based model. Animals showed increased levels of activity, compared to control worms, immediately after pre-exposure to 30 °C. This high level of activity in C. elegans translated into frequent turns by making 'complex' shapes, higher velocity of locomotion, and higher chemotaxis index (CI) in presence of a gradient of chemoattractant. The effect of pre-exposure was observed to be persistent for about 20 minutes after which the behavior (including velocity and CI) appeared to be comparable to that of control animals (maintained at 20 °C). Surprisingly, after 30 minutes of recovery, the behavior of C. elegans continued to deteriorate further below that of control worms with a drastic reduction in the curvature of the worms' body. A majority of these worms also showed negative chemotaxis index indicating a loss in their chemotaxis ability.

Chain flexibility for tuning effective interactions in blends of polymers and polymer-grafted nanoparticles.

We present molecular dynamics simulations of polymer-grafted nanoparticles in a homopolymer matrix to demonstrate the effect of chain flexibility on the potential of mean force (PMF) between various species in the nanocomposite. For a relatively high grafting density of Σg = 0.76 chains/σp(2) (where σp is the polymer monomer diameter), when the brush chain length is significantly smaller than (<∼ 1/4) the matrix chain length, the brushes exhibit autophobic dewetting with matrix polymers resulting in a strong attractive well in the particle-particle PMF. As the chain flexibility is decreased, we observe significant changes in particle-particle and particle-matrix PMFs that are strongly coupled with the length (or molecular weight) of grafted chains. For low molecular weight grafted chains, the change in the well-depth of particle-particle PMFs, with increasing chain stiffness, is non-monotonous, while that for longer grafted chains (still shorter than matrix chains), the attractive well exhibits a monotonous decrease in its depth. The particle-matrix PMF and the matrix penetration depth into the brush layer indicate that wetting of the grafted layer by matrix chains is enhanced with increasing chain stiffness.

Confinement enhances dispersion in nanoparticle-polymer blend films.

Polymer nanocomposites constitute an important class of materials whose properties depend on the state of dispersion of the nanoparticles in the polymer matrix. Here we report the first observations of confinement-induced enhancement of dispersion in nanoparticle-polymer blend films. Systematic variation in the dispersion of nanoparticles with confinement for various compositions and matrix polymer chain dimensions has been observed. For fixed composition, strong reduction in glass transition temperature, Tg, is observed with decreasing blend-film thickness. The enhanced dispersion occurs without altering the polymer-particle interactions and seems to be driven by enhanced matrix-chain orientation propensity and a tendency to minimize the density gradients within the matrix. This implies the existence of two different mechanisms in polymer nanocomposites, which determines their state of dispersion and glass transition.

Percolation of high-density polymer regions in nanocomposites: the underlying property for mechanical reinforcement.

Polymer nanocomposites have shown to exhibit improved mechanical properties compared to their pure host polymers. These property changes have been primarily attributed to the nature of polymer/nanoparticle interactions. Molecular dynamics simulations of model polymer nanocomposites have provided new insights into the molecular origin of property-changes in these nanocomposites. It was observed that addition of nanoparticles, induced adsorption of monomer segments onto the surface of nanoparticles creating high-density regions of polymer segments in the interfacial zones. A closer look into the morphology of these regions surrounding the nanoparticles revealed that mechanical reinforcement and changes in flow properties may be attributed to the formation of a percolated network of these high-density regions.

Effect of grafting on nanoparticle segregation in polymer/nanoparticle blends near a substrate.

Nanoparticles in polymer films have shown the tendency to migrate to the substrate due to an entropic-based attractive depletion interaction between the particles and the substrate. It is also known that polymer-grafted nanoparticles show better dispersion in a polymer matrix. Here, molecular dynamics simulations are employed to study the effect of grafting on the nanoparticle segregation to the substrate. The nanoparticles were modeled as spheres and the polymers as bead-spring chains. The polymers of the grafts and the matrix are identical in nature. For a purely repulsive system, the nanoparticle density near the surface was found to decrease as the length of grafted chains and the number of grafts increased and in the bulk, the nanoparticles are well-dispersed. Whereas, in case of attractive systems with interparticle interactions on the order of thermal energy, the nanoparticles segregated to the substrate even more strongly, essentially forming clusters on the wall and in the bulk. However, due to the presence of grafted chains on the nanoparticles, the clusters formed in the bulk are structurally anisotropic. The effect of grafts on nanoparticle segregation to the surface was found to be qualitatively similar to the purely repulsive case.

Locomotion of C. elegans: a piecewise-harmonic curvature representation of nematode behavior.

Caenorhabditis elegans, a free-living soil nematode, displays a rich variety of body shapes and trajectories during its undulatory locomotion in complex environments. Here we show that the individual body postures and entire trails of C. elegans have a simple analytical description in curvature representation. Our model is based on the assumption that the curvature wave is generated in the head segment of the worm body and propagates backwards. We have found that a simple harmonic function for the curvature can capture multiple worm shapes during the undulatory movement. The worm body trajectories can be well represented in terms of piecewise sinusoidal curvature with abrupt changes in amplitude, wavevector, and phase.

Surface-induced phase behavior of polymer/nanoparticle blends with attractions.

In an athermal blend of nanoparticles and homopolymer near a hard wall, there is a first order phase transition in which the nanoparticles segregate to the wall and form a densely packed monolayer above a certain nanoparticle density. Previous investigations of this phase transition employed a fluids density functional theory (DFT) at constant packing fraction. Here we report further DFT calculations to probe the robustness of this phase transition. We find that the phase transition also occurs in athermal systems at constant pressure, the more natural experimental condition than constant packing fraction. Adding nanoparticle-polymer attractions increases the nanoparticle transition density, while sufficiently strong attractions suppress the first-order transition entirely. In this case the systems display a continuous transition to a bulk layered state. Adding attractions between the polymers and the wall has a similar effect of delaying and then suppressing the first-order nanoparticle segregation transition, but does not lead to any continuous phase transitions.

Gelation in semiflexible polymers.

Molecular dynamics simulations have been employed to study the formation of a physical gel by semiflexible polymer chains. The formation of a geometrically connected network of these chains is investigated as a function of temperature and rate of cooling. The stiffness of the molecules is controlled via a potential between beads separated by two bonds. As the temperature is lowered, a percolated homogeneous solution phase separates to form a high-density, non-percolated nematic fluid and a low-density gas phase. On further decreasing the temperature, the chains are dynamically arrested preventing the completion of the vapor-liquid (VL) phase separation. As a result, the chains are stuck in a three-dimensional network of nematic bundles forming a percolated gel. Apart from temperature, the rate of cooling also plays an important role in the formation of the gel. Cooling the system at a faster rate yields gel while slower rates result in complete VL phase separation.