Rheology of nanosized hairy grain suspensions

Suspensions of nanosized hairy grains have been prepared by grafting long polydimethylsiloxane chains (molecular weight ) onto silica particles (radius ), dispersed into a good solvent of PDMS. Depending on the particle volume fraction, different rheological behaviors are observed. In the very dilute regime, the suspensions are perfectly stable and the particles behave almost as hard spheres: flow penetration inside the corona is then very weak. When the particle volume fraction goes to the close packing volume fraction, the suspension viscosity does not diverge as for hard spheres due to the increase of flow penetration inside the corona and to corona entanglements. The particles have then the same behavior as polymer stars having an intermediate number of arms (). Finally, in the concentrated regime (), the suspensions form irreversible gels. We shown that this unexpected gelation phenomenon is related to the presence of the silica cores: grafted PDMS chains can adsorb onto different particles and form irreversible bonds between the cores. The viscosity and elastic modulus evolutions during gelation are well described by the scalar percolation model of sol-gel transition. Received 23 March 1998     

On the continuity of the critical value for long range percolation in the exponential case

We show that for a long range percolation model with exponentially decaying connections, the limit of critical values of any sequence of long range percolation models approaching the original model from below is the critical value for the original long range percolation model. As an interesting corollary, this implies that if a long range percolation model with exponential connections is supercritical, then it still percolates even if all long bonds are removed. We also show that the percolation probability is continuous (in a certain sense) in the supercritical regime for long range percolation models with exponential connections.Research supported by a grant from the Swedish National Science Foundation.     

DNA-wrapped carbon nanotubes aligned in stretched gelatin films: Polarized resonance Raman and absorption spectroscopy study

We present the study of DNA-wrapped single-walled carbon nanotubes (SWNTs) embedded in the stretched gelatin film by the polarized resonance Raman spectroscopy and visible-NIR optical absorption. The polarized dependent absorption spectra taken along and normal to the stretching direction demonstrate a comparatively high degree of the alignment of isolated SWNTs in the gelatin matrix. The analysis of Raman spectra of isolated SWNTs in the gelatin stretched films showed that the degree of the alignment of carbon nanotubes along the stretching direction is about 62%. The dependence of the peak position of G⁺-band in Raman spectra on the polarization angle θ between the polarization of the incident light and the direction of the stretching of films was revealed. This shift is explained by the different polarization dependence of the most intensive A and E₁ symmetry modes within the G⁺-band. The performed studies of embedded DNA-wrapped nanotubes in the gelatin film show the simple method for obtaining the controlled ordered biocompatible nanotubes inside a polymer matrix. It can be used for manufacturing sizable flexible self-transparent films with integrated nanoelectrodes.     

Percolation model for enzyme gel degradation

We study a model for the gel degradation by an enzyme, where the gel is schematized as a cubic lattice, and the enzyme as a random walker, that cuts the bonds over which it passes. The model undergoes a (reverse) percolation transition, which for low density of enzymes falls in a universality class different from random percolation. In particular, we have measured a gel fraction critical exponent beta=1.0+/-0.1, in excellent agreement with experiments made on the real system.     

Sol-Gel transition of concentrated colloidal suspensions

Diffusing-wave spectroscopy (DWS) was used to follow the sol-gel transition of concentrated colloidal suspensions. We present a new technique based on a sandwich of two scattering cells aimed to overcome the problem of nonergodicity in DWS of solidlike systems. Using this technique we obtain quantitative information about the microscopic dynamics all the way from an aggregating suspension to the final gel, thereby covering the whole sol-gel transition. At the gel point a dramatic change of the particle dynamics from diffusion to a subdiffusive arrested motion is observed. A critical-power-law behavior is found for the time evolution of the maximum mean square displacement delta(2) probed by a single particle in the gel.     

Jamming, two-fluid behavior, and "self-filtration" in concentrated particulate suspensions

We study the flow of model hard-sphere colloidal suspensions at high volume fraction Phi driven through a constriction by a pressure gradient. Above a particle-size dependent limit Phi(0), direct microscopic observations demonstrate jamming and unjamming-conversion of fluid to solid and vice versa-during flow. We show that such a jamming flow produces a reduction in colloid concentration Phi(x) downstream of the constriction. We propose that this "self-filtration" effect is due to a combination of jamming of the particulate part of the system and continuing flow of the liquid part, i.e., the solvent, through the pores of the jammed solid. Thus we link jamming in colloidal and granular media with a "two-fluid-like" picture of the flow of concentrated suspensions. Results are also discussed in the light of the original experiments of Reynolds on dilation in granular materials.     

Robustness of a network of networks

Network research has been focused on studying the properties of a single isolated network, which rarely exists. We develop a general analytical framework for studying percolation of n interdependent networks. We illustrate our analytical solutions for three examples: (i) For any tree of n fully dependent Erd?s-Rényi (ER) networks, each of average degree k, we find that the giant component is P∞ =p[1-exp(-kP∞)](n) where 1-p is the initial fraction of removed nodes. This general result coincides for n = 1 with the known second-order phase transition for a single network. For any n>1 cascading failures occur and the percolation becomes an abrupt first-order transition. (ii) For a starlike network of n partially interdependent ER networks, P∞ depends also on the topology-in contrast to case (i). (iii) For a looplike network formed by n partially dependent ER networks, P∞ is independent of n.     

Rigidity percolation in particle-laden foams

We study the viscoelastic behavior of aqueous foam mixed with solid noncolloidal particles. We show that adding a tiny amount of grains can enhance the elastic and loss shear moduli by more than 1 order of magnitude. The scaling of these moduli with solid volume fraction is in qualitative agreement with that predicted by an effective-medium rigidity percolation model. We present a simple model, based on capillary attraction, to explain the particle-size dependence of the threshold.     

Elasticity,fracture and thermoreversible gelation of highly filled physical gels<Superscript>⋆</Superscript>

We describe a physically associating triblock copolymer-based gel that exhibits a reversible transition between solid and liquid states at a temperature of approximately 55^°C. The thermal transition of the gel enables us to compare the properties of liquid suspensions and elastic composites with identical particle loadings, with particle volume fractions as large as 0.55. The suspension viscosity and the composite elasticity scale in a similar manner with the overall particle volume fraction, a result that is rationalized in terms of an effective strain amplification factor that depends only on the particle loading. Measured values of the strain amplification factor are in good agreement with the expected form for well-dispersed spheres. We also find that the elastic composites are exceptionally strong, with fracture strengths that exceed the modulus of the base gel by a factor of 100 or more. Deviations from purely elastic behavior became important for high particle volume fractions, and were probed by stress relaxation experiments.     

Scaling of the viscoelasticity of weakly attractive particles

The rheological data of weakly attractive colloidal particles are shown to exhibit a surprising scaling behavior as the particle volume fraction, straight phi, or the strength of the attractive interparticle interaction, U, are varied. There is a critical onset of a solid network as either straight phi or U increase above critical values. For all solidlike samples, both the frequency-dependent linear viscoelastic moduli, and the strain-rate dependent stress can be scaled onto universal master curves. A model of a solid network interspersed in a background fluid qualitatively accounts for this behavior.     

Stretching of polymer chains by fluctuating flow fields

We investigate polymer stretching by fluctuating flow fields via numerical solutions of the Brownian dynamics of multibead polymer chains taking into account nonlinear elasticity, hydrodynamic interactions and good solvent, excluded volume interaction effects. By varying the scaling exponent of the energy spectrum whilst keeping the same Reynolds and Deborah numbers, as well as microscale length and turnover times, we show that steeper spectra are associated with stronger stretching. We compute the probability density functions of chain length, and explain their main features by examining explicit molecular histories. We quantify the interaction between strain rate tensor structure and chain geometry as a means of understanding better the different stretching mechanisms in mild, moderate and strong polymer stretching regimes.     

Critical behavior of a random diode network

We study the percolation properties of a random diode network (RDN) which contains two kinds of directed bonds on a square lattice. This network is a special case of the random insulation-resistor-diode network. Both Monte Carlo simulations and series expansion for the percolation probability show that an estimated critical exponent, beta=0.1794+/-0.008, is different from known values for a conventional insulation-resistor-diode network. RDN belongs to neither the isotropic percolation universality class nor to the directed percolation universality, which we attribute to a difference of symmetry breakdown around the critical point.     

Monte Carlo study of percolation on disordered triangular lattices

A simple model for amorphous solids, consisting of a mixed bond triangular lattice with a fraction of attenuated bonds randomly distributed (which simulate the presence of defects in the surface), is studied here by using computational simulation. The degree of disorder of the surface is tunable by selecting the values of (1) the fraction of regular [attenuated] bonds ρ [1−ρ] (0≤ρ≤1) and (2) the factor r, which is defined as the ratio between the value of the conductivity associated to an attenuated bond and that corresponding to a regular bond (0≤r≤1). The results obtained show how the percolation properties of the disordered system are modified with respect to the standard random bond percolation problem (r=0).     

Optical properties of single wall carbon nanotubes dispersed in biopolymers

In this paper we report the optical studies of single wall carbon nanotubes dispersed in biomaterials. We have obtained very stable suspensions of SWNTs, which allowed us to get good photoluminescence signal from the individually dispersed nanotubes. These new hybrid systems may find some applications in bionanocomposites with photoluminescence properties and in biosensors. Furthermore, the dispersion of carbon nanotubes in these biocompatible materials is important for evaluating the toxicity of either isolated or lightly bundled single wall carbon nanotubes.     

Temperature‐dependent magneto‐photoluminescence spectroscopy of carbon nanotubes: evidence for dark excitons

We review recent experimental and theoretical studies on the radiative properties of excitons in single‐walled carbon nanotubes (SWNTs) as a function of magnetic field and temperature. These studies not only provide new insight into the fundamental properties of excitons in the ultimate one‐dimensional (1D) limit but also reveal new phenomena associated with the unique crystal and electronic structure of SWNTs. During the past several years, SWNTs have emerged as one of the most ideal systems available for the systematic study of 1D excitons, which are predicted to possess a set of properties that are distinctly different from excitons in higher dimensions. In addition, their tubular nature allows them to exhibit non‐intuitive quantum phenomena when subjected to a parallel magnetic field, which breaks time reversal symmetry and adds an Aharonov‐Bohm phase to the electronic wavefunction. In particular, a series of recent experiments demonstrate that such a symmetry‐breaking magnetic field can dramatically “brighten” an optically‐inactive, or dark, exciton state at low temperature (see the title figure on the right). We show that this phenomenon, magnetic brightening, can be understood as a consequence of interplay between the strong intervalley Coulomb mixing and field‐induced lifting of valley degeneracy. Detailed temperature‐dependent photoluminescence studies of excitons in SWNTs in a varying magnetic field have thus provided one of the most critical tests for recently proposed theories of 1D excitons taking into account the strong 1D Coulomb interactions and unique band structure on an equal footing. Furthermore, results of these studies suggest the intriguing possibility of manipulating the optical properties of SWNTs by judicious symmetry control, which can lead to novel devices and applications in lasers and optoelectronics.     

Nonequilibrium phase diagram of sticky nanotube suspensions

We report a universal phase diagram describing the evolution from solidlike networks to flowing nematics for "sticky" nanotube suspensions under an applied shear stress. Although the nanotubes are strongly non-Brownian, we find features characteristic of first-order phase transitions, including a discontinuity in the nematic order parameter at the isotropic-(para)nematic phase boundary. Using simple physical arguments, we account for the shape of the coexistence curves, as well as the dependence of the order parameter on concentration and stress.     

Elastic “hard” fibers. I.

Elastic “hard” fibers may be prepared from a number of semicrystalline polymers, notably polypropylene, poly-3-methylbutene-1, and polyoxymethylene. These materials show typically a high degree of length recovery from large extensions, a marked, more-or-less recoverable reduction of apparent density on stretching, and the generation of very large amounts of accessible volume and surface area on stretching. Wide- and low-angle X-ray and electron-microscopic observations indicate that the morphological basis for these properties lies in an array of closely packed lamellae of which the normals lie predominantly parallel to the fiber extrusion direction. It is the tilting and splaying apart of the lamellar network which creates the internal volume and surface area on stretching. The long-range elasticity is believed to be distinctly nonrubberlike, as reflected in an insensitivity of mechanical properties to low temperatures, and to arise from bending of the lamellae. This unusual class of materials provides a significant link between macroscopic properties and a particular morphological structure.     

Magnetic separation from superparamagnetic particle suspensions

We investigate the magnetophoretic separation of magnetic microparticles from a non-dilute flow in a microfluidic channel and their subsequent field-induced aggregation under the influence of an externally applied magnetic force. This force induces dipolar interactions between the particles that aid in their separation from the flow. Existing analytical models for dilute suspensions cannot be extended to non-dilute suspensions in which interparticle magnetic interactions play an important role. We therefore conduct a parametric investigation of the mechanics of this problem in a microcapillary flow through simulations and experimental visualization. When a magnetic field is applied, the magnetic microparticles form an aggregate on the channel wall that is influenced by the competition between the holding magnetic force and the aggregate-depleting flow shear force. Microparticle collection in the aggregate increases linearly with increasing magnetic field strength and is characterized by distinct buildup and washaway phases. The collected microparticle volume fraction in an aggregate is found to depend on a single dimensional group that depends upon characteristic system parameters.     

Dynamics of individual single-walled carbon nanotubes in water by real-time visualization

Individual single-walled carbon nanotubes (SWNTs) in aqueous suspension are visualized directly by fluorescence video microscopy. The fluorescent tagging is simple, biocompatible, and does not modify the SWNTs. The dynamics of individual SWNTs in water are observed and quantified for the first time. We measure the confined rotational diffusion coefficient and find it in reasonable agreement with predictions based on confined diffusion of dilute Brownian rods. We determine the critical concentration at which SWNTs in suspensions start interacting. By analyzing the fluctuating shape of SWNTs in the 3 to 5 microm range, we determine that their persistence length ranges between 32 and 174 microm, in agreement with theoretical estimates; thus, commonly available SWNTs in liquids can be considered as rigid Brownian rods in the absence of imposed external fields or self-attractive forces.