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We characterize via small-angle neutron scattering the structural properties of a mixture of all-DNA particles with functionalities 4 (A) and 2 (B) constrained by design to reside close to the percolation threshold. DNA base sequences are selected such that A particles can only bind with B ones and that at the studied temperature (10 °C) all AB bonds are formed and long-lived, originating highly polydisperse persistent equilibrium clusters. The concentration dependence of the scattered intensity and its wavevector dependence is exploited to determine the fractal dimension and the size distribution of the clusters, which are found to be consistent with the critical exponents of the 3-D percolation universality class. The value of DNA nanoparticles as nanometric patchy colloids with well-defined functionality, bonding selectivity, and exquisite control of the interaction strength is demonstrated.

High-density polyethylene (HDPE)-based nanocomposites incorporating three different types of graphene nanoplatelets (GnPs) were fabricated to investigate the size effects of GnPs in terms of both lateral size and thickness on the morphological, thermal, electrical, and mechanical properties. The results show that the inclusion of GnPs enhance the thermal, electrical, and mechanical properties of HDPE-based nanocomposites regardless of GnP size. Nevertheless, the most significant enhancement of the thermal and electrical conductivities and the lowest electrical percolation threshold were achieved with GnPs of a larger lateral size. This could have been attributed to the fact that the GnPs of larger lateral size exhibited a better dispersion in HDPE and formed conductive pathways easily observable in scanning electron microscope (SEM) images. Our results show that the lateral size of GnPs was a more regulating factor for the above-mentioned nanocomposite properties compared to their thickness. For a given lateral size, thinner GnPs showed significantly higher electrical conductivity and a lower percolation threshold than thicker ones. On the other hand, in terms of thermal conductivity, a remarkable amount of enhancement was observed only above a certain filler concentration. The results demonstrate that GnPs with smaller lateral size and larger thickness lead to lower enhancement of the samples' mechanical properties due to poorer dispersion compared to the others. In addition, the size of the GnPs had no considerable effect on the melting and crystallization properties of the HDPE/GnP nanocomposites. © 2020 Evgin et al., 2/0010/18, 2/0093/16, This work was partially supported by the Science Grant Agency VEGA, project no. 2/0010/18, and 2/0093/16 (Slovakia).

Percolation is a fundamental concept that has brought new understanding of the robustness properties of complex systems. Here we consider percolation on weakly interacting networks, that is, network layers coupled together by much fewer interlinks than the connections within each layer. For these kinds of structures, both continuous and abrupt phase transitions are observed in the size of the giant component. The continuous (second-order) transition corresponds to the formation of a giant cluster inside one layer and has a well-defined percolation threshold. The abrupt transition instead corresponds to the merger of coexisting giant clusters among different layers and is characterized by a remarkable uncertainty in the percolation threshold, which in turns causes an anomalous behavior of the observed susceptibility. We develop a simple mathematical model able to describe this phenomenon, using a susceptibility measure that defines the range where the abrupt transition is more likely to occur. Finite-size scaling analysis in the abrupt region supports the hypothesis of a genuine first-order phase transition.

Electrical, mechanical and piezoresistive behavior of flexible thin films of multi-walled carbon nanotubes (MWCNT) embedded in poly(methyl methacrylate) (PMMA) matrix are investigated for structural health monitoring applications. Three sets of MWCNT/PMMA nanocomposite thin films at various weight percentage of MWCNT are fabricated using solvent casting method. Dichloromethane (DCM) is used as a solvent. The percolation threshold for electrical conductivity is found to be 3 weight percentage of MWCNT. The mechanical properties of thin films are evaluated via monotonic uniaxial tensile test. The rate of loading is 1 mm/min and applied load and crosshead displacement are sampled at 10 Hz frequency. Experimental results showed that addition of 10 weight percentage of MWCNT leads to a significant improvement in the tensile strength of PMMA by 291% and tensile strain by 122%. The piezoresistive behavior at different weight percentage of MWCNT is evaluated and highest gage factor of 4.37 is achieved at the percolation threshold. � 2015 Elsevier Ltd.

cited By 2; International audience; Nascent powder particles of Ultra High Molecular Weight Polyethylene have been covered by multi-walled carbon nanotubes and then processed by means of sintering. The prelocalization of carbon nanotubes in the interfacial region between powder particles of UHMWPE allowed reaching an electrical percolation threshold as low as 0.04 wt%. It is also a possible way to reinforce specifically the interfacial regions with a very small amount of fillers. Indeed, the nucleation effect of the nanotubes is very strong on the strain-induced crystallization in the melting state of the composite. The tensile experiments above the melting point allowed by the extremely broad rubbery plateau of the UHMWPE show a significant increase in strain-hardening due to the addition of CNTs from 0.02 wt%. In the solid state the elastic properties, such as yield stress, and the crystallinity can also be increased for higher CNT concentrations despite the presence of aggregates which reduce the elongation at break. © 2017

Electromagnetic field enhancement (FE) effects occurring in thin gold films 3-12-nm are investigated with two-photon photoluminescence (TPL) and Raman scanning optical microscopies. The samples are characterized using scanning electron microscopy images and linear optical spectroscopy. TPL images exhibit a strong increase in the level of TPL signals for films thicknesses 3-8-nm, near the percolation threshold. For some thicknesses, TPL measurements reveal super-cubic dependences on the incident power. We ascribe this feature to the occurrence of very strongly localized and enhanced electromagnetic fields due to multiple light scattering in random nanostructures that might eventually lead to white-light generation. Raman images exhibit increasing Raman signals when decreasing the film thickness from 12 to 6-nm and decreasing signal for the 3-nm-film. This feature correlates with the TPL observations indicating that highest FE is to be expected near the percolation threshold.

The degree of graphite exfoliation and edge-carboxylated layers can be controlled and balanced to design lightweight materials characterized by both low electrical percolation thresholds (EPT) and improved mechanical properties. So far, this challenging task has been undoubtedly very hard to achieve. The results presented in this paper highlight the effect of exfoliation degree and the role of edge-carboxylated graphite layers to give self-assembled structures embedded in the polymeric matrix. Graphene layers inside the matrix may serve as building blocks of complex systems that could outperform the host matrix. Improvements in electrical percolation and mechanical performance have been obtained by a synergic effect due to finely balancing the degree of exfoliation and the chemistry of graphene edges which favors the interfacial interaction between polymer and carbon layers. In particular, for epoxy-based resins including two partially exfoliated graphite samples, differing essentially in the content of carboxylated groups, the percolation threshold reduces from 3 wt% down to 0.3 wt%, as the carboxylated group content increases up to 10 wt%. Edge-carboxylated nanosheets also increase the nanofiller/epoxy matrix interaction, determining a relevant reinforcement in the elastic modulus.

This work reports the film formation process from surfactant-free polystyrene (PS) latex particles. Steady state fluorescence and photon transmission techniques were used to study the evolution of film formation. The films were prepared from fluorescein (F)-labeled PS latex particles at room temperature and annealed in 2.5-min-time intervals above the glass transition temperature (T g) of PS. Fluorescence intensity (I F) from F was measured after each annealing step to monitor the stages of film formation. Evolution of transparency of latex films was monitored by using the photon transmission intensity, I tr. Drastic increase in I tr and I F above the critical annealing times, t r and t c, respectively, were attributed to the percolation behavior of the PS material. Critical exponents, β, of percolation clusters were measured and found to be around 0.31 and 0.37 for I tr and I F measurement, respectively, which were attributed to the site percolation model.

We investigated the electrical conductivity and percolation behavior of binary and ternary nanocomposites based on multiwalled carbon nanotubes (MWCNs) using polypropylene (PP) and a blend of PP with cyclic butylene terephthalate (CBT). The nanocomposites were prepared by diluting a commercial 20 %wtMWCNT PP masterbatch using optimized melt-mixing conditions. The concentration of carbon nanotubes in the diluted PP samples was as low as 0.5 % and as high as 15 % in weight. For the PP/CBT blend CBT concentration was varied up to 40 %wt while the loading of CNT was from 0 to 5 %wt. SEM and TEM techniques were used to examine the quality of the dispersion and the formation of nanotube networks within the polymer matrix. TEM and Raman spectroscopy results showed that for the diluted PP/MWCNT composites the nanotubes are well aligned in samples obtained the microinjection molding process, although the level of alignment is less with crystalline PP than in an amorphous matrix such as polycarbonate (PC). FTIR and XRD results revealed that the orientation of both polymer chains and crystals decreased with the incorporation of nanotubes into PP. The electrical conductivity was also significantly altered by the nanotube alignment in a PP matrix, as was previously observed for PC/MWCNT composites; the conductivity decreased and the percolation threshold rose in highly sheared samples; however, the presence of a crystalline phase improved the conductivity even for high shear conditions through the phenomenon of double percolation threshold. This last concept refers to the requirement that the filler-rich phase be continuous and conductive and not to the existence of two percolation thresholds at two different CNT concentrations. The electrical conductivity of PP/CBT blends was also improved through a double percolation that is the basic requirement for the conductivity of the ternary nanocomposites.

The morphology and the microscopic internal dynamics of a bidimensional gel formed by spontaneous aggregation of gold nanoparticles confined at the water surface are investigated by a suite of techniques, including grazing-incidence x-ray photon correlation spectroscopy (GI-XPCS). The range of concentrations studied spans across the percolation transition for the formation of the gel. The dynamical features observed by GI-XPCS are interpreted in view of the results of microscopical imaging; an intrinsic link between the mechanical modulus and internal dynamics is demonstrated for all the concentrations. Our work presents, to the best of our knowledge, the first example of a transition from stretched to compressed correlation function actively controlled by quasistatically varying the relevant thermodynamic variable. Moreover, by applying a model proposed time ago by Duri and Cipelletti [A. Duri and L. Cipelletti, Europhys. Lett. 76, 972 (2006)] we are able to build a novel master curve for the shape parameter, whose scaling factor allows us to quantify a 'long time displacement length'. This characteristic length is shown to converge, as the concentration is increased, to the 'short time localization length' determined by pseudo Debye-Waller analysis of the initial contrast. Finally, the intrinsic dynamics of the system are then compared with that induced by means of a delicate mechanical perturbation applied to the interface.

In this paper, we present numerical investigation of the contact between an elastic solid and a randomly rough surface. In agreement with recent results, we find that the contact area vs load relation depends on the statistical parameters only through the root mean square slope of the heights distribution. Such result extends to contact pressure regimes where the area/load relation is non-linear. Moreover, we show that fractal self-affine surfaces give a good representation of real surfaces from both topographical and contact mechanics points of view. Finally, we investigate how the network of non-contact areas evolves as the real contact area is increased, finding that the percolation threshold is smaller than the one predicted by Bruggeman's theory.

We have applied time-resolved THz spectroscopy to probe the transient photoexcited carrier dynamics and THz conductivity in Si nanocrystal films with varying silicon volume filling fractions and nanocrystal sizes on picosecond time scales. The THz conductivity reveals microscopic carrier motion with significant interface scattering within nanocrystals as well as percolative transport between nanocrystals. The time variation of the THz conductivity is analyzed within the framework of the Drude-Smith model, an extension of the Drude model that characterizes carrier localization in nanostructured materials. Below the percolation threshold, transport between nanocrystals is inhibited and photoexcited carriers are localized within individual nanocrystals. These films also exhibit efficient optical emission. In films with Si filling fractions above the percolation threshold, photoluminescence is suppressed and a transition from long-range inter-nanocrystal transport immediately after photoexcitation to increased carrier localization over a 50 ps time scale due to accumulation of charges at interface defect sites is observed., 2nd International Symposium on Nanoscale Luminescent Materials - 221st ECS Meeting, May 6-10, 2012, Seattle, WA, USA, Series: ECS Transactions

Aligned nanocomposite electrospun fibers are investigated for electrical (dc, ac, and dielectric) and thermal properties (10-40 wt.). This nanocomposite consists of poly(methylmethacrylate) (PMMA) grafted core-shell magnetite (CSM) nanoparticles and PMMA. Electrical properties as a function of tunnel gap (in between the CSM nanoparticles) are studied as the polymer shell stays intact and the cores do not touch each other well above the percolation threshold. The depleted improvement in dc conductivity ( dcwt) with increasing wt. (the improvement percentage: dc10 to dc20 ? 100; dc20 to dc30 ? 40 and dc30 to dc40 ? 1.2) affirms the non-touching cores of CSM. Interestingly, the observed ac conductive behavior (0.1-13 MHz) in the high end of the frequency range is in clear contrast to that of a typical percolating system, in fact it does not explicitly follow the universal power law. Some of the obtained critical exponents are not accommodated by the universal theory and significantly different from the present theoretical/experimental predictions. Additionally, an improvement in thermal stability of ?30 C and an overall increase in glass transition temperature are reported. � 2011 American Institute of Physics.

Several series of nanocomposites were prepared using a latex-based process, the main step of which consisted of mixing an aqueous suspension of exfoliated carbon nanotubes (CNTs) and a polymer latex. In the present work, a systematic study on the electrical properties of fully amorphous (polystyrene - PS) as well as semi-crystalline (isotactic polypropylene - iPP) nanocomposites containing either single-wall (SWCNTs) or multi-wall carbon nanotubes (MWCNTs) has been conducted. Percolation thresholds as low as 0.05 wt.% or 0.1 wt.% were observed for SWCNT/iPP and MWCNT/iPP nanocomposites, respectively. The formation of a conductive percolating network at such a low CNT concentration is favored by the high intrinsic conductivity and the low viscosity of the polymer matrix. The electrical percolation threshold of the iPP-based system was found to be lower than its rheological percolation threshold. Beyond the percolation threshold, MWCNT-based nanocomposites generally exhibited higher conductivity levels than those based on SWCNTs, most probably due to the higher intrinsic conductivity of the MWCNTs as compared to that of the SWCNTs. These excellent electrical properties, associated with the strong nucleating effect of the CNTs reported earlier [1,2], render this type of nanocomposites extremely attractive from a technological point of view. © 2010 Elsevier Ltd. All rights reserved.

Several series of nanocomposites were prepared using a latex-based process, the main step of which consisted of mixing an aqueous suspension of exfoliated carbon nanotubes (CNTs) and a polymer latex. In the present work, a systematic study on the electrical properties of fully amorphous (polystyrene - PS) as well as semi-crystalline (isotactic polypropylene - iPP) nanocomposites containing either single-wall (SWCNTs) or multi-wall carbon nanotubes (MWCNTs) has been conducted. Percolation thresholds as low as 0.05 wt.% or 0.1 wt.% were observed for SWCNT/iPP and MWCNT/iPP nanocomposites, respectively. The formation of a conductive percolating network at such a low CNT concentration is favored by the high intrinsic conductivity and the low viscosity of the polymer matrix. The electrical percolation threshold of the iPP-based system was found to be lower than its rheological percolation threshold. Beyond the percolation threshold, MWCNT-based nanocomposites generally exhibited higher conductivity levels than those based on SWCNTs, most probably due to the higher intrinsic conductivity of the MWCNTs as compared to that of the SWCNTs. These excellent electrical properties, associated with the strong nucleating effect of the CNTs reported earlier [1,2], render this type of nanocomposites extremely attractive from a technological point of view. © 2010 Elsevier Ltd. All rights reserved.

We studied film formation of composites of surfactant-free polystyrene (PS) nanoparticles and modified Na-activated bentonite (MLB), by steady state fluorescence (SSF) technique. The films were prepared from a mixture of pyrene (P)-labeled PS particles and MLB at various compositions at room temperature. These films were annealed at elevated temperatures above the glass transition ( T g ) temperature of polystyrene for 10 min. Scattered light ( I s ) and fluorescence intensities ( I P ) from P were measured after each annealing step to monitor the stages of film formation. Evolution of transparency of the composite films was monitored by using photon transmission intensity, I tr . Atomic force microscopy (AFM) was used to detect the variation in physical structure of annealed composite films. The nanocomposite films exhibited a percolation threshold at 20 wt.% MLB content. Below this fraction two distinct film formation stages were observed which are known as void closure and interdiffusion and above this fraction no film formation was detected. At 0–20 wt.% MLB, minimum film formation, T 0 , void closure, T v and healing, T h temperatures were determined. Void closure and interdiffusion stages were modeled and related activation energies were determined. Void closure activation energies decreased as the percent of MLB increased, no variation was observed in backbone activation energies.

Composite fibers of single walled carbon nanotubes dispersed in poly(methyl methacrylate) and polystyrene are prepared using electrospinning. The single fiber electrical conductivity is measured as a function of the composition of carbon nanotubes. A noncontact method of measuring the carrier mobility at microwave frequency (14 GHz) using bimodal cavity is employed. The mobility measurements indicate lower percolation threshold for mobility compared to electrical conduction. For higher concentrations of carbon nanotubes, the mobility is found to decrease indicating possible carrier-lattice scattering. � 2008 American Institute of Physics.

Thermal phase transitions of kappa-carrageenan in NaCl, KCl and CaCl2 solutions were studied using steady state fluorescence (SSF) technique. Pyranine was introduced as a fluorescence probe for studying sol-gel phase transitions. Scattered light, I-sc and fluorescence intensity, I was monitored against temperature to determine the sol-gel (T-sg) phase transition temperatures. It was observed that T-sg values are strongly correlated to NaCl, KCl and CaCl2 contents. The weight average degree of polymerization, DPw, and gel fraction G, exponents (gamma and beta) were measured and found to be in accord with the classical Flory-Stockmayer model, i.e., gamma and beta were found to be close to 1.0, independent of salt content. Publisher's Version Q3 WOS:000248376800001

We study spatio-temporal intermittency (STI) in a system of coupled sine circle maps. The phase diagram of the system shows parameter regimes with STI of both the directed percolation (DP) and non-DP class. STI with synchronized laminar behaviour belongs to the DP class. The regimes of non-DP behaviour show spatial intermittency (SI), where the temporal behaviour of both the laminar and burst regions is regular, and the distribution of laminar lengths scales as a power law. The regular temporal behaviour for the bursts seen in these regimes of spatial intermittency can be periodic or quasi-periodic, but the laminar length distributions scale with the same power-law, which is distinct from the DP case. STI with traveling wave (TW) laminar states also appears in the phase diagram. Soliton-like structures appear in this regime. These are responsible for cross-overs with accompanying non-universal exponents. The soliton lifetime distributions show power law scaling in regimes of long average soliton life-times, but peak at characteristic scales with a power-law tail in regimes of short average soliton life-times. The signatures of each type of intermittent behaviour can be found in the dynamical characterisers of the system viz. the eigenvalues of the stability matrix. We discuss the implications of our results for behaviour seen in other systems which exhibit spatio-temporal intermittency., 25 pages, 11 figures. Submitted to Phys. Rev. E

A non-linear state space model is developed for describing groundwater fluctuations. Non-linearity is introduced by modeling the (unobserved) degree of water saturation of the root zone. The non-linear relations are based on physical concepts describing the dependence of both the actual evapotranspiration and the percolation rate on the degree of saturation of the root zone. Precipitation and reference evaporation are the input variables. Recharge from the root zone is transferred through the percolation zone to the water table by means of a linear reservoir model. The flux in the percolation zone is assumed to be independent of the groundwater level. Errors due to model assumptions and parameter uncertainties are modeled as a noise process. The parameters of the resulting stochastic model are calibrated on time series by combining an extended Kalman filter with a maximum-likelihood criterion. The model is tested at two locations and compared with a linear time series model. It is shown that the non-linear model estimated extreme groundwater levels better than the linear time series model. The variance of the stochastic component reduced significantly. This implies that effects from natural influences can be separated from non-natural influences with less uncertainty. Another advantages of the non-linear model is that it also gives an indication of fluctuations in the degree of saturation in the root zone. © 2005 Elsevier Ltd. All rights reserved.

A non-linear state space model is developed for describing groundwater fluctuations. Non-linearity is introduced by modeling the (unobserved) degree of water saturation of the root zone. The non-linear relations are based on physical concepts describing the dependence of both the actual evapotranspiration and the percolation rate on the degree of saturation of the root zone. Precipitation and reference evaporation are the input variables. Recharge from the root zone is transferred through the percolation zone to the water table by means of a linear reservoir model. The flux in the percolation zone is assumed to be independent of the groundwater level. Errors due to model assumptions and parameter uncertainties are modeled as a noise process. The parameters of the resulting stochastic model are calibrated on time series by combining an extended Kalman filter with a maximum-likelihood criterion. The model is tested at two locations and compared with a linear time series model. It is shown that the non-linear model estimated extreme groundwater levels better than the linear time series model. The variance of the stochastic component reduced significantly. This implies that effects from natural influences can be separated from non-natural influences with less uncertainty. Another advantages of the non-linear model is that it also gives an indication of fluctuations in the degree of saturation in the root zone. © 2005 Elsevier Ltd. All rights reserved.

A continuum model that possesses several desirable features of the electrical conduction process in carbon-nanotube (CNT) based nanocomposites is developed. Three basic elements are included: (i) percolation threshold, (ii) interface effects, and (iii) tunneling-assisted interfacial conductivity. We approach the first one through the selection of an effective medium theory. We approach the second one by the introduction of a diminishing layer of interface with an interfacial conductivity to build a thinly coated CNT. The third one is introduced through the observation that interface conductivity can be enhanced by electron tunneling which in turn can be facilitated with the formation of CNT networks. We treat this last issue in a continuum fashion by taking the network formation as a statistical process that can be represented by Cauchy's probability density function. The outcome is a simple and yet widely useful model that can simultaneously capture all these fundamental characteristics. It is demonstrated that, without considering the interface effect, the predicted conductivity would be too high, and that, without accounting for the additional contribution from the tunneling-assisted interfacial conductivity, the predicted conductivity beyond the percolation threshold would be too low. It is with the consideration of all three elements that the theory can fully account for the experimentally measured data. We further use the developed model to demonstrate that, despite the anisotropy of the intrinsic CNT conductivity, it is its axial component along the CNT direction that dominates the overall conductivity. This theory is also proved that, even with a totally insulating matrix, it is still capable of delivering non-zero conductivity beyond the percolation threshold. NSF Mechanics of Materials Program under CMMI-1162431 and by Qatar National Research Fund under NPRP 09-508-2-192. Scopus

Charge exchange at the bulk heterojunctions of composites made by mixing single wall nanotubes (SWNTs) and polymers show potential for use in optoelectronic devices such as solar cells and optical sensors. The density/total area of these heterojunctions is expected to increase with increasing SWNT concentration but the efficiency of solar cell peaks at low SWNT concentrations. Most researchers use current–voltage measurements to determine the evolution of the SWNT percolation network and optical absorption measurements to monitor the spectral response of the composites. However, these methods do not provide a detailed account of carrier transport at the concentrations of interest; i.e., near or below the percolation threshold. In this article, we show that capacitance–voltage (C–V) response of (metal)-(oxide)-(semiconducting composite) devices can be used to fill this gap in studying bulk heterojunctions. In an approach where we combine optical absorption methods withC–V measurements we can acquire a unified optoelectronic response from P3HT-SWNT composites. This methodology can become an important tool for optoelectronic device optimization.