Low Percolation Threshold Research Articles

Carbon nanotube/polyvinylidene fluoride flexible composite material with low percolation threshold and adjustable negative permittivity

Carbon nanotube/polyvinylidene fluoride flexible composite material with low percolation threshold and adjustable negative permittivity

Effect of graphite fillers on electrical and thermal conductivity in epoxy-based composites: Percolation behavior and analysis

This work investigated a method for producing epoxy-based composites using various graphite fillers, such as natural, synthetic, and thermally expanded graphite. The study aimed to determine the impact of the filler type, size, and volume fraction on the composites’ thermal and electrical conductivity. Results indicate that the percolation model accurately represents electrical and thermal conductivity behavior, with graphite fillers forming conductive clusters in the polymer matrix. The percolation threshold for electrical conductivity varies between 2.8 and 8.5 vol.%, while for thermal conductivity, it ranges from 5.0 to 18.0 vol.%, which is twice that of electrical conductivity. This observation is due to both the electron transfer tunneling effect and the necessity of higher filler content to facilitate effective phonon transport. Notably, composites filled with thermally expanded graphite exhibit lower percolation thresholds. Understanding percolation behavior facilitates the prediction and optimization of composites with specific electrical and thermal properties for diverse applications.

A Facile Method in Fabricating Flexible Conductive Composites with Large-Size Segregated Structures for Electromagnetic Interference Shielding.

To resist the plastic deformation of polymer particles during hot press molding, high molecular weights, and moduli are required for composites with segregated structures, thus the prepared composites exhibit poor flexibility. Also, larger particle sizes can bring lower percolation thresholds while the ensuing greater deformation destroys the conductive network. Moreover, segregated composites still face preparation complexities. Herein, a facile method for developing flexible composites with large-size segregated structures is proposed. First, silver-coated polydopamine-modified reduced graphene oxide (Ag@PrGO), as conductive fillers, is prepared by electroless plating. Next, polydimethylsiloxane (PDMS)-coated polyolefin elastomer (POE) beads are put into a bag containing the fillers. After a simple shaking, the fillers are adhered to the POE surface as the cohesive property of cured PDMS. Finally, flexible composites with large-size segregated structures are obtained via hot pressing. Benefiting from the 2D structure of the Ag@PrGO and the ability to slip, the conductive networks possess adaptable deformability. The prepared composites exhibit excellent electrical conductivity (203.55 Scm-1) at filler volume fractions of 3.4 vol%. The EMI shielding effectiveness can reach 70dB in the X-band at a thickness of 1.9mm and remains stable after bending and rubbing damage. This work paves the way for constructing large-size segregated structures.

Kill Two Birds with One Stone: Cracking Lithography Technology for High-Performance Flexible Metallic Network Transparent Conductors and Metallic Micronano Sheets.

Flexible electronics have sparked a wide range of exciting applications, such as flexible display technologies, lighting, sensing, etc. Flexible conductors are essential components of flexible electronics and seriously affect efficiency and overall performance. Here, a facile and kill-two-birds-with-one-stone strategy of cracking lithography technology has been proposed to simultaneously fabricate two high-performance flexible conductors, flexible metallic network transparent conductors (f-NTCs) and metallic micronano sheets (MMNSs). The PET substrate flexible transparent conductors (FTCs) based on this strategy yield 88.1% transparency within the visible spectrum and a sheet resistance of 9 Ω/sq. In addition, the FTCs show exceptional mechanical stability, with the sheet resistance remaining virtually unchanged even after 6000 s of bending tests. Subsequently, the remaining MMNSs are recycled to manufacture a Ag paste, showing a very low conductive percolation threshold (∼13%) and excellent flexibility with 140% breaking elongation. After 1000 s of stretching tests, it showed excellent mechanical stability. Furthermore, flexible electroluminescent devices based on the FTCs and sensors fabricated with MMNSs both show excellent performance, demonstrating their potential wide applications in flexible electronics.

Complex Permittivity Spectra of Granular Polymer Composites with Dispersed Ag-Coated Cu Flakes

AbstractConductive particle-containing granular composites with tuneable negative permittivity are being studied to improve the performance of electromagnetic devices, such as shielding materials. In this study, we investigated the relative complex permittivity and electrical conductivity of granular composites of polyphenylene sulfide (PPS) resin and Ag-coated Cu flakes in the radio- to microwave-frequency range and compared them with those of PPS/bare Cu flake composites. Electrical conductivity measurements revealed that the PPS/Ag-coated Cu flake composites have a lower percolation threshold (φc) than the PPS/bare Cu flake composites, whereas the electrical conductivity of the PPS/Ag-coated Cu flake composites in the percolated particle state was higher at the same particle volume fraction. At particle contents above φc, a low-frequency plasmonic state of conduction electrons was achieved in the percolated particle chains in both composites, and negative permittivity spectra were obtained. The percolated PPS/Ag-coated Cu flake composites had a negative permittivity up to a higher frequency than the percolated PPS/bare Cu flake composites. Furthermore, the Drude model was used to analyze the negative permittivity spectra of the composites in the percolated particle state. The plasma frequency of the composites with percolated Ag-coated Cu flakes was higher than that of the composites with percolated bare Cu flakes. Thus, coating Ag on Cu particles improved the conductivity of the composite, leading to negative permittivity up to higher frequencies. This study contributes to the enhancement of the negative permittivity achieved by granular composites, which is useful for microwave technology applications. Graphical Abstract

Conductivity of PLA/PBAT blends with carbon black as a conductive filler

Conductive composites of PLA/PBAT/CB were prepared by melt blending. CB selectively distributes in the PBAT matrix, and at a PLA to PBAT ratio of 1:1, the composite achieves a conductivity of 1.01 × 10−6 S/m with a percolation threshold of 0.42 wt%. Compared to PLA/CB and PBAT/CB, the PLA/PBAT/CB composite has a lower percolation threshold. The E2 processing sequence most effectively enhanced conductivity by optimizing carbon black distribution in the PBAT phase, promoting a co-continuous structure and improving conductive pathways and electrical properties. Key methods used include contact angle measurements, polarized light microscopy, scanning electron microscopy, and a high-resistance meter.

Percolation Statistics in the MillenniumTNG Simulations

The statistical analysis of cosmic large-scale structure is most often based on simple two-point summary statistics, like the power spectrum or the two-point correlation function of a sample of galaxies or other types of tracers. In contrast, topological measures of clustering are also sensitive to higher-order correlations and thus offer the prospect to access additional information that may harbor important constraining power. We here revisit one such geometric measure of the cosmic web in the form of the so-called percolation analysis, using the recent MillenniumTNG simulation suite of the ΛCDM paradigm. We analyze continuum percolation statistics both for high-resolution dark matter particle distributions and for galaxy mock catalogs from a semianalytic galaxy formation model within a periodic simulation volume of 3000 Mpc on a side. For comparison, we also investigate the percolation statistics of random particle sets and neutrino distributions with two different summed particle masses. We find that the percolation statistics of the dark matter distribution evolves strongly with redshift and thus clustering strength, yielding a progressively lower percolation threshold toward later times. However, there is a sizable residual dependence on numerical resolution, which we interpret as a residual influence of different levels of shot noise. This is corroborated by our analysis of galaxy mock catalogs, whose results depend on sampling density more strongly than on galaxy selection criteria. While this limits the discriminative power of percolation statistics, our results suggest that it still remains useful as a complementary cosmological test when controlled for sampling density.

Sedimentation-controlled double BSRs and implications for paleo hydrate dissociation in the Shenhu area, south China sea

Double/multiple bottom-simulating reflectors (BSRs) have been discovered worldwide, but their preservation and formation mechanism remain unclear because most studies are based on seismic data, lacking direct evidence like well logging data. This study introduces a novel well log-based interpretation of double BSR, suggesting that the secondary BSR (BSR2) is the interface between little residual gas and the overlying water-saturated sediment, and the free gas is trapped by capillary seals. The BSR2's amplitude is influenced by the nearby porosity, with lower porosity resulting in stronger reflections. Seismic attributes reveal a dynamic process of hydrate cycle that hydrate dissociation occurs above BSR2, followed by gas migrate to form a new BSR1. The upshift of BSR2 is mainly controlled by sedimentation rate, which varies across different regions, leading to larger upshifts in areas with higher sedimentation rates. Moreover, BSR2's upshift is negatively related to the reflection magnitude of BSR2, because rapidly depositing sediments with higher porosity and lower percolation threshold allow lesser gas sealed beneath the BSR2. Our findings suggest that double BSRs are predominantly formed in muddy sediments under rapid geological events like rapid sedimentation. However, each BSR can be preserved as well as observed to indicate that the BSR has existed for an extended period of time during which the geologic environment has been relatively stable, e.g., low sedimentation rates. This detailed sedimentation-controlled BSR adjustment provides new insights for the interpretation of double BSR and the paleo hydrate dissociation.

Investigation on the loading rate dependence of electromechanical properties of graphene-cement composites under compressive loading

In this paper, the dependence of the electromechanical properties of graphene-cement composites on the loading rate is studied by combining experiment and theory. The graphene-cement composites are prepared using a wet dispersion technique combined with surfactant assist and ultrasonication treatment. Both monotonic and cyclic compressive experiments with different loading rates are conducted on the graphene-cement composites with different graphene contents to measure their mechanical, electrical and piezoresistive properties. The optimum dosage of graphene in cement matrix is about 0.05 wt%, which can increase the compressive strength by 35.7 % and 34.1 %, and decrease the electrical resistivity to 1.43 and 3.48 × 105 Ω•cm, respectively, after 14 and 28 d curing periods. The uniform dispersion of graphene with less layers endows the graphene-cement composites with very low percolation threshold of electrical conductivity (0.007 wt%), stable piezoresistive response, and good reproducibility. Furthermore, the mechanism of the loading rate on the strain sensing behavior is discussed, and a rate dependent theoretical model of resistance change is proposed to quantitatively predict the electromechanical responses. This study provides guidelines for the fabrication of highly strain-sensitive graphene-cement composites and the rate-dependent evaluation of their electromechanical properties in the fields of intelligent construction.

Epsilon‐negative materials with lower percolation threshold derived from segregated structures

AbstractEpsilon‐negative materials (ENM) at radio frequency, usually designed based on percolation theory, recently drew much attention because of their potential applications in capacitors, transistors, and antennas. However, randomly distributed conductive functional materials cannot achieve directional long‐range electron transportation within the material, resulting in decreased utilization efficiency. The morphology design of the substrate material can change the distribution state and electron transfer pathway of conductive fillers. By controlling the size of the polystyrene (PS) and the content of multi‐walled carbon nanotubes (MWCNTs), PS/MWCNTs composites with random structures and segregated structures were designed, both of which exhibited negative permittivity with increasing MWCNTs content. Further investigation revealed that negative permittivity behavior is due to the establishment of the conductive network and the plasma oscillation of free electrons. Moreover, components with segregated structures have lower percolation thresholds, as directional electron transport is achieved and conductive fillers are efficiently utilized. This work provides a new method for guiding the electron transport pathway and effectively changing the distribution state of conductive fillers in ENM.Highlights Negative permittivity is achieved by plasma oscillation at radio frequency. The segregated structure leads to a decrease in the percolation threshold. Epsilon‐negative materials have good prospects in inductive components.

Honeycomb network structure constructed by silver nanoparticles achieving negative permittivity at low percolation threshold

Continuous conductive network is associated with the percolation effect, yet the method of fabricating network structure at low content is still a challenge. Herein, this work proposed a “honeycomb” structure via hot pressing to realize weak negative permittivity at low percolation threshold. By polydopamine (PDA) self-polymerization and silver mirror reaction plating, Ag nanoparticles coated polystyrene (PS) microsphere (PS@PDA@Ag) was prepared. Through hot pressing, the microspheres were compressed into “honeycomb”. The percolation threshold was reduced because the thin silver layer oscillated at low frequency plasma. Besides, by controlling the slivering time, weak negative permittivity in the range of −139 to −95 was observed and the percolation threshold was merely 2.23 vol%. The ac conductivity increased by four orders of magnitude and the thermal conductivity enhanced 79.08 %. The electric field and power loss density were simulated by finite element method. More than 100 V/m of electric field mode and 3 × 1011 W/m3 of power loss density were presented, explaining the generation of negative permittivity and the enhancement of dielectric loss. This work presented a method of achieving weak negative dielectric via honeycomb structure, and provided a novel perspective for the development of metal-based metacomposites.

Thermal, Mechanical and Electrical Properties of Ag Nanoparticle–Polymethyl Methacrylate Composites Under Different Service Temperatures

Ag-nanoparticle-reinforced polymethyl methacrylate (AgNP/PMMA) composites are widely used in healthcare, electronics, construction, transportation and many other fields. As the service temperature fluctuates easily, it is necessary to study the temperature effect on the properties of AgNP/PMMA composites. In this work, a preparation method of mixing and hot-pressing was used to fabricate multifunctional AgNP/PMMA composites that are suitable for large-scale industrial production. AgNPs are found to disperse homogeneously in the PMMA matrix. The thermal conductivity of the composite with 15 vol% AgNPs is 116.19% higher than that of PMMA and decreases as the temperature rises. Flexural strength increases first and then decreases with the rising of AgNP content and service temperature, while the flexural modulus decreases gradually. The minimum electrical resistivity of the composite achieves 1.37 × 10−3 Ω·m, with a low percolation threshold of 5 vol%, an improvement of nine orders of magnitude over PMMA. The results demonstrate that the service temperature has a significant effect on the comprehensive properties of AgNP/PMMA composites.

Multifunctional basalt fiber reinforced polymer composites with in-situ damage self-sensing and temperature-sensitive behavior

In this work, a multifunctional basalt fiber reinforced polymer composite (BFRP) with damage self-sensing and temperature-sensitive behavior was developed. Firstly, carbon nanotubes (CNTs) were deposited on basalt fibers (BF) by electrostatic self-assembly. Then, strong shear forces were applied during melt mixing with polyarylene ether nitrile (PEN) to construct a structure of CNTs surrounding the BF (CSB). This CSB structure endowed the composite with a low percolation threshold (0.82 wt% CNTs), a high conductivity (1.53 × 10−2 S/m at 1.12 wt% CNTs) and enhanced mechanical properties. The combination of resistance and acoustic emission real-time measurements confirmed that the composite achieved an excellent damage self-sensing capability with a maximum gauge factor (GF) of 7.68. Moreover, the composite exhibited a temperature-sensitive behavior with a temperature coefficient of resistance (TCR) of 0.542 %/°C. This study provides a significant guidance for the development of multifunctional BFRP with damage self-sensing and temperature sensitive behavior.

Excess noise and thermoelectric effect in magnetron-sputtered VO2 thin films

This work presents the excess noise and thermoelectric (Seebeck) measurements on polycrystalline vanadium dioxide (VO2) thin films. Noise spectral power density (SPD) of current fluctuations in the semiconducting (SC) phase had a typical flicker noise (f−γ) characteristic with an average slope parameter γ of 1.13. Normalized SPD (Sn) values obtained in the SC-phase indicate that the noise originates in the bulk of the film. On the contrary, in the metallic (M)-phase, γ values were greater than unity, and the observed Sn values indicated that the origin of the noise is most likely from the contacts or surface rather than the bulk. A general decrease was observed in Sn by a factor of 4–5 from the SC- to M-phase. Moreover, Sn in the SC-phase showed no temperature dependence. An interpretation based on the number of charge carrier fluctuations in Hooge's model led to an unrealistically high Hooge parameter and had to be ruled out. We propose that the fluctuations are related to the mobility fluctuations of carriers arising primarily from grain-boundary scattering which explains the observed characteristics well. The Seebeck coefficients (S) obtained under both heating and cooling schedules showed the n-type nature of magnetron-sputtered VO2 films in the SC-phase. Differently, in the M-phase, the S value was positive. The S values obtained from the cooling schedule signified the low percolation threshold of the metal-to-insulator transition already demonstrated for VO2 thin films grown on r-cut sapphire using the Efros–Shklovskii percolation model.

Enhancing the properties of epoxidized natural rubber-graphene nanocomposites through crosslinking with imidazole-activated dicarboxylic acid-cured system

The epoxidized natural rubber containing 25 mol% epoxide (ENR-25) was cured through crosslinking reactions with dodecanedioic acid (DA), both with and without activation by 1,2-dimethylimidazole (DMI). Analysis of the Fourier Transform Infrared (FTIR) spectroscopy of the DMI-activated DA-cured ENR revealed new absorption peaks at 1440 cm−1 and 1505 cm−1, indicating the presence of C-N stretching vibrations and carboxylate ions compared to samples without DMI activation. Additionally, ENR-graphene (GP) nanocomposites with various GP loadings were investigated, which revealed the formation of inter- and intramolecular hydrogen and covalent bonds within the ENR and GP networks. Furthermore, DMI activation of ENR cured with dicarboxylic acid accelerated the crosslinking reaction, reducing scorch and cure times while enhancing properties such as tensile strength, toughness, and 100 % modulus. Moreover, the incorporation and increased loading of GP in ENR nanocomposites synergistically enhanced strength properties, delta torque, crosslink density, initial relaxation modulus, thermal resistance, and electrical conductivity. This enhancement is attributed to interactions between the polar functional groups on GP surfaces and the functional groups of ENR adducts cured with DMI-activated dicarboxylic acid. Moreover, the ENR-GP nanocomposites exhibited a low percolation threshold concentration at 1.25 phr, enabling the formation of fully conductive GP networks within the ENR matrix. The significance of this study is to simplify the curing and production processes of ENR composites, offering promising self-healing capabilities and potential for reuse and recycling.

Modulating multiple interfaces, defects, and dual-scale interlinked frameworks of cotton-derived spiral CF@Ni@CNT fibers for boosted thermal conduction and microwave absorption

Developing dual-functional materials with excellent thermal conduction and microwave absorption has emerged as a critical strategy for addressing increasingly serious electromagnetic pollution and heat dissipation difficulties. While the advancements in these materials are constrained by their high loading and incompatible performance. To develop a thermally conductive and microwave-absorbing material with a low load, this work fabricates a series of cotton-derived spiral fibers, i.e., carbon fibers (CFs), carbon fiber/Ni (CF@Ni) fibers, and carbon fiber/Ni/carbon nanotube (CF@Ni@CNT) fibers, via a freeze-drying calcination method. By controlling the amount of nickel acetate (n) and methylbenzene volume (V), we finely modulated the multiple heterostructure interfaces, dual-scale interconnected network, defects, and magnetic/dielectric-loss of the spiral CF@Ni@CNT fibers. Results show that the comprehensive properties of spiral CF@Ni and CF@Ni@CNT fibers, obtained by combining spiral CFs with magnetic Ni nanoparticles and/or CNTs, are significantly improved. The spiral CF@Ni fibers formed at n = 8.4 mmol exhibit a lower thermal conductivity (TC = 3.64 W/m⋅K) but a wider absorption bandwidth (EAB = 6.4 GHz; 10 wt% load) than CFs. Besides, the spiral CF@Ni@CNT fibers formed at n = 4.2 mmol and V = 2 mL bear a higher TC (4.27 W/m⋅K) and a larger EAB (7.52 GHz/mm) at the same load (10 wt%). The low load could be ascribed to the low percolation threshold of a dual-scale interconnected framework consisting of CFs, CNTs, and Ni0. Additionally, the simultaneous improvement in thermal conduction and microwave absorption of the spiral CF@Ni@CNT fibers is associated with their magnetic-dielectric dual loss, electron-phonon co-transmission, and dual-scale interconnected framework.

Porous PVDF composites with ultralow percolation threshold for wide-range dynamic and static pressure sensing

Porous conductive polymer composites are very attractive for static pressure sensing due to high sensitivity and good elasticity contributed by the porous structure, while they are hard to detect dynamic pressure. Herein, we report a porous conductive poly (vinylidene fluoride) (PVDF) composite capable of detecting static and dynamic pressure over a pressure range of 0–1 MPa, which was fabricated by melt mixing PVDF, polyethylene oxide (PEO) and carbon nanofillers, followed by etching PEO with water. Such porous PVDF composites have a very low percolation threshold (0.035 wt%) of carbon nanostructures (i.e., branched carbon nanotubes) thanks to the selective distribution of conductive fillers in the pore wall after etching. At the same time, the pore size and porosity of the porous PVDF composites can be tuned by the molecular weight (Mw) and blending ratios of two polymers, leading to the kinetically-tailorable blend morphology for tunable mechanical and electrical properties. The as-fabricated porous PVDF composites with a good combination of mechanical properties and electrical conductivities, which can be used as pressure sensors toward wide-range (0–1 MPa) dynamic and static pressure sensing. Such pressure sensors demonstrate potential applications in detecting the degree of finger bending, distinguishing the walking and running, and monitoring a series of technical movements in playing soccer, i.e., static and dynamic exercises.

Morphology and electrical conductivity of carbon-coated Nickel reinforced high-performance polymer nanocomposites

Novel nanocomposites of poly (ether-ketone) (PEK) reinforced with carbon-coated Nickel nanoparticles (CCNi) were synthesized through a sequential process involving cost-effective ball milling and hot compaction. Scanning electron microscopy revealed an excellent dispersion and a three-dimensional network of CCNi nanoparticles in the matrix, causing a significant improvement in the electrical conductivity and electromagnetic interference shielding effectiveness (SE). Carbon coating of about 5 nm thick over Ni nanoparticle probably helps in uniform dispersion, avoids its oxidation and reduces its agglomeration in the matrix. An exceptionally low percolation threshold of 2.1 vol.% CCNi was found, and eight-orders of magnitude enhancement in the dc-electrical conductivity was achieved. The highest dc- and ac-electrical conductivities achieved were more than 0.01 S cm−1 at 5.89 vol.% CCNi nanoparticles content which were the highest values amongst reported Ni-filled polymer composites and comparable with those of carbon nanotubes filled PEK nanocomposites. Electromagnetic interference SE of the CCNi/PEK nanocomposites was measured in the X-band, and a total SE (SET) of 17.52 dB was obtained for 5.89 vol.% CCNi reinforced PEK nanocomposite.

Polydopamine/SWCNT Ink Functionalization of Silk Fabric to Obtain Electroconductivity at a Low Percolation Threshold.

This study presents the functionalization of silk fabric with SWCNT ink. The first step was the formation of a polydopamine (PDA) thin coating on the silk fabric to allow for effective bonding of SWCNTs. PDA formation was carried out directly on the fabric by means of polymerization of dopamine in alkali conditions. The Silk/PDA fabric was functionalized with SWCNT ink of different SWCNT concentrations by using the dip-coating method. IR and Raman analyses show that the dominant β-sheet structure of silk fibroin after the functionalization process remains unchanged. The heat resistance is even slightly improved. The hydrophobic silk fabric becomes hydrophilic after functionalization due to the influence of PDA and the surfactant in SWCNT ink. The ink significantly changes the electrical properties of the silk fabric, from insulating to conductive. The volume resistance changes by nine orders of magnitude, from 2.4 × 1012 Ω to 2.3 × 103 Ω for 0.12 wt.% of SWCNTs. The surface resistance changes by seven orders of magnitude, from 2.1 × 1012 Ω to 2.4 × 105 Ω for 0.17 wt.% of SWCNTs. The volume and surface resistance thresholds are determined to be about 0.05 wt.% and 0.06 wt.%, respectively. The low value of the percolation threshold indicates efficient functionalization, with high-quality ink facilitating the formation of percolation paths through SWCNTs and the influence of the PDA linker.

DISTINCTIVE FEATURES OF CELLULOSE NANOCRYSTALLITES

In this paper, a set of methods was used to study the structural characteristics and properties of cellulose nanocrystallites and free cellulose nanocrystalline particles (CNCs). It was shown that cellulose nanocrystallites have three main distinctive features. The first distinctive feature of cellulose nanocrystallites is their rod-like shape with a quite high aspect ratio and a low percolation threshold. The second distinctive feature of nanocrystallites is their highly developed specific surface area that leads to the spontaneous crystallization and aggregation of rod-like crystallites by their lateral planes. This aggregation process is thermodynamically favorable because it leads to a decrease in the specific surface area of nanocrystallites and a reduction of the thermodynamic potential. The third distinctive feature of cellulose nanocrystallites is the paracrystalline structure of their surface layers, which significantly affects structural characteristics such as lattice distortion, interplanar spacings, parameters, and volume of the crystalline unit cell, etc. Along with structure, the paracrystalline fraction affects also important physical and physical-chemical properties of cellulose, such as accessibility to deuteration, the content of CII-allomorph after cellulose alkalization, melting point of nanocrystallites, etc. Correlation equations were derived that provide to predict the structural characteristics and properties of nanocrystallites using the content of the paracrystalline fraction.