Enhanced thermal conductivity and dielectric properties of Al/β-SiCw/PVDF composites

Polymeric composites with high thermal conductivity, high dielectric permittivity but low dissipation factor have wide important applications in electronic and electrical industry. In this study, three phases composites consisting of poly(vinylidene fluoride) (PVDF), Al nanoparticles and β-silicon carbide whiskers (β-SiC_w) were prepared. The thermal conductivity, morphological and dielectric properties of the composites were investigated. The results indicate that the addition of 12 vol% β-SiC_w not only improves the thermal conductivity of Al/PVDF from 1.57 to 2.1 W/m K, but also remarkably increases the dielectric constant from 46 to 330 at 100 Hz, whereas the dielectric loss of the composites still remain at relatively low levels similar to that of Al/PVDF at a wider frequency range from 10⁻¹ Hz to 10⁷ Hz. With further increasing the β-SiC_w loading to 20 vol%, the thermal conductivity and dielectric constant of the composites continue to increase, whereas both the dielectric loss and conductivity also rise rapidly.     

Graphene sheets segregated by barium titanate for polyvinylidene fluoride composites with high dielectric constant and ultralow loss tangent

In this paper, we report a unique method to develop polyvinylidene fluoride (PVDF) composites with high dielectric constant and low loss tangent by loading relatively low content of graphene-encapsulated barium titanate (BT) hybrid fillers. BT particles encapsulated with graphene oxide (BT-GO) were prepared via electrostatic self-assembly and subsequent chemical reduction resulted in BT-RGO particles. SEM morphology revealed that RGO sheets were segregated by BT particles. The hybrid fillers have two advantages for tuning dielectric properties: loading extremely low content of RGO can be exactly controlled and individual RGO sheets segregated by BT particles would prevent leakage current. As a result, PVDF composites filled with BT-RGO displayed improved dielectric properties before percolative behavior occurred. Composites filled with 30 vol% BT-RGO have a dielectric constant and loss tangent (tan δ) value of 67.5 and 0.060 (1 kHz), respectively. By contrast, dielectric constant and tan δ of composites filled with 30 vol% BT-GO and BT were 57.7 and 38.3, 0.076 and 0.042 (1 kHz), respectively. The improvement of dielectric constant is attributable to the formation of microcapacitors by highly conductive RGO sheets segregated by BT particles. Meanwhile, the distance between adjacent RGO sheets is large enough to prevent leakage current from tunneling conductance, by which tan δ is remarkably constrained. The composites could achieve excellent dielectric properties by loading relatively low amount of ceramic fillers, which indicates that this method can be used as guideline for reduce the usage amount of ceramic fillers.     

Polydopamine coating layer on graphene for suppressing loss tangent and enhancing dielectric constant of poly(vinylidene fluoride)/graphene composites

Graphene with polydopamine (PDA) coating layer which displays promoted dispersibility in organic solvent was prepared through self-polymerization of dopamine onto graphene oxide (GO) and subsequent chemical reduction. The PDA coated reduced GO (RDGO) is homogeneously incorporated into poly(vinylidene fluoride) (PVDF) matrix, which exhibit a percolation threshold at 0.643 wt%. The dielectric constant of PVDF with 0.70 wt% RDGO increases to 176, about 17 times of neat PVDF. Importantly, the loss tangent is suppressed to 0.337 due to reduction of the concentration and mobility of ionizable carboxylic groups by PDA. The enhancement of dielectric constant probably rises from duplex interfacial polarization induced by graphene–semiconductor interface, and semiconductor–insulator interface. The composites displays advantages in excellent dielectric properties and good flexibility and processability guaranteed by low loading of RDGO, which is suitable for the development of dielectric materials for energy storage.     

Effect of coupling agents on the dielectric properties of CaCu3Ti4O12/PVDF composites

Phase-pure calcium copper titanate (CaCu₃Ti₄O₁₂, CCTO) ceramic particles were synthesized via a sol–gel route. The CCTO was treated by bis[3-(triethoxysilyl)propyl]tetrasulfide (Si69) to give CCTO@Si69. The dielectric composites based on CCTO (or CCTO@Si69) and polyvinylidene fluoride (PVDF) were molded with desirable dielectric properties by mechanical mixing process and hot-pressing. The structures of CCTO and CCTO@Si69 were investigated by scanning electron microscopy (SEM) energy spectrum, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy. The stretching vibration of SO at 1096 cm⁻¹ in FTIR is an indication that chemical bond was formed between Si69 and CCTO. The influence of Si69 on the preparation and the dielectric properties of CCTO/PVDF dielectric composites were discussed. When the content of Si69 was 0.1 mL (relative to 1 g of CCTO), the dielectric constant (ε) (at a frequency of 1 kHz) of CCTO@Si69/PVDF composites reached the maximum value of 84, this value is 5.25 times that of an equal amount of CCTO of CCTO/PVDF composites (ε ≈ 16). The CCTO/PVDF and CCTO@Si69/PVDF composites had very stable dielectric properties over a wide range of temperatures (20–160 °C). These composites can be applied as high-energy–density capacitors in electronic and electrical engineering fields.     

Tunable BT@SiO2 core@shell filler reinforced polymer composite with high breakdown strength and release energy density

Barium titanate@silicon dioxide (BT@SiO₂) core@shell fillers with an average diameter of 100 nm were prepared by a facile sol–gel synthesis. The thickness of SiO₂ shell can be easily tuned by varying different mass ratio of BT to tetraethyl orthosilicate (TEOS). Polyvinylidene fluoride (PVDF) based composite films reinforced by BT and BT@SiO₂ were fabricated via a solution casting method. The effects of SiO₂ shell on morphology structure, wettability, interfacial adhesion, dielectric, electrical and energy performances of composites were investigated. Compared with BT/PVDF, BT@SiO₂/PVDF composites show significantly increased breakdown strength due to enhanced interfacial adhesion and suppressed charge carrier conduction. Benefiting from enhanced breakdown strength and reduced remnant polarization induced by SiO₂ shell, BT@SiO₂/PVDF shows increased release energy density (energy density which can be fully discharged and applicable). Especially, BT@SiO₂/PVDF with SiO₂ thickness of 4 nm exhibits the highest release energy density of 1.08 J/cm³ under applied electric field of 145 kV/mm.     

Segregated poly(vinylidene fluoride)/MWCNTs composites for high-performance electromagnetic interference shielding

Conductive polymer composites (CPCs) that contain a segregated structure have attracted significant attentions because of their promising for fulfilling low filler contents with high electromagnetic interference (EMI) properties. In the present study, segregated poly(vinylidene fluoride) (PVDF)/multi-walled carbon nanotubes (MWCNTs) composites were successfully prepared by mechanical mixing and hot compaction. The PVDF/MWCNTs samples with 7 wt% filler content possess high electrical conductivities and high EMI shielding effectiveness (SE), reaching 0.06 S cm⁻¹ and 30.89 dB (in the X-band frequency region), much higher than lots of reported results for CNT-based composites. And the EMI SE greatly increased across the frequency range as the sample thickness was improved from 0.6 to 3.0 mm. The EMI shielding mechanisms were also investigated and the results demonstrated absorption dominating shielding mechanism in this segregated material. This effective preparation method is simple, low-cost, and environmentally-friendly and has potential industrial applications in the future.     

Investigation of thermal conductivity and dielectric properties of LDPE-matrix composites filled with hybrid filler of hollow glass microspheres and nitride particles

The hybrid filler of hollow glass microspheres (HGM) and nitride particles was filled into low-density polyethylene (LDPE) matrix via powder mixing and then hot pressing technology to obtain the composites with higher thermal conductivity as well as lower dielectric constant (D_k) and loss (D_f). The effects of surface modification of nitride particles and HGMs as well as volume ratio between them on the thermal conductivity and dielectric properties at 1 MHz of the composites were first investigated. The results indicate that the surface modification of the filler has a beneficial effect on thermal conductivity and dielectric properties of the composites due to the good interfacial adhesion between the filler and matrix. An optimal volume ratio of nitride particles to HGMs of 1:1 is determined on the basis of overall performance of the composites. The thermal conductivity as well as dielectric properties at 1 MHz and microwave frequency of the composites made from surface-modified fillers with the optimal nitride to HGM volume ratio were investigated as a function of the total volume fraction of hybrid filler. It is found that the thermal conductivity increases with filler volume fraction, and it is mainly related to the type of nitride particle other than HGM. The D_k values at 1 MHz and microwave frequency show an increasing trend with filler volume fraction and depend largely on the types of both nitride particles and HGMs. The D_f values at 1 MHz or quality factor (Q × f) at microwave frequency show an increasing or decreasing trend with filler volume fraction and also depend on the types of both nitride particle and HGM. Finally, optimal type of HGM and nitride particles as well as corresponding thermal conductivity and dielectric properties is obtained. SEM observations show that the hybrid filler particles are agglomerated around the LDPE matrix particles, and within the agglomerates the smaller-sized nitride particles in the hybrid filler can easily form thermally conductive networks to make the composites with high thermal conductivity. At the same time, the increase of the value D_k of the composites is restricted due to the presence of HGMs.     

Fabrication and characterization of 3-D Cf/ZrC composites by low-temperature liquid metal infiltration

Three-dimensional braided carbon fiber-reinforced ZrC matrix composite, 3-D C_f/ZrC, were prepared by liquid metal infiltration process at 1200 °C using a Zr₂Cu intermetallic compound as infiltrator. The microstructure and properties of the composites were investigated. The results indicated that ZrC with a yield of 35.2 ± 1.8 vol.% was certified as the major phase of the composites. The formation of ZrC was controlled by a solution-precipitation mechanism. The obtained composites exhibited good mechanical properties, with a flexural strength of 293.0 ± 12.1 MPa, a flexural modulus of 82.7 ± 6.4 GPa and a fracture toughness of 9.8 ± 0.9 MPa m^1/2. The mass and linear ablation rates of the composites exposed to oxyacetylene torch were 0.0013 ± 0.0005 g s⁻¹ and −0.0009 ± 0.0003 mm s⁻¹, respectively. The formation of a dense ZrO₂ protective layer and the evaporation of residual Cu contributed mainly to the excellent ablation resistance.     

Enhancement of dielectric and electrical properties in BT/SiC/PVDF three-phase composite through microstructure tailoring

A polymer composite with high dielectric permittivity was prepared by embedding silicon carbide (SiC) whisker with an average diameter of 500 nm–1 μm in poly(vinylidene fluoride) (PVDF). However, the high dielectric loss and electrical conductivity of the two-phase composite prohibits its potential applications. Barium titanate (BT) particles with average diameter of 100 nm and 1 μm were incorporated as a third phase to fabricate a three-phase composite. The morphology structure, dielectric and electrical properties before and after the addition of BT particles were investigated. The three-phase composite exhibits largely suppressed dielectric loss and electrical conductivity without sacrificing the high dielectric permittivity, which was extremely hard to be realized for two-phase composite. It is also found that the nano-size BT is more favorable in achieving high dielectric permittivity than the micro-size BT, where their dielectric loss and electrical conductivity are similar. Furthermore, electric modulus analysis confirms the largely suppressed electron conduction process which results in the enhanced dielectric and electrical properties in three-phase composite.     

Polydimethylsiloxane–barium titanate composites: Preparation and evaluation of the morphology,moisture, thermal,mechanical and dielectric behavior

Polydimethylsiloxane-α,ω-diols were used as matrix for barium titanate particles to obtain electroactive elastomeric composites. Filler particles were previously treated with a surfactant to improve the compatibility with and dispersibility in the matrix. The composites, processed as films and crosslinked with methyltriacetoxysilane, were investigated from point of view of the morphology, moisture sorption and thermal properties, as well as mechanical and dielectric behavior. Maximum strain value of 850% at 0.32 MPa and dielectric permittivity of 4.41 at 10 Hz and 20 °C were obtained. Two parameters of interest for potential future application of such materials in electromechanical devices (actuation or harvesting), electromechanical sensitivity and harvesting energy capacity, were estimated and discussed in correlation with the molecular mass of the polymeric matrix and the content of the active filler.     

Electromagnetic shielding effectiveness of aluminum alloy–fly ash composites

The cenosphere and precipitator fly ash particulates were used to produce two kinds of aluminum matrix composites with the density of 1.4–1.6 g cm⁻³ and 2.2–2.4 g cm⁻³ separately. The electromagnetic interference shielding effectiveness (EMSE) properties of the composites were measured in the frequency range of 30.0 kHz–1.5 GHz. The results indicated the EMSE properties of the two types of composites were nearly the same. By using the fly ash particles, the shielding effectiveness properties of the matrix aluminum have been improved in the frequency ranges 30.0 kHz–600.0 MHz and the increment varied with increasing frequency. The EMSE properties of 2024Al are in the range −36.1 ± 0.2 to −46.3 ± 0.3 dB while the composites are in the range −40.0 ± 0.8 to −102.5 ± 0.1 dB in the frequency range 1.0–600.0 MHz. At higher frequency, the EMSE properties of the composites are similar to that of the matrix. The tensile strength of the matrix aluminum has been decreased by addition of the fly ash particulate and the tensile strength of the composites were 110.2 MPa and 180.6 MPa separately. The fractography showed that one composite fractured brittly and the other fractured in a microductile manner.     

Effect of surface functionalization on mechanical properties and decomposition kinetics of high performance polyetherimide/MWCNT nano composites

In this investigation, Polyetherimide (PEI) reinforced with multi-walled carbon nanotube (MWCNT) using novel melt blending technique. Surface of MWCNTs are modified by acid treatment as well as by plasma treatment. PEI nano composites with 2 wt% treated MWCNT shows about 15% improvement in mechanical properties when compared to unfilled PEI. The thermal decomposition kinetics of PEI/MWCNT nano composites has been critically analyzed by using Coats – Redfern model. The increase in activation energy for thermal degradation by 699 kJ/mol for 2 wt% MWCNT implies improvement in the thermal properties of PEI. Studies under Fourier Transform Infrared Spectroscopy (FTIR) and Transmission Electron Microscopy (TEM) depict significant interfacial adhesion with uniform dispersion of MWCNT in polymer matrix due to surface functionalization. 0.5 wt% chemically modified MWCNT shows typical alignment of MWCNT. There is a significant improvement in mechanical properties and thermal properties for surface functionalized MWCNT reinforced.     

The effect of polymer spatial configuration on the microwave absorbing properties of non-covalent modified MWNTs

The polar polymer of linear and star polymethyl methacrylate (PMMA) was used to modify the surface of multi-walled carbon nanotubes (MWNTs). Raman and TGA were used to characterize structure of the functionalized MWNTs. The effect of polymer spatial configuration on the MWNTs dispersion, morphology and interfacial interaction was investigated by scanning electron microscopy and transmission electron microscopy. The aim of the work is to investigate the effect of polymer spatial configuration on the microwave absorbing properties. The results showed that the maximum reflection loss of linear PMMA/MWNTs hybrids was −37 dB in the frequency of 8.8 GHz, and the bandwidth below −10 dB was more than 2.1 GHz. While the maximum reflection loss of the S-PMMA/MWNTs hybrids reached −50 dB in the frequency of 8.4 GHz, and the bandwidth below −10 dB was 2.3 GHz. The results indicated that the microwave absorbing properties of star PMMA polymers modified MWNTs were superior to that of linear PMMA polymers.     

Enhanced thermal conductivity of SiCp/PS composites by electrospinning–hot press technique

Silicon carbide particle/polystyrene (SiCp/PS) electrospun mats are firstly prepared by electrospinning technology, then to be fabricated the corresponding thermally conductive SiCp/PS composites by the method of “laminating-hot press”. The mass fraction of SiCp and laminating mode of SiCp/PS electrospun mats affecting on the thermal conductivities, dielectric and thermal properties of the composites are investigated. The addition of 32.8 vol% SiCp improves the thermally conductive coefficient λ of pure PS from 0.182 to 0.566 W/m K and thermal diffusivity of pure PS from 0.169 to 0.376 mm²/s, whereas the dielectric constant values still remain at relatively low levels. The thermal stabilities of the SiCp/PS composites are increased with the increasing addition of SiCp. For a given SiCp loading, the SiCp/PS composites from warp–weft arrangement of SiCp/PS electrospun mats possess relative higher thermally conductive coefficient λ and dielectric constant values than those of SiCp/PS composites from warp–warp arrangement of SiCp/PS electrospun mats.     

Assessment of three oxide/oxide ceramic matrix composites: Mechanical performance and effects of heat treatments

Mechanical performance of three oxide/oxide ceramic matrix composites (CMCs) based on Nextel 610 fibers and SiOC, alumina, and mullite/SiOC matrices respectively, is evaluated herein. Tensile strength and stiffness of all materials decreased at 1000 °C and 1200 °C, probably because of degradation of fiber properties beyond 1000 °C. Microstructural changes in the composites during exposure at 1000 °C and 1200 °C for 50 h reduce their flexural strength, fracture toughness and work of fracture. A literature review regarding mechanical properties of several oxide/oxide CMCs revealed lower influence of fiber properties on composite strength compared with elastic modulus. The tested composites exhibit comparable stiffness and strength but higher fracture toughness compared with average values determined from a literature review. Considering CMCs with different compositions, we observed an interesting linear trend between strength and fracture toughness. The validity of the linear relationship between fracture strength and flexural toughness for CMCs is discussed.     

Tailoring of thermal and dielectric properties of LDPE-matrix composites by the volume fraction,density, and surface modification of hollow glass microsphere filler

Hollow glass microsphere (HGM) filled low-density polyethylene (LDPE) composites were prepared, and the effects of density, content, and surface modification of HGM on the thermal and dielectric properties of the composites were investigated. It is found that the thermal conductivity of the composites decreases with increasing HGM content or decreasing HGM density. At the same HGM content and density, the composites filled with suitable amount of silane coupling agent (KH570) modified HGM exhibit higher thermal conductivity than unmodified-HGM filled composites. The dielectric constant at 1 MHz of the composites also decreases with increasing HGM content or decreasing HGM density, but their dielectric loss increases with increasing HGM content or increasing HGM density. By modifying the surface of HGM with suitable amount of KH570, the dielectric constant and loss at 1 MHz of the composites can be decreased at the same time. The results of microwave dielectric properties of the composites indicate that the dielectric constant decreases with increasing HGM content or decreasing HGM density, the quality factor (Q × f) decreases with increasing HGM content or increasing HGM density, but both dielectric constant and quality factor are slightly affected by the surface modification of HGM. Due to lower intrinsic thermal conductivity and dielectric constant but higher dielectric loss of HGM than LDPE, the thermal conductivity and dielectric properties of the composites can be controlled with adding HGM and varying its volume fraction. The surface modification of HGM improves the interface contact between HGM and LDPE in the composites, which is confirmed by the SEM observation, and thus the heat conduction and dielectric properties at low frequency are improved. Based on calculated thermal conductivity and dielectric constant of HGM, the experimental trends of thermal conductivity and dielectric constant at 1 MHz of the composites are analyzed by using different models, including typical models for particles-filled composites and special models developed for hollow microsphere filled composites. The results from suitable models show close correlation with the experimental values.     

Preparation of high k expanded graphite/CaCuTi4O12/cyanate ester composites with low dielectric loss through controlling the interfacial action between conductors and ceramics

New composites with high dielectric constant and low dielectric loss, based on expanded graphite (EG), CaCuTi₄O₁₂ (sCCTO) and cyanate ester (CE) resin, were developed by controlling the interaction between EG and sCCTO. Difference from EG, surface modified EG (mEG) has an additional strong chemical interaction with sCCTO, this not only improves the dispersion of fillers, but also enhances the filler-matrix interfacial adhesion, leading to different micro-structures and dielectric properties. Specifically, the percolation thresholds of mEG/sCCTO/CE and EG/sCCTO/CE composites are 3.45 vol% and 2.86 vol%, respectively. When the loading of conductors approaches the percolation threshold, mEG/sCCTO/CE composite has much higher dielectric constant and lower dielectric loss than EG/sCCTO/CE composite. The nature behind these attractive data was revealed by building an equivalent circuit.     

Highly thermally conductive POSS-g-SiCp/UHMWPE composites with excellent dielectric properties and thermal stabilities

Polyhedral oligomeric silsesquioxane grafting thermally conductive silicon carbide particle (POSS-g-SiCp) fillers, are performed to fabricate highly thermally conductive ultra high molecular weight polyethylene (UHMWPE) composites combining with optimal dielectric properties and excellent thermal stabilities, via mechanical ball milling followed by hot-pressing method. The POSS-g-SiCp/UHMWPE composite with 40 wt% POSS-g-SiCp exhibits relative higher thermal conductivity, lower dielectric constant and more excellent thermal stability, the corresponding thermally conductive coefficient of 1.135 W/mK, the dielectric constant of 3.22, and the 5 wt% thermal weight loss temperature of 423 °C, which holds potential for packaging and thermal management in microelectronic devices. Agari’s semi-empirical model fitting reveals POSS-g-SiCp fillers have strong ability to form continuous thermally conductive networks.     

High-temperature dielectric and electromagnetic interference shielding properties of SiCf/SiC composites using Ti3SiC2 as inert filler

Ti₃SiC₂ filler has been introduced into SiC_f/SiC composites by precursor infiltration and pyrolysis (PIP) process to optimize the dielectric properties for electromagnetic interference (EMI) shielding applications in the temperatures of 25–600 °C at 8.2–12.4 GHz. Results indicate that the flexural strength of SiC_f/SiC composites is improved from 217 MPa to 295 MPa after incorporating the filler. Both the complex permittivity and tan δ of the composites show obvious temperature-dependent behavior and increase with the increasing temperatures. The absorption, reflection and total shielding effectiveness of the composites with Ti₃SiC₂ filler are enhanced from 13 dB, 7 dB and 20 dB to 24 dB, 21 dB and 45 dB respectively with the temperatures increase from 25 °C to 600 °C. The mechanisms for the corresponding enhancements are also proposed. The superior absorption shielding effectiveness is the dominant EMI shielding mechanism. The optimized EMI shielding properties suggest their potentials for the future shielding applications at temperatures from 25 °C to 600 °C.     

Enhancement of fracture toughness,mechanical and thermal properties of rubber/epoxy composites by incorporation of graphene nanoplatelets

Carboxyl terminated butadiene acrylonitrile (CTBN) was added to epoxy resins to improve the fracture toughness, and then two different lateral dimensions of graphene nanoplatelets (GnPs), nominally <1 μm (GnP-C750) and 5 μm (GnP-5) in diameter, were individually incorporated into the CTBN/epoxy to fabricate multi-phase composites. The study showed that GnP-5 is more favorable for enhancing the properties of CTBN/epoxy. GnPs/CTBN/epoxy ternary composites with significant toughness and thermal conductivity enhancements combined with comparable stiffness to that of the neat resin were successfully achieved by incorporating 3 wt.% GnP-5 into 10 wt.% CTBN modified epoxy resins. According to the SEM investigations, GnP-5 debonding from the matrix is suppressed due to the presence of CTBN. Nevertheless, apart from rubber cavitation and matrix shear banding, additional active toughening mechanisms induced by GnP-5, such as crack deflection, layer breakage and separation/delamination of GnP-5 layers contributed to the enhanced fracture toughness of the hybrid composites.