Dielectric properties of polymer/ceramic composites based on thermosetting polymers

Summary A series of thermosetting polymer/ceramic composites were prepared. Three kinds of thermosetting polymers, i.e. cyanate resin, bismaleimide resin, and epoxy resin, were used as matrixes, and BaTiO₃ particles were as fillers. The dielectric properties of these composites were investigated. Experimental data of the dielectric constants were fitted to several theoretical equations in order to obtain the best-fitting equations of the dielectric constants of these composites. The result indicates that the dielectric constants of composites all increase with the increase of BaTiO₃ content. Using bismaleimide resin and epoxy resin as matrixes, the dielectric losses both increase obviously as the amount of BaTiO₃ particles is increased, but the dielectric loss of cyanate/BaTiO₃ composite decreases. With the increase of the frequency, the variation ranges of the dielectric constant and dielectric loss of cyanate/BaTiO₃ composite are both the smallest. The predications of the effective dielectric constants by Lichterecker mixing rule are in good agreement with experiment data.     

Effects of BaTiO3 and FeAlSi as fillers on the magnetic,dielectric and microwave absorption characteristics of the epoxy-based composites

A systematic study was carried out on the magnetic, dielectric and microwave absorption properties of the two-phase FeAlSi/epoxy and three-phase FeAlSi/BaTiO₃/epoxy composites through experimental and simulation method. A percolation effect was observed in the dielectric, but not in the magnetic behavior of the FeAlSi/epoxy composites when the FeAlSi content was high. The 2D modeling shows that the high electric energy density is responsible for the high permittivity near the percolation threshold (49 vol%). On the other hand, the permeability of the composites matches well with the effective medium theory model (EMT), indicating that the permeability of FeAlSi/epoxy composite is more associated with the filler size and shape. Theoretical calculations show that the increment of the FeAlSi and BaTiO₃ loading, as well as the thickness will cause the absorption peak position to shift to low frequencies. The microwave absorption of these composites can be mainly attributed to the dielectric loss and magnetic loss.     

Thermal and dielectric properties of the aluminum particle/epoxy resin composites

Microsized aluminum/epoxy resin composites were prepared, and the thermal and dielectric properties of the composites were investigated in terms of composition, aluminum particle sizes, frequency, and temperature. The results showed that the introduction of aluminum particles to the composites hardly influenced the thermal stability behavior, and decreased T_g of the epoxy resin; moreover, the size, concentration, and surface modification of aluminum particles had an effect on their thermal conductivity and dielectric properties. The dielectric permittivity increased smoothly with a rise of aluminum particle content, as well as with a decrease in frequency at high loading with aluminum particles. While the dissipation factor value increased slightly with an increase in frequency, it still remained at a low level. The dielectric permittivity and loss increased with temperature, owing to the segmental mobility of the polymer molecules. We found that the aluminum/epoxy composite containing 48 vol % aluminum‐particle content possessed a high thermal conductivity and a high dielectric permittivity, but a low loss factor, a low electric conductivity, and a higher breakdown voltage. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of the modification of barium titanate on the permittivity of its composites with cyanoethyl ester of polyvinyl alcohol

The effect of chemical modification of submicron barium titanate particles by the deposition of M _x O _y (x = Ti, Co, Ni) oxide layers from aqueous solutions of the corresponding precursors is studied upon the surface properties of modified BaTiO₃ particles and dielectric permittivity of organo-inorganic composites obtained by their dispersion in the matrix of cyanoethyl ester of polyvinyl alcohol and useful in electroluminescent light sources. It is shown that a significant increase (by about 25%) of the dielectric permittivity is observed only when adding Nb₂O₅, in comparison with a similar composite which contains unmodified BaTiO₃. A correlation is found between the dielectric permittivity of the organo-inorganic composites and the presence of Brensted neutral and basic centers with pK _a = 6−13, localized on the surface of a filler, being capable of interacting with the polymer matrix. It is shown that an increase of the dielectric permittivity upon deposition of niobium oxide on the surface of BaTiO₃ is caused by formation of such centers and modification of the surface layer structure of BaTiO₃ particles, with transformation of rutile-like Ti-O bonds to anataselike ones.     

Effect of the filler morphology on the crystallization behavior and dielectric properties of the polyvinylidene fluoride-based composite

Ceramic/polymer composites can be chemically stable, mechanically strong, and flexible, which make them candidates for electric devices, such as pressure or temperature sensors, energy storage or harvesting devices, actuators, and so forth. Depending on the application, various electrical properties are of importance. Polymers usually have low dielectric permittivity, but increased dielectric permittivity can be achieved by the addition of the ceramic fillers with high dielectric constant. With the aim to enhance dielectric properties of the composite without loss of flexibility, 5 wt% of BaTiO₃-Fe₂O₃ powder was added into a polyvinylidene fluoride matrix. The powder was prepared by different synthesis conditions to produce core/shell structures. The effect of the phase composition and morphology of the BaTiO₃-Fe₂O₃ core/shell filler on the structure and lattice dynamics of the polymer composites was investigated. Based on the results of the thermal analysis, various parameters of ceramic/polymer composites were determined. Differences in the phase composition and morphology of the filler have an influence on the formation of various polyvinylidene fluoride allomorphs and the degree of crystallinity. Furthermore, the dielectric performances of pure polyvinylidene fluoride and the polymer/ceramic composites were measured.     

BaTiO3–Epoxy Composites for Electronic Applications

A brief review related with dielectric properties of BaTiO₃/epoxy composites is presented. The composites were obtained using the dipping technique. To facilitate the mixing and modify the filler surface, a solvent and a surface coupling agent were used. Intermediate and low concentrations of solvent and silane improved microstructure and dielectric properties of the composite material, whereas higher concentrations led to composites of poor quality. Finally, a model using finite elements was used, in order to predict the composite permittivity in relation to the percentage of filler. Model results were compared with the effective medium theory and experimental results.     

Flexible BaTiO3/SiC@PbTiO3/epoxy composite films with enhanced dielectric performance at high frequency

Flexible polymer composites with high dielectric constants and low dielectric losses at high frequencies are highly desired in microwave and RF applications. However, a high dielectric constant is often obtained at the expense of flexibility because a high loading of filler is needed. In this work, we synthesize a core-shell structured 1D filler by coating high-dielectric-constant PbTiO₃ onto the surface of low-thermal-expansion-coefficient SiC nanofibers, which are then incorporated into the epoxy matrix together with BaTiO₃ nanoparticles to form the multi-phase BaTiO₃/SiC@PbTiO₃/epoxy composite film. A high dielectric constant (35 at 100 Hz and 20 at 5 GHz) and a low dielectric loss (0.023 at 100 Hz and 0.13 at 5 GHz) are achieved as the filling content of SiC@PbTiO₃ and BaTiO₃ is 5.24 wt% and 80 wt%, respectively. Prediction models of the effective dielectric constant of polymer-based composites reveal that a continuous polarization network is constructed in the composites owing to the physical contact between BaTiO₃ and PbTiO₃. The construction of the multi-phase filler provides a feasible way to effectively adjust and improve the dielectric properties of polymer-based composite films.     

Flexible 0–3 Ceramic‐Polymer Composites of Barium Titanate and Epoxidized Natural Rubber

Flexible composites with a high electrical permittivity are pursued in materials research, due to their potential applications in electrical devices. We synthesized such ceramic‐polymer composites from BaTiO₃ and epoxidized natural rubber. The influence of BaTiO₃ concentration on cure characteristics, mechanical (static & dynamic), dielectric, and morphological properties of the composites was investigated. The tensile strength and elongation at break decreased with BaTiO₃ loading, while the storage modulus and permittivity of composites increased. As for dynamic electrical properties, the dielectric loss factor and tan δ of the composites showed a maximum peak within the frequency range extending up to 10⁵ Hz, reflecting the relaxation process of the polymer matrix. All of the composites showed two peaks in the frequency dependence of electric modulus, due to conductivity and molecular relaxation. Scanning electron microscopy micrographs confirmed the 0–3 structure of composites, with isolated BaTiO₃ particles.     

BaTiO3 incorporation effect on the dielectric properties of polymer from aqueous emulsion: An enhanced dispersion technique

An economic and environment friendly process was adapted to synthesize new dielectric composite materials. Using ethylene vinyl acetate (EVA)/vinyl ester of versatic acid (VeoVa) terpolymer as an aqueous emulsion provides a homogenous dispersion of BaTiO₃ (BT) particles, due to the high viscosity and polarity of the vinyl resin (VR). Composites films were obtained from these dispersions by water evaporation. The evolution of the dielectric properties as a function of the BaTiO₃ content, was correctly fitted by a Maxwell‐Garnett model. This fitting of the experimental curve shows a good dispersion of filler in the vinyl resin and the particles separation by a layer of resin as expected for the preparation method used in this study. The VR/BT composites show good synergy between the dielectric properties of the different phases of the composites due to the formation of macrodipoles and to the strong interactions between polar EVA/VeoVa groups and the BaTiO₃ particles surface. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44333.     

Multi-phase coexistence and temperature-stable dielectric properties in BaTiO3/ZnO composite ceramics

BaTiO₃:100xZnO composite ceramics with different ZnO particle sizes were prepared by using a conventional solid-state method. Phase constitution, microstructure and dielectric properties of BaTiO₃:100xZnO composite ceramics are investigated. Compared to micrometer scaled ZnO particles, nanometer scaled ZnO particles tend to agglomerate at lower ZnO contents in the BaTiO₃:100xZnO composite ceramics. The introduction of ZnO in BaTiO₃ leads to the reduction of grain size, decrease of the tetragonality and shift of phase transition temperature. The optimum composition is BaTiO₃ with 20 wt. % nanometer scaled ZnO particles, which has stable permittivity and low dielectric loss from -100 to 160 °C. The stable dielectric properties are proposed to be beneficiated from the stress induced multi-phase coexistence.     

Flexible /PET/batio3/ layer–layer composite film with enhanced dielectric properties fabricated by highly loaded /batio3/ coating with acrylic resin as binder

Flexible layer–layer poly(ethylene phthalate) (PET)/BaTiO₃ composite films with enhanced dielectric permittivity were fabricated by spin coating method, consisting of PET substrate film layer and modified BaTiO₃/acrylic resin hybrid coating layer. The thickness of coating layer was less than 3 μm (about 2% of PET film thickness), and therefore, the PET/barium titanate (BT) composite films remained flexible even at high volume fraction of BaTiO₃ fillers. The volume contents of BaTiO₃ were varied from 0 to 80%, and the solid contents of BaTiO₃/acrylic resin were in the range of 51.8–72.9%. Scanning electron microscopy showed strong interaction of finely dispersed BaTiO₃ particles with acrylic resin. Morphological profile also displayed uniform coating layer of modified BaTiO₃/acrylic resin and its strong adhesion with PET film. The dielectric constant of the PET/BaTiO₃ composite films increased by about 26% at 60 vol % BaTiO₃ loading when compared with the pristine PET film, whereas the dielectric loss decreased slightly. In addition, PET‐grafted poly(hydroxylethyl methacrylate) brushes were used as substrate to introduce covalent bonding with the coating layer. Further enhancement of dielectric constant and reduction of dielectric loss were realized when compared with the composite films with bare PET substrate. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42508.     

Composition dependence of dielectric properties,elastic modulus,and electroactivity in (carbon black‐BaTiO3)/silicone rubber nanocomposites

The dielectric properties, elastic modulus, and electromechanical responses of dielectric elastomers (DEs) consisting of silicone rubber and carbon black (CB) incorporated with BaTiO₃ (BT) were studied. When compared with single filler/rubber composites, the resulting three‐component nanocomposites yielded very abnormal phenomena. They might be attributed to the interactions between the two kinds of fillers. The increase in concentration of CB (BT) would play a destructive role to the network structure formed by BT (CB) particles. The maximum electromechanical strain of the nanocomposites achieved at mass fraction m_CB = 0.03 and m_BT = 0.06. The resultant electromechanical strain would be attributed to the large dielectric permittivity in the three‐component nanocomposites, in which the BT particles themselves have a high dielectric permittivity and the electrical networks of CB particles have a contribution on the increase in dielectric permittivity of the three‐component nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Lamellar BaTiO3 and its composites fabricated by the freeze casting technique

In this investigation, the freeze casting technique was employed to fabricate ceramic–epoxy composites. Porous BaTiO₃ ceramics exhibited lamellae architectures with strong anisotropy but with poor mechanical property. BaTiO₃–epoxy composites in longitudinal direction showed high dielectric constants which were 1 order of magnitude higher than those of conventional composites with randomly distributed ceramic particles. With the addition of alumina, the compressive strength of porous BaTiO₃ ceramics could be enhanced and the dielectric constants of ceramic–epoxy composites were lowered, but they were still much higher than those of the traditional composites. In a word, the properties of the composites could be optimized by adding proper amount of alumina.     

Microstructure and dielectric properties of Ag-BaTiO3 composite ceramics

Di-phase composite ceramics based on BaTiO₃ with 5?vol% of Ag filler have been prepared by sintering the mixture of powders at temperatures above the silver melting point (1000?°C–1300?°C/2?h). As predicted by finite element calculations, the addition of metallic particles should produce a field concentration in some regions of the BaTiO₃ matrix and therefore, an enhanced dielectric response with respect to pure BaTiO₃. The role of oxygen vacancies on the dielectric relaxation mechanisms of Ag-BaTiO₃ composites has been investigated. The sintering temperature of 1200?°C provided optimized ceramics with excellent dielectric properties, i.e. with low losses (tanδ?<?3%) and room temperature permittivity measured at 50?kHz exceeding 6500 (and above 13,000 at the Curie temperature), as result of a good densification (94% relative density) and a synergy effect of the metallic particles inclusions and ceramic grain size in the range of ≈1?μm, where BaTiO₃ has a well-known maximum of its permittivity.     

High permittivity ceramics loaded silicone elastomer composites for flexible electronics applications

The dielectric properties of silicone elastomer composites are important in designing flexible electronic devices. The recent explosive growth in wireless communication, automotive and biomedical applications increases the demand for flexible dielectric materials. However, it is very difficult to identify a homogeneous material which possesses these desired properties. Flexible silicone rubber- ceramic composites based BaTiO₃ (BT), SrTiO₃ (ST) and Ca_(1−x)Nd_(2x/3)TiO₃ (CNT) ceramic fillers have been prepared. The relative permittivity, thermal conductivity and water absorption increase whereas the coefficient of linear thermal expansion decrease as the volume fraction of filler increases. In the case of dielectric loss; a decreasing trend is shown by SR-ST and SR-CNT composites with filler volume fraction whereas SR-BT composites show a reverse trend since BT is a lossy material. The composites have εr in the range 3–14 in the microwave frequency range. The composites with high filler loading are suitable candidates for core of flexible dielectric waveguide and embedded capacitor applications and the composites with ST and CNT are suitable for cladding of flexible dielectric waveguide and also for microwave substrate applications     

Rheological,mechanical, and electrical properties of Sr0.7Bi0.2TiO3 modified BaTiO3 ceramic and its composites

Porous BaTiO₃-based relaxor ferroelectric ceramics with lamellar structure were achieved by ice templating method, and the rheological properties of ceramic slurry for freeze casting were deeply studied. Epoxy resin was then backfilled to generate ceramic–epoxy resin composites. Ceramic–epoxy composites with a lamellar structure were obtained when using a slurry with a ceramic content of 45 wt.%. The nanoindentation results showed that the introduction of ceramic materials into the epoxy resin can significantly improve the penetration resistance and hardness of the material. The dielectric and ferroelectric properties of the composites were also characterized. The interaction between the highly coupled dipoles in the polymers results in a decrease in the breakdown field strength of the composite. The dielectric constant reached up to ∼800. At 220 kV/cm, W_rec = 0.62 J/cm³, and η was ∼80%. At low frequencies, W_rec was ∼0.16 J/cm³, which indicated good stability.     

Toward green three‐phase composites with enhanced dielectric permittivity

This work aims to investigate the dielectric potential of microcrystalline cellulose, a green biosourced material, as a third constituent in the three‐phase composites based on ethylene vinyl acetate‐vinyl ester of versatic acid (EVA‐VeoVa) terpolymer and BaTiO₃. For that, new green three‐phase composites were prepared using an economic and green process, with simple implementation at room temperature and using water as a solvent. Compared with the binary composite EVA‐VeoVa/BaTiO₃, the three‐phase composite EVA‐VeoVa/BaTiO₃/microcrystalline cellulose showed an improvement of the BaTiO₃ particles dispersion, enhanced relative permittivity, and reduced dielectric loss, which explains the significance of this study. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46147.     

Enhancing Dielectric Properties of Poly(vinylidene fluoride)-Based Hybrid Nanocomposites by Synergic Employment of Hydroxylated BaTiO3 and Silanized Graphene

The poly(vinylidene fluoride)-based hybrid composites with a blended BaTiO₃–exfoliated graphene as filler were fabricated with the efficient method of solution casting and hot pressing and their dielectric properties were investigated in detail. In advance, both of the nanoparticles are functionalized to improve the interfacial bonding between fillers and matrix. Synergistic effects arising from blending zero-dimensional BaTiO₃ and two-dimensional exfoliated grapheneare identified by the improved distribution of nanoparticles in poly(vinylidene fluoride) host and mitigating the concomitant increase in dielectric loss while maintaining the high dielectric constant values of the composites.     

Properties and processing characteristics of dielectric-filled epoxy resins

A family of casting composites, epoxy resins with mineral fillers, having a range of electrical properties, are being developed. In such composites, the dielectric constant is controlled primarily by varying the filler material in composition and proportions. The present work reports on the mechanical properties of composites made with two types of filler, an alumina powder (XA3500 from ALCOA) and a BaTiO₃/TiO₂ ceramic powder (ATD-50 from Ampex). Dependence of mechanical properties on curing agents was also determined. Filler contents from 0 to 40 percent volume were used. Epoxy systems contained single epoxy resin with both amine and anhydride hardeners. Processing of the anhydride-cured systems was easier than that of the amine-based systems because of their lower viscosity and longer gel time of the former. However, the anhydride-cured systems required higher processing temperatures. Curing kinetics and molecular bonding were investigated using a combination of differential scanning calorimetry, dynamic mechanical thermal analysis, and scanning electron microscopy. Activation energies of 11.2 kcal/mole and 12.1 kcal/mole were obtained for the curing of the amine-based and the anhydride-based composites respectively, and a small difference in the glass transition temperature was also observed. These effects can be attributed to the difference in the structure of the curing agents. The epoxy resin cured with NMA is less ductile compared with those cured with MTHPA or MHHPA due to slight chemical modification on the ring structures. This dependence of ductility on curing agent was observed in specimens with different filler contents. Although the presence of the filler materials was found to enhance the mechanical properties of the epoxy, the fracture mode in these materials is still brittle.     

Influence of Ca[(Li1/3Nb2/3)0.8Ti0.2]O3‐δ filler on the microwave dielectric properties of polyethylene and polystyrene for microelectronic applications

Ceramic reinforced polyethylene and polystyrene composites were prepared by melt mixing and hot molding techniques. Temperature stable low‐loss Ca[(Li_1/3Nb_2/3)_0.8Ti_0.2]O_3‐δ (CLNT) ceramic was used as the filler to improve the dielectric properties of the polymers. The relative permittivity and dielectric loss in the microwave frequency range were increased with increase in the ceramic loading. As the filler content increased from 0 to 0.50 volume fraction, the relative permittivity increased from 2.3 to 9 and dielectric loss tangent from 0.0006 to 0.005 for polyethylene‐CLNT composite. In the case of polystyrene‐CLNT composite, the relative permittivity and dielectric loss tangent increased from 2.1 to 10.5 and 0.0005 to 0.0032 respectively with increase in filler content from 0 to 0.50 volume fractions. The thermal stability of the relative permittivity of polymer ceramic composites was also investigated. The experimentally observed relative permittivity was compared with theoretical models. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers