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.     

Influence of polarity of polymer on inorganic particle dispersion in dielectric particle/polymer composite systems

The influence of the polarity of polymers on the degree of dispersion of BaTiO₃ particles in BaTiO₃/polymer composite systems was investigated. The BaTiO₃ polymer composite systems were prepared from BaTiO₃ particles and low-density polyethylene (LDPE) or ethylene vinyl acetate copolymer (EVA) with 7 and 15 wt % vinyl acetate. Scanning electron microscopy observation showed that BaTiO₃ particles aggregated in the polymer matrices and dispersed more readily into the EVA matrix than into LDPE. The shift of the β-peak temperature by ca. +5°C in the temperature dispersion of the loss modulus was observed for EVA–BaTiO₃ composite systems in dynamic mechanical property measurement. On the other hand, the β-peak temperature of the polymers filled with graphite particles, which have hydrophobic surfaces, was almost constant in a volume fraction region of 0–0.3. The ellipsoidal axes' ratios given by comparison of experimental dielectric constant values and theoretical ones using the Maxwell equation were 4.2, 3.6, and 3.1 for LDPE/BaTiO₃, EVA(7%)/BaTiO₃, and EVA(15%)/BaTiO₃ composite systems, respectively. The axes' ratio decreased by the introduction of polar vinyl acetate groups into nonpolar LDPE. The results confirmed that the polarity of the polymers was one of the key factors governing the dispersibility of BaTiO₃ particles in the polymer matrix. © 1995 John Wiley & Sons, Inc.     

Characteristics of polyimide/barium titanate composite films

In this study, the characteristics of the polyimide/BaTiO₃ composite films with various amounts of BaTiO₃ were evaluated. Modifier 1-methoxy-2-propyl acetate was added during composite preparation to disperse the BaTiO₃ particles in polyimide matrix. Conversion of polyamic acid (PAA) to polyimide was not completed for the composite film with a high BaTiO₃ loading (90 wt%). Dielectric constant of the film increases from 3.53 to 46.50, at the sweep frequency of 10 kHz, as the BaTiO₃ content increases from 0 to 90 wt% (0–67.5 vol.%), which is mainly due to the relatively high dielectric constant of BaTiO₃ particles in the polyimide matrix. The dielectric losses at 10 kHz is ranging from 0.005 to 0.015, which is due to the switching of the domain wall. Water absorption decreases considerably with increasing BaTiO₃ content. With 10 wt% (2.5 vol.%) BaTiO₃ addition, the water absorption of the composite film reduces 45% from that of pure polyimide. Also, high loading of BaTiO₃ is not beneficial to reduce the water absorption of the composite film.     

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.     

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.     

Preparation and performance analysis of barium titanate incorporated in corn starch‐based polymer electrolytes for electric double layer capacitor application

Polymer electrolyte membranes composing of corn starch as host polymer, lithium perchlorate (LiClO₄) as salt, and barium titanate (BaTiO₃) as composite filler are prepared using solution casting technique. Ionic conductivity is enhanced on addition of BaTiO₃ by reducing the crystallinity and increasing the amorphous phase content of the polymer electrolyte. The highest ionic conductivity of 1.28 × 10^?2 S cm^?1 is obtained for 10 wt % BaTiO₃ filler in corn starch‐LiClO₄ polymer electrolytes at 75°C. Glass transition temperature (T_g) of polymer electrolytes decreases as the amount of BaTiO₃ filler is increased, as observed in differential scanning calorimetry analysis. Scanning electron microscopy and thermogravimetric analysis are employed to characterize surface morphological and thermal properties of BaTiO₃‐based composite polymer electrolytes. The electrochemical properties of the electric double‐layer capacitor fabricating using the highest ionic conductivity polymer electrolytes is investigated using cyclic voltammetry and charge‐discharge analysis. The discharge capacitance obtained is 16.22 F g^?1. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43275.     

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.     

Enhancement on electric responses of BaTiO3 particles with polymer‐coating

To enhance electric response by polymer coating, BaTiO₃/polymer shell–core composite particles were prepared by emulsion polymerization with polyimide, chitosan, polystyrene, polyacrylic acid, and polyacrylamide. Their micro structure was characterized by transmission electron microscopy, Fourier transform infrared, and automatic X‐ray diffraction, their properties were investigated using optical contact angle and dielectric constant, and their electric responses were studied indirectly by dynamic viscoelasticity analyzer. The results showed that BaTiO₃ cores remained in cubic, the surface hydrophilic of the particles changed as follows: BaTiO₃ > BaTiO₃/PI > BaTiO₃/PAM > BaTiO₃/Chitosan > BaTiO₃/PAA > BaTiO₃/PS, and the dielectric constants of the particles varied with the order of that BaTiO₃ > BaTiO₃/PI > BaTiO₃/PAM > BaTiO₃/Chitosan > BaTiO₃/PAA > BaTiO₃/PS. Eventually, the particles' electric response activities exhibited the order of BaTiO₃/PI > BaTiO₃/PAM > BaTiO₃/Chitosan > BaTiO₃/PAA > BaTiO₃/PS > BaTiO₃. Furthermore, the electric response of the particles showed a chief dependence on polymer‐coating, surface hydrophilic, and dielectric constant. As a result, BaTiO₃ particles' electric response was much enhanced by polymer‐coating, and their compatibility to aqueous continuous phase was ameliorated. For the BaTiO₃/polymer particles, fine surface hydrophile and high dielectric constant dominated the strong response to electric field. Ultimately, BaTiO₃/PI and BaTiO₃/PAM particles possessed the strongest electric response in the five composite particles. The conclusion suggests an effective approach to prepare excellent hydrous electrorheological elastomers. POLYM. COMPOS., 34:897–903, 2013. © 2013 Society of Plastics Engineers     

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.     

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.     

Fabrication of BaTiO3-PTFE composite film for embedded capacitor employing aerosol deposition

The potential for using aerosol deposition (AD) as an alternative fabrication method to the conventional polymer composite process for embedded capacitors was examined. In order to achieve a high relative dielectric permittivity, BaTiO₃-polytetrafluoroethylene (PTFE) composite thick films were attempted by AD at room temperature. For the high dielectric constant, the BaTiO₃-PTFE composite films grown by AD should satisfied the following two critical conditions: a reduced decrement in ceramic particle size and a relieved distortion of the crystal structure. However, the relative permitivity of the composite films was too low compared with that of the BaTiO₃ films grown by AD. By predicting the dielectric constant in several composite models using the Hashin-Shtrikman bounds theory and 3-dimenstional (3-D) electrostatic simulation, we confirmed that the connectivity between ceramic particles is a highly critical factor for achieving a high dielectric constant in composite films.     

Enhanced dielectric constant of acrylonitrile–butadiene rubber/barium titanate composites with mechanical reinforcement by nanosilica

Acrylonitrile–butadiene rubber (NBR), a synthetic rubber having C≡N dipoles, was chosen as a polymer matrix with a higher dielectric constant than other non-polar rubber like silicone rubber or ethylene–propylene–diene monomer. Barium titanate (BaTiO₃), as a ferroelectric material, with a high dielectric constant and low dielectric loss was selected as a main filler to further enhance the dielectric constant of NBR. An effective silane coupling agent (KH845-4), selected from five types of silane coupling agents with different characteristic functional groups, was used to modify the surface of BaTiO₃ particles to enhance its interfacial adhesion to the matrix. Fourier transform infrared spectroscopy (FTIR) was used to verify the successful modification. The addition of BaTiO₃ obviously enhanced the dielectric constants. In particular, an uncommon pattern of dielectric loss has been displayed and analyzed in this paper. Nevertheless, the reinforcing effect of mechanical strength of the NBR/treated BaTiO₃ composites is limited. On this basis, the addition of nanosilica (SiO₂), replacing part of NBR, improved the mechanical strength. Confirmed by scanning electron microscopy (SEM), the SiO₂ and treated BaTiO₃ particles were dispersed well in the NBR matrix. The tensile strength was increased from 4.33 to 6.12 MPa when SiO₂ accounted for 4%. Moreover, the curing characterizations, crosslinking density, resistivity, and oil resistance were evaluated. This composite material can be used in manufacturing electronic devices, which are subjected to oily environments for a long time.     

Preparation,characterization and dielectric properties of polyetherimide nanocomposites containing surface‐functionalized BaTiO3 nanoparticles

Polyetherimide (PEI)/hydroxyl‐functionalized barium titanate (BaTiO₃) nanocomposite films were successfully prepared through solution‐casting followed by subsequent thermal imidization. The results of Fourier transform infrared spectroscopy confirmed that the chemical treatment with hydrogen peroxide (H₂O₂) could efficiently derive hydroxyl groups on the surface of BaTiO₃ nanoparticles. The strong interaction between the hydroxyl‐functionalized BaTiO₃ and the PEI matrix greatly enhanced the particle dispersion as well as the interfacial adhesion, as evidenced by scanning electron microscopy. The PEI nanocomposite with hydroxyl‐functionalized BaTiO₃ nanoparticles (50 vol% BaTiO₃ loading) showed an increased dielectric permittivity of 52.78 at 1 kHz compared with the dielectric permittivity (33.87) of PEI/raw BaTiO₃ composite. The loss tangent was still low (less than 0.03) when the content of hydroxyl‐functionalized BaTiO₃ was 50 vol%. For PEI/BaTiO₃ nanocomposites, the frequency and temperature dependences of the dielectric properties were significantly reduced through functionalizing the surface of BaTiO₃ nanoparticles with H₂O₂. Different theoretical approaches were employed to predict the effective permittivity of the nanocomposite systems and the results are compared with the experimental results. Copyright © 2012 Society of Chemical Industry     

Improvement of dielectric characteristics of cyanoethyl ether of polyvinyl alcohol-BaTiO3 composites by modifying filler surface

The effect of modifying the surface of submicron barium titanate by pure silica sol and silica sol mixed with Al(NO₃)₃ on the dielectric characteristics of composites produced by introducing modified BaTiO₃ to cyanoethyl ether of polyvinyl alcohol is studied. An increase in the dielectric permittivity and a decrease in the dielectric loss of the composites are achieved through modifying the surface of BaTiO₃ by applying a SiO₂ layer. On the contrary, the simple hydration of BaTiO₃ and the application of a SiO₂-Al₂O₃ mixed layer lead to a sharp drop of the dielectric characteristics of the composite.     

Multifunctional fiberglass-reinforced PMMA-BaTiO3 structural/dielectric composites

Fiberglass-reinforced polymer composites were investigated for potential use as structural dielectrics in multifunctional capacitors that require simultaneous excellent mechanical properties and good energy storage characteristics. Composites were fabricated employing poly(methyl methacrylate), PMMA, as the structural matrix. While barium titanate (BaTiO₃) nanopowder was added to the composites for its high room temperature dielectric constant, fiberglass was employed to confer high stiffness. A conductive polymer blend of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonate (PEDOT:PSS) was used to coat the BaTiO₃ nanoparticles with the purpose of further elevating the dielectric constant of the resultant PMMA-composites. FTIR spectroscopy, TGA and SEM measurements were conducted to prove the successful coating of BaTiO₃ nanoparticles with the PEDOT:PSS blend. TEM measurements revealed a good dispersion of coated nanoparticles throughout the PMMA matrix. The fiberglass-reinforced-PMMA composites containing neat and coated BaTiO₃ were found to exhibit excellent stiffness. In addition, the use of PEDOT:PSS in conjunction with BaTiO₃ was observed to improve the dielectric constant of the composites. Finally, the dielectric constant of the structural composites was found to vary only slightly with temperature.     

Synthesis,characterisation and flame,thermal and electrical properties of poly (<Emphasis Type="Italic">n</Emphasis>-butyl methacrylate)/titanium dioxide nanocomposites

Nanocomposites based on poly (n-butyl methacrylate) (PBMA) with various concentrations of titanium dioxide (TiO₂) nanoparticles were synthesised by in situ free radical polymerisation method. The formation of nanocomposite was characterised by FTIR, UV, XRD, DSC, TGA, impedance analyser and flame retardancy measurements. FTIR and UV spectrum ascertained the intermolecular interaction between nanoparticles and the polymer chain. The XRD studies indicated that the amorphous region of PBMA decreased with the increase in content of metal oxide nanoparticles. The SEM revealed the uniform dispersion of nanoparticles in the polymer composite. The DSC and TGA studies showed that the glass transition temperature and thermal stability of the nanocomposites were increased with the increase in the concentration of nanoparticles. The conductivity and dielectric properties of nanocomposites were higher than pure PBMA and the maximum electrical property was observed for the sample with 7 wt% TiO₂. As the concentration of nanoparticles increased above 7 wt%, the electrical property of nanocomposite was decreased owing to the agglomeration of nanoparticles in the polymer. Nanoparticles could impart better flame retardancy to PBMA/TiO₂ composite and the flame resistance of the materials improved with the addition of nanoparticles in the polymer matrix.     

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.     

Low-loss insulating-conductive ceramic composite with giant permittivity and high permeability using glass phase as separating layer

The control of dielectric loss in insulating-conductive ceramic composites is of great significance for the enhancement of the comprehensive performance of next-generation devices. In this work, a low-activity precursor co-sintering method was proposed to prepare low-loss BaTiO₃(BTO)/Ni_0.5Zn_0.5Fe₂O₄(NZFO) ceramic composite by using 2PbO–B₂O₃(PBO) glass as insulating layer. XRD and SEM were used to reveal the phase composition and the morphology of the composite. Results showed that the conductive networks can be successfully cut off by PBO glass separating layer inside the composite (1−x)BTO/xNZFO where x is the molar fraction of NZFO ferrite, giving rise to decreased dielectric loss in a wide compositional range between x=0.1–0.7 while retaining considerable effective permittivity and initial permeability. Excess amount of PBO glass is not favorable for the formation of separating layer due to the chemical reactions occurring between the constituent phases and the glass phase; meanwhile, accompanied by the decrement in dielectric loss, the initial permeability of the composite decreases linearly with increasing PBO content.     

Embedded Capacitor Technology Using Aerosol Deposition

Embedded passives, which achieve miniaturization, cost reduction, and higher performance, are regarded as one of the most promising technologies for a future RF module substrate. Currently, a BaTiO₃/Polymer composite is being used for the embedded capacitors in printed wiring boards. One of the drawbacks of this composite is its relatively low dielectric constant, because the polymer component with a low dielectric constant suppresses the dielectric constant of the whole composite. We propose a resin build-up circuit board with passive functions embedded in a ceramic film without any polymer component for the next-generation low-cost RF modules. We have already manufactured a prototype board with ceramic capacitors embedded in an FR-4 substrate using a unique ceramic deposition technology: aerosol deposition (ASD) in which many kinds of ceramics can be deposited on a substrate at room temperature by making use of accelerated ceramic nanoparticle aerosol bombardment with a nozzle. In this study, first we examine the effects of the characteristics of raw ceramic powder on the crystal structure and the dielectric properties of ASD films. As a result, we confirmed that dense BaTiO₃ dielectric films can be deposited when raw powder without strain is used. From the resulting polarization versus electrical field (P–E curve), we confirmed that paraelectric was observed in the dense films, while the porous BaTiO₃ films deposited using milled powder exhibit a small hysteresis loop. We also clarified that dense BaTiO₃ dielectric films exhibit a nanostructure with a texture consisting of particles under 10 nm in diameter. We also examine the interfacial behavior between BaTiO₃ dielectric films and the Cu electrode, in order to investigate the deposition temperature and the reliability of a BaTiO₃ ASD film under high temperature (250°C), high humidity (100 Rh%), thermal cycle condition (−55°C to 150°C), and bias DC voltage (5 V). We clarified that the BaTiO₃ ASD film satisfies the criteria of reliability in the microelectronic packaging area.     

Dielectric performance of composites of BaTiO3 and polymers for capacitor applications under microwave frequency

Composites of nano-sized barium titanate (BaTiO₃) with volume fractions up to 0.5 and poly(butylene terephthalate) (PBT) or linear low-density polyethylene (LLDPE) were made via extrusion. Scanning electron microscopy demonstrated that BaTiO₃ is well dispersed in the polymer matrices. The crystalline content (DSC) and thermal stability (TGA) of both polymers decreased with increasing BaTiO₃ loading. Dielectric properties of the composites were measured using a vector network analyzer. Both dielectric permittivity and tangent loss increased with increasing BaTiO₃ content. At 2.45 GHz, the dielectric permittivity for 48 vol% BaTiO₃-filled LLDPE and 43 vol% BaTiO₃-filled PBT was 25 and 21.2, respectively. There was a good fit between the Lichtenecker model and experimental data obtained up to a certain value, with the permittivity variations being dependent on volume fraction. The improved dielectric performance achieved on inclusion of BaTiO₃ confirms both composite systems as potential candidates for microwave frequency capacitor applications.