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 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 /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.     

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.     

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.     

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.     

Polyimide dielectric nanocomposites containing functional nanofillers based on multilayer structure: Design,preparation, and properties

Polyimide (PI) dielectric nanocomposites containing functional nanofillers based on layered structure (single-layer: BT@Al₂O₃@PI, double-layer: PI/BT@Al₂O₃@PI, three-layer: PI/BT@Al₂O₃@PI/PI) were designed and prepared by using PI as matrix, barium titanate (BT)@alumina (Al₂O₃) as nanofillers through in-situ polymerization compounding technology. FTIR tests indicated that PI and PI dielectric nanocomposites have been synthesized successfully. The molecular mass of BaTiO₃@Al₂O₃@PAA oligomer was higher than that of pure PAA when BT and Al₂O₃ nanofillers were incorporated simultaneously, as verified by GPC and intrinsic viscosity tests. XRD analysis showed that the addition of nanofillers destroyed the order of PI molecular structure and reduced the arrangement density of PI molecular chains. Both FESEM and HRTEM observations showed that the nanofillers were homogeneously dispersed in the PI matrix, contributing to the property improvements of PI dielectric nanocomposites. TGA results indicated that adding nanofillers improved the thermal stability and heat resistance of PI dielectric nanocomposites. The dielectric constant of PI/BT@Al₂O₃@PI double-layer nanocomposites was between the single-layer nanocomposites and pure PI. Due to the effective medium theory, the dielectric constant of three-layer PI/BT@Al₂O₃@PI/PI nanocomposites containing 5 wt% BT@Al₂O₃ reached 5.43. This work can be expected to provide an effective strategy to fabricate PI dielectric nanocomposite films for energy storage applications.     

High permittivity nanocomposites fabricated from electrospun polyimide/BaTiO3 hybrid nanofibers

High dielectric permittivity, good mechanical properties, and excellent thermal stability are highly desired for the dielectric materials used in the embedded capacitors and energy‐storage devices. This study reports polyimide (PI)/barium titanate (BaTiO₃) nanocomposites fabricated from electrospun PI/BaTiO₃ hybrid nanofibers. The PI/BaTiO₃ nanocomposites were investigated using Fourier transform infrared spectroscopy, scanning electron microscope, transmission electron microscope, thermal gravimetric analysis, an electromechanical testing machine, a LCR meter and an electric breakdown strength tester. The results showed that BaTiO₃ fillers were uniformly dispersed up to 50 vol% in PI matrix. The dielectric permittivity of the composite (50 vol% BaTiO₃) was 29.66 with a dielectric loss of 0.009 at 1 kHz and room temperature. The dielectric permittivity showed a very small dependence on temperature (up to 150°C) and frequency (100 Hz–100 kHz). The nanocomposites also showed high thermal stability and good mechanical properties. The PI/BaTiO₃ nanocomposites will be a promising candidate for uses in embedded capacitors, especially in high temperature circumstance. POLYM. COMPOS., 37:794–801, 2016. © 2014 Society of Plastics Engineers     

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.     

Porous Polyimide Membranes Prepared by Wet Phase Inversion for Use in Low Dielectric Applications

A wet phase inversion process of polyamic acid (PAA) allowed fabrication of a porous membrane of polyimide (PI) with the combination of a low dielectric constant (1.7) and reasonable mechanical properties (Tensile strain: 8.04%, toughness: 3.4 MJ/m³, tensile stress: 39.17 MPa, and young modulus: 1.13 GPa), with further thermal imidization process of PAA. PAA was simply synthesized from purified pyromellitic dianhydride (PMDA) and 4,4-oxydianiline (ODA) in two different reaction solvents such as γ-butyrolactone (GBL) and N-methyl-2-pyrrolidinone (NMP), which produce M_w/PDI of 630,000/1.45 and 280,000/2.0, respectively. The porous PAA membrane was fabricated by the wet phase inversion process based on a solvent/non-solvent system via tailored composition between GBL and NMP. The porosity of PI, indicative of a low electric constant, decreased with increasing concentration of GBL, which was caused by sponge-like formation. However, due to interplay between the low electric constant (structural formation) and the mechanical properties, GBL was employed for further exploration, using toluene and acetone vs. DI-water as a coagulation media. Non-solvents influenced determination of the PAA membrane size and porosity. With this approach, insight into the interplay between dielectric properties and mechanical properties will inform a wide range of potential low-k material applications.     

Electric‐field response behaviors of chitosan/barium titanate composite hydrogel elastomers

Chitosan/barium titanate (BaTiO₃) composite hydrogel elastomers were prepared in the presence or absence of an applied direct‐current (dc) electric field. Scanning electron microscopy was used to observe the microstructure of the elastomers and the dispersion of particles in it. Tests of the storage moduli (Gs) of the elastomers were investigated with a dynamic mechanical analyzer. On this basis, the G increment and increment sensitivity were explored. The results show that the particles were sequentially dispersed, and the values of the G values for the elastomer were higher under an external applied dc electric field; this indicated that the composite elastomers exhibited excellent electric field response. Furthermore, the electric‐field response of the composite elastomers changed with the particle concentration, and the maximum response occurred when the mass fraction of BaTiO₃ was 2.0%. The G value of the composite elastomer with a BaTiO₃ weight percentage of 2.0 increased with increasing electric field; this revealed that the composite elastomer had a positive electric field response. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42094.     

Enhancement of piezoelectric and ferroelectric properties of BaTiO3 ceramics by aluminum doping

Ferroelectric and piezoelectric properties of BaTiO₃ and Al-doped BaTiO₃ ceramics were investigated. The ferroelectric study demonstrated that, by doping Al³⁺ ions in the A-site of BaTiO₃, the polarization–electric field loop exhibited enhanced remnant polarization (from 12 to 17.5  μC/cm²), saturation and switching. In addition, the piezoelectric constant (d₃₃) increased with Al-doping for both static and dynamic strain values (from 75 to 135 and from 29.2 to 57.9 pC/N, respectively, at a maximum applied electric field of 16 kV/cm). Furthermore, the dielectric constant values increased and both the dielectric loss factor and leakage current decreased, even though the transition temperature shifted to lower temperature (from 121 to 113 °C) for the Al-doped sample. Therefore, the Al-doped BaTiO₃ has adjustable piezoelectric and ferroelectric properties.     

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.     

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.     

Nano-sized Ag–BaTiO3 composite powders with various amount of Ag prepared by spray pyrolysis

The preparation of precursors of BaTiO₃ nanopowders with various amounts of Ag by spray pyrolysis is reported. The precursor powders obtained with hollow and thin-wall particles are composed of uniformly dispersed Ba, Ti, and Ag components. After post-treatment and a simple milling process, the precursor powders, irrespective of the amount of Ag, are transformed into Ag–BaTiO₃ composite nanoparticles. The mean particle size of the Ag (10 mol%)–BaTiO₃ powders is 142 nm. BaTiO₃ pellets containing Ag exhibit dense structures even at a low sintering temperature of 1000 °C. BaTiO₃ pellets with 10 mol% Ag show the highest dielectric constant of 2950, as opposed to the pure BaTiO₃ pellets (without Ag), whose dielectric constant is 1827.     

Improved Energy Storage Properties of Fine‐Crystalline BaTiO3 Ceramics by Coating Powders with Al2O3 and SiO2

The multilayer structure of capacitor demands for fine grain size of dielectric ceramics in devices, because the thinner layer which needs ceramics with fine grain size is helpful in enlarging the capacitance. In this paper, the aqueous chemical coating method was utilized to modify the BaTiO₃ particles. The fine‐crystalline BaTiO₃ ceramics with an average grain size below 200 nm without abnormal grain growth by co‐coating Al₂O₃ and SiO₂ has been prepared. The phase composition, microstructures of coated particles and ceramics, and dielectric properties were investigated. For samples containing 3 wt% of Al₂O₃ and 1 wt% of SiO₂, the energy storage density is 0.725 J/cm³ and the efficiency of the ceramic samples can keep above 80%. The breakdown strength was improved to about 190 kV/cm.     

Uniform Coating of BaTiO3–Dy2O3–SiO2 Compound Nano Layer on Ni Particles for MLCC Electrode

Uniform coating of nanometer‐scale BaTiO₃–Dy₂O₃–SiO₂ layers on spherical Ni particles are achieved by controlled hydrolysis of tetrabutyl titanate (TBT), hydrothermal reaction with Ba(OH)₂, and co‐precipitation of tetraethylorthosilicate (TEOS) and Dy(NO₃)₃. The composition of the coating layer is similar to rare earth oxide‐silica–doped BaTiO₃, which is the main component of dielectric layer for base metal electrode (BME) multilayer ceramic capacitors (MLCCs). After coating, the shrinkage onset temperature of Ni particles is significantly increased. After sintered to pellets, the electrode has good electrical conductivity. This electrode material has good compatibility with rare earth oxide and silica‐doped BaTiO₃ dielectric materials, and could serve as promising candidate for application in the next generation BME‐MLCCs.     

Novel polymer–ceramic nanocomposite based on high dielectric constant epoxy formula for embedded capacitor application

Embedded capacitor technology can increase silicon packing efficiency, improve electrical performance, and reduce assembly cost compared with traditional discrete capacitor technology. Developing a suitable material that satisfies electrical, reliability, and processing requirements is one of the major challenges of incorporating capacitors into a printed wiring board (PWB). Polymer–ceramic composites have been of great interest as embedded capacitor material because they combine the processability of polymers with the high dielectric constant of ceramics. A novel nanostructure polymer–ceramic composite with a very high dielectric constant (ε_r ～110, a new record for the highest reported ε_r value of a nanocomposite) was developed in this work. A high dielectric constant is obtained by increasing the dielectric constant of the epoxy matrix (ε_r >6) and using the combination of lead magnesium niobate–lead titanate (PMN–PT)/BaTiO₃ as the ceramic filler. This nanocomposite has a low curing temperature (<200°C); thus, it is multichip‐module laminate (MCM‐L) process‐compatible. An embedded capacitor prototype with a capacitance density of 50 nF/cm² was manufactured using this nanocomposite and spin‐coating technology. The effect of the composite microstructure on the effective dielectric constant was studied. This novel nanocomposite can be used for integral capacitors in PWBs. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1084–1090, 2002     

Reinforced properties of ethylene–propylene–diene monomer composites by vinyltrimethoxysiloxane functionalised barium titanate

In this study, non-conductive ethylene–propylene–diene monomer (EPDM)/barium titanate (BaTiO₃) composites with high dielectric constant and low dielectric loss are prepared. Fourier transform infrared (FT-IR) spectra show the chemical adherence of vinyltrimethoxysiloxane oligomer (SG-Si6490) to the surface of BaTiO₃ particles. Functionalised BaTiO₃ particles have better compatibility with EPDM matrix and promote the cure properties of EPDM composites. It is found that when the content of BaTiO₃ increases to 40?vol.-%, the resistivity, rheological, dielectric and mechanical properties of EPDM/BaTiO₃ composites change drastically. The dielectric constant of EPDM with 50?vol.-% BaTiO₃ at 10?MHz is 15, which is 7.5 times higher than that of EPDM control. Meanwhile, the volume resistivity results show EPDM with 50?vol.-% BaTiO₃ is still non-conductive. As for mechanical properties, the tensile and tear strength of EPDM control increase from 1.45?MPa and 8.73?kN?m^?1 to 10.02?MPa (about seven times higher) and 24.65?kN?m^?1 (about three times higher), respectively.