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Title: Dielectric performance of high permitivity nanocomposites: impact of polystyrene grafting on BaTiO 3 and TiO 2

Abstract

Polymer nanocomposites are a promising concept to improve energy storage density of capacitors, but realizing their hypothetical gains has proved challenging. The introduction of high permittivity fillers often leads to reduction in breakdown strength due to field exclusion, which intensifies the applied electric field within the polymer matrix near nanoparticle interfaces. This has prompted research in developing new nanoparticle functionalization chemistries and processing concepts to maximize particle separation. Herein, we compare the dielectric performance of blended nanocomposites to matrix free assemblies of hairy (polymer-grafted) nanoparticles (HNPs) that exhibit comparable overall morphology. The dielectric breakdown strength of polystyrene-grafted BaTiO3 (PS@BaTiO3) systems was over 40% greater than a blended nanocomposite with similar loading (~25% v/v BaTiO3). Hairy nanoparticles with TiO2 cores followed similar trends in breakdown strength as a function of inorganic loading up to 40% v/v. Dielectric loss for PS@BaTiO3 HNPs was 2-5 times lower than analogous blended films for a wide frequency spectrum (1 Hz to 100 kHz). For BaTiO3 content above 7% v/v, grafting the polymer chains to the nanoparticle significantly improved energy storage density and efficiency, likely due to the polymer canopy mitigating interfacial transport and restricting particle-particle hot-spots by establishing a finite minimum particle separation.

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [2];  [1];  [1]
  1. Air Force Research Lab. (AFRL), Wright-Patterson AFB, OH (United States)
  2. Univ. of Southern California, Los Angeles, CA (United States)
Publication Date:
Research Org.:
Univ. of Southern California, Los Angeles, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Org.:
Air Force Research Laboratory, Materials and Manufacturing Directorate
OSTI Identifier:
1374189
Grant/Contract Number:
SC0006812
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nanocomposites
Additional Journal Information:
Journal Volume: 2; Journal Issue: 3; Journal ID: ISSN 2055-0324
Publisher:
Taylor & Francis
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; polymer nanocomposites; hairy nanoparticles; dielectric breakdown; barium titanate; titanium dioxide

Citation Formats

Grabowski, Christopher A., Fillery, Scott P., Koerner, Hilmar, Tchoul, Maxim, Drummy, Lawrence, Beier, Christopher W., Brutchey, Richard L., Durstock, Michael F., and Vaia, Richard A.. Dielectric performance of high permitivity nanocomposites: impact of polystyrene grafting on BaTiO 3 and TiO 2. United States: N. p., 2016. Web. doi:10.1080/20550324.2016.1223913.
Grabowski, Christopher A., Fillery, Scott P., Koerner, Hilmar, Tchoul, Maxim, Drummy, Lawrence, Beier, Christopher W., Brutchey, Richard L., Durstock, Michael F., & Vaia, Richard A.. Dielectric performance of high permitivity nanocomposites: impact of polystyrene grafting on BaTiO 3 and TiO 2. United States. doi:10.1080/20550324.2016.1223913.
Grabowski, Christopher A., Fillery, Scott P., Koerner, Hilmar, Tchoul, Maxim, Drummy, Lawrence, Beier, Christopher W., Brutchey, Richard L., Durstock, Michael F., and Vaia, Richard A.. Thu . "Dielectric performance of high permitivity nanocomposites: impact of polystyrene grafting on BaTiO 3 and TiO 2". United States. doi:10.1080/20550324.2016.1223913. https://www.osti.gov/servlets/purl/1374189.
@article{osti_1374189,
title = {Dielectric performance of high permitivity nanocomposites: impact of polystyrene grafting on BaTiO 3 and TiO 2},
author = {Grabowski, Christopher A. and Fillery, Scott P. and Koerner, Hilmar and Tchoul, Maxim and Drummy, Lawrence and Beier, Christopher W. and Brutchey, Richard L. and Durstock, Michael F. and Vaia, Richard A.},
abstractNote = {Polymer nanocomposites are a promising concept to improve energy storage density of capacitors, but realizing their hypothetical gains has proved challenging. The introduction of high permittivity fillers often leads to reduction in breakdown strength due to field exclusion, which intensifies the applied electric field within the polymer matrix near nanoparticle interfaces. This has prompted research in developing new nanoparticle functionalization chemistries and processing concepts to maximize particle separation. Herein, we compare the dielectric performance of blended nanocomposites to matrix free assemblies of hairy (polymer-grafted) nanoparticles (HNPs) that exhibit comparable overall morphology. The dielectric breakdown strength of polystyrene-grafted BaTiO3 (PS@BaTiO3) systems was over 40% greater than a blended nanocomposite with similar loading (~25% v/v BaTiO3). Hairy nanoparticles with TiO2 cores followed similar trends in breakdown strength as a function of inorganic loading up to 40% v/v. Dielectric loss for PS@BaTiO3 HNPs was 2-5 times lower than analogous blended films for a wide frequency spectrum (1 Hz to 100 kHz). For BaTiO3 content above 7% v/v, grafting the polymer chains to the nanoparticle significantly improved energy storage density and efficiency, likely due to the polymer canopy mitigating interfacial transport and restricting particle-particle hot-spots by establishing a finite minimum particle separation.},
doi = {10.1080/20550324.2016.1223913},
journal = {Nanocomposites},
number = 3,
volume = 2,
place = {United States},
year = {Thu Sep 22 00:00:00 EDT 2016},
month = {Thu Sep 22 00:00:00 EDT 2016}
}

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  • (0.95-x)(Bi{sub 1/2}Na{sub 1/2})TiO{sub 3}-x(Bi{sub 1/2}K{sub 1/2})TiO{sub 3}-0.05BaTiO{sub 3} lead-free piezoelectric ceramics (abbreviated as BNT-BKT-BT100x with x varying from 0 to 20 mol %) are prepared by a solid-state reaction process. Variation of the dielectric properties and microstructure of BNT-BKT-BT100x ceramics with BKT content is studied. The results indicate that the relative permittivity {epsilon}{sub r} and loss tangent tan {delta} vary with the BKT amount. Scanning electron microscope observation also indicates that BKT in high amount affects the microstructure. X-ray diffraction analysis shows that the incorporated BKT diffuses into the BNT-BT lattice to form a solid solution during sintering.
  • Noble fluorescence nanocomposite compound based on barium titanate nanoparticles (BTO), polystyrene (PSt), and terbium ion (Tb{sup 3+}) was synthesized by a combination of surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization, Friedel-Crafts alkylation reaction and coordinate chemistry. Initially, a modification of surface of BTO was conducted by an exchange process with S-benzyl S’-trimethoxysilylpropyltrithiocarbonate to create macro-initiator for polymerization of styrene. Subsequently, aryl carboxylic acid functionalized polystyrene grafted barium titanate (BTO-g-PSt-COOH) was generated by substitution reaction between 4-(Chloromethyl) benzoic acid and PSt chains. The coordination of the nanohybrids with Tb{sup 3+} ions afforded fluorescent Tb{sup 3+} tagged aryl carboxylic acid functionalized polystyrenemore » grafted barium titanate (BTO-g-PSt-Tb{sup 3+}) complexes. Structure, morphology, and fluorescence properties of nanohybrid complexes were investigated by respective physical and spectral studies. FT-IR and SEM analyses confirmed the formation of BTO-g-PSt-Tb{sup 3+}nanohybrids. Furthermore, TGA profiles demonstrated the grafting of aryl carboxylic acid functionalized polystyrene on BTO surface. Optical properties of BTO-g-PSt-Tb{sup 3+} complexes were investigated by fluorescence spectroscopy.« less
  • SnO{sub 2} nanoparticles with an average diameter of about 4 nm were coated on the surface of BaTiO{sub 3} (BT) (∼100 nm) by chemical treatment. With the introduction of BT@SnO{sub 2}, the dielectric permittivity of poly(vinylidene fluoride) (PVDF) composite was significantly increased to 90 at 10{sup 3} Hz, which is ∼40% higher than that of the BT/PVDF composites. It was attributed to the enhanced interfacial polarization in the interlayers between BT and PVDF due to the addition of SnO{sub 2} nanodots. The distance of SnO{sub 2} nanodots on the adjacent BT surfaces is close enough for the electron transport in the matrix bymore » tunneling effect. Besides, the semiconductive SnO{sub 2} leads to the weak insulating-conducting transition close to the percolation threshold.« less
  • The room temperature reflectivity of BaTiO/sub 3/, SrTiO/sub 3/, and TiO/ sub 2/ was measured from 5000 to 70 cm/sup -1/. These data were analyzed by the Kramers-Kronig method and by classical dispersion theory. All of the infrared- active fundamental vibrations allowed by crystal symmetry were measured and characterized by their dispersion parameters. The low-frequency mode is responsible for ferroelectricity in BaTiO/sub 3/ and SrTiO/sub 3/ and is found at 33.8 and 87.7 cm/sup -1/, respectively. The unusually large damping found for this mode can explain the observed microwave loss tangents. The strength of the mode accounts for the largemore » values of the low-frequency dielectric constant. This mode, as well as the highest frequency mode, 510 and 546 cm/sup -1/ in BaTiO/ sub 3/ and SrTiO/sub 3/, respectively, is associated with TiO/sub 6/ octahedra vibrations. A mode at 183 and 178 cm/sup -1/ for BaTiO/sub 3/ and SrTiO/sub 3/, respectively, was found and assigned to a cation-(TiO//sub 3/) vibration. In rutile, three resonances are observed for the ordinary ray and one for the extraordinary ray, as required by theory. As with the titanates, the high dielectric constant is associated with the low-frequency mode. An analysis of the strengths of all of the resonances shows that they involve reasonable effective charges for ionic crystals. (auth)« less