This work was supported by the Taiyuan University of Science and Technology Scientific Research Initial Funding (20182028), the doctoral starting foundation of Shanxi Province (20192006), the Natural Science Foundation of Shanxi Province (201703D111003), the Science and Technology Major Project of Shanxi Province (MC2016-01), and Project U610256 supported by National Natural Science Foundation of China.

1. Surface modification of BT fillers
<ol>
	<li>Prepare 20 mL of KH550 solution (1 wt% KH550 in 95 wt% ethanol-water solvent) and ultrasonicate for 15 min.</li>
	<li>Weigh BT nanoparticles (i.e., the filler) and KH550, respectively, so that fillers can be coated with 1, 2, 3, 4, 5 wt% of the coupling agent. Treat 1 g of BT nanoparticles in 1.057, 2.114, 3.171, 4.228, and 5.285 mL of KH550 solution by 30 min ultrasonication.</li>
	<li>Evaporate the water-ethanol solvent from the mixture at 80 &#176;C for 5 h and then at 120 &#176;C for 12 h in a vacuum oven.</li>
	<li>Use the dry BT nanoparticles as the surface modified fillers to prepare BT-VC91 nanocomposites.</li>
</ol>
2. Preparation of BT-VC91 nanocomposites
<ol>
	<li>Dissolve 0.3 g of VC91 powders in 10 mL of N,N-dimethylformamide (DMF) at room temperature by magnetic stirring for 8 h to obtain a homogeneous VC91-DMF solution.</li>
	<li>Add 0.0542, 0.1145, 0.1819, 0.2578, 0.3437, and 0.4419 g of BT nanoparticles into 10 mL of VC91-DMF solution to obtain a final BT percentage of 5, 10, 15, 20, 25, and 30 vol% in the nanocomposites. Mix BT nanoparticles by magnetic stirring for 12 h and ultrasonication for 30 min to form a homogeneous BT-VC91-DMF suspension. 
	NOTE: Both the unmodified BT and BT nanoparticles coated with the coupling agent are used.</li>
	<li>Cast the suspension by evenly pouring the BT-VC91-DMF onto a preheated 75 mm x 25 mm glass substrate (3 mL per substrate). Keep the glass substrates with suspensions in the oven at 70 &#176;C for 8 h to evaporate the DMF solvent to form composite films.</li>
	<li>Release the composites from glass substrates using sharp tweezers to obtain free-standing BT-VC91 films. Anneal the films on a preheated dust-free paper at 160 &#176;C in air for 12 h.</li>
</ol>
3. Characterization and measurement
<ol>
	<li>Characterize the morphology and uniformity of nanocomposites using a scanning electron microscope (SEM). To do this, freeze BT-VC91 samples in liquid nitrogen and break to show fresh cross section with an approximate size of 5 mm x 30 &#181;m (i.e., the ceramic-polymer interface). Then coat one side of the cross section with a gold layer with a thickness of 3&#8722;5 nm and characterize the composite structure using an SEM (Table of Materials).</li>
	<li>Using a gold coater (Table of Materials), sputter gold layers with a positive circle shape, a diameter of 3 mm, and a thickness of ~50 nm on both sides of the nanocomposite prepared from step 2 to form the electrode for impedance testing.</li>
	<li>Characterize the capacitance and dielectric loss of the nanocomposites over a frequency range from 100 Hz to 1 MHz using an impedance analyzer (Table of Materials) with the Cp-D function. In the testing, connect gold layers on both sides of the composite film with the two poles of fixture.</li>
	<li>Calculate the dielectric constant (&#949;r) of nanocomposites from the capacitance obtained by impedance analyzer using the parallel capacitor model: 
	 
	&#949;r = dCp/&#949;0A 
	 
	where &#949;0 = 8.85 x 10-12, A is the area of gold electrodes, d is the thickness of sample, and Cp is parallel capacitance obtained by connecting the gold electrodes with the fixture of impedance analyzer.</li>
	<li>Characterize the breakdown strength of nanocomposites using a 10 kV high voltage supplier (Table of Materials). Increase the applied electric field evenly and continuously until the breakdown of each sample.</li>
	<li>Characterize the polarization-electric (P-E) field hysteresis loop of nanocomposites using a ferroelectric tester. Record the P-E loops at each electric field while continuously increasing the electric field.</li>
</ol>

<ol><li>Lines, M. E., Glass, A. M. <a target="_blank" href="http://scholar.google.com/scholar?hl=en&safe=off&q=author%3aLines%2C+ME+%22Principles+and+applications+of+ferroelectrics+and+related+materials%22">Principles and applications of ferroelectrics and related materials</a>. , Oxford University Press. (2001).</li>
<li>Nalwa, H. S. <a target="_blank" href="http://scholar.google.com/scholar?hl=en&safe=off&q=author%3aNalwa%2C+HS+%22Handbook+of+low+and+high+dielectric+permittivity+materials+and+their+applications%2C+phenomena%2C+properties+and+applications%22">Handbook of low and high dielectric permittivity materials and their applications, phenomena, properties and applications</a>. , Academic. San Diego, CA. (1999).</li>
<li>Kao, K. C. <a target="_blank" href="http://scholar.google.com/scholar?hl=en&safe=off&q=author%3aKao%2C+KC+%22Dielectric+phenomena+in+solids%22">Dielectric phenomena in solids</a>. , Academic Press. (2004).</li>
<li>Tong, Y., Li, L., Liu, J., Zhang, K., Jiang, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Influence+of+coupling+agent+on+the+microstructure+and+dielectric+properties+of+free-standing+ceramic-polymer+composites%5BTitle%5D)+AND+%22Materials+Research+Express%22%5BJournal%5D)">Influence of coupling agent on the microstructure and dielectric properties of free-standing ceramic-polymer composites.</a> Materials Research Express. 6 (9), 095322(2019).</li>
<li>Zhang, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Controlled+functionalization+of+poly%284-methyl-1-pentene%29+films+for+high+energy+storage+applications%5BTitle%5D)+AND+%22Journal+of+Materials+Chemistry+A%22%5BJournal%5D)">Controlled functionalization of poly(4-methyl-1-pentene) films for high energy storage applications.</a> Journal of Materials Chemistry A. 4 (13), 4797-4807 (2016).</li>
<li>Zhang, L., Cheng, Z. Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Development+of+polymer-based+0-3+composites+with+high+dielectric+constant%5BTitle%5D)+AND+%22Journal+of+Advanced+Dielectrics%22%5BJournal%5D)">Development of polymer-based 0-3 composites with high dielectric constant.</a> Journal of Advanced Dielectrics. 1 (04), 389-406 (2011).</li>
<li>Barsoum, M., Barsoum, M. W. <a target="_blank" href="http://scholar.google.com/scholar?hl=en&safe=off&q=author%3aBarsoum%2C+M+%22Fundamentals+of+ceramics%22">Fundamentals of ceramics</a>. , CRC press. (2002).</li>
<li>Jaffe, B. <a target="_blank" href="http://scholar.google.com/scholar?hl=en&safe=off&q=author%3aJaffe%2C+B+%22Piezoelectric+ceramics%22">Piezoelectric ceramics</a>. , Elsevier. (2012).</li>
<li>Zhang, L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((All-organic+dielectric+nanocomposites+using+conducting+polypyrrole+nanoclips+as+filler%5BTitle%5D)+AND+%22Composites+Science+Technology%22%5BJournal%5D)">All-organic dielectric nanocomposites using conducting polypyrrole nanoclips as filler.</a> Composites Science Technology. 167, 285-293 (2018).</li>
<li>Liao, X., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Flexible+hdC-G+reinforced+polyimide+composites+with+high+dielectric+permittivity%5BTitle%5D)+AND+%22Composites+Part+A%3A+Applied+Science+and+Manufacturing%22%5BJournal%5D)">Flexible hdC-G reinforced polyimide composites with high dielectric permittivity.</a> Composites Part A: Applied Science and Manufacturing. 101, 50-58 (2017).</li>
<li>Xu, W., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Highly+foldable+PANi%40+CNTs%2FPU+dielectric+composites+toward+thin-film+capacitor+application%5BTitle%5D)+AND+%22Materials+Letters%22%5BJournal%5D)">Highly foldable PANi@ CNTs/PU dielectric composites toward thin-film capacitor application.</a> Materials Letters. 192, 25-28 (2017).</li>
<li>Zhang, L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Nano-clip+based+composites+with+a+low+percolation+threshold+and+high+dielectric+constant%5BTitle%5D)+AND+%22Nano+Energy%22%5BJournal%5D)">Nano-clip based composites with a low percolation threshold and high dielectric constant.</a> Nano Energy. 26, 550-557 (2016).</li>
<li>Zhou, S., Zhou, G., Jiang, S., Fan, P., Hou, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Flexible+and+refractory+tantalum+carbide-carbon+electrospun+nanofibers+with+high+modulus+and+electric+conductivity%5BTitle%5D)+AND+%22Materials+Letters%22%5BJournal%5D)">Flexible and refractory tantalum carbide-carbon electrospun nanofibers with high modulus and electric conductivity.</a> Materials Letters. 200, 97-100 (2017).</li>
<li>Zhang, L., Du, W., Nautiyal, A., Liu, Z., Zhang, X. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Recent+progress+on+nanostructured+conducting+polymers+and+composites%3A+synthesis%2C+application+and+future+aspects%5BTitle%5D)+AND+%22Science+China+Materials%22%5BJournal%5D)">Recent progress on nanostructured conducting polymers and composites: synthesis, application and future aspects.</a> Science China Materials. 61 (3), 303-352 (2018).</li>
<li>Xie, Y., Yu, Y., Feng, Y., Jiang, W., Zhang, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Fabrication+of+Stretchable+Nanocomposites+with+High+Energy+Density+and+Low+Loss+from+Cross-Linked+PVDF+Filled+with+Poly%28dopamine%29+Encapsulated+BaTiO3%5BTitle%5D)+AND+%22ACS+Applied+Materials+%26+Interfaces%22%5BJournal%5D)">Fabrication of Stretchable Nanocomposites with High Energy Density and Low Loss from Cross-Linked PVDF Filled with Poly(dopamine) Encapsulated BaTiO3.</a> ACS Applied Materials & Interfaces. 9 (3), 2995-3005 (2017).</li>
<li>Zhang, L., Wu, P., Li, Y., Cheng, Z. Y., Brewer, J. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Preparation+process+and+dielectric+properties+of+Ba0.5Sr0.5TiO3-P%28VDF-CTFE%29+nanocomposites%5BTitle%5D)+AND+%22Composite+Part+B%3A+Engineering%22%5BJournal%5D)">Preparation process and dielectric properties of Ba0.5Sr0.5TiO3-P(VDF-CTFE) nanocomposites.</a> Composite Part B: Engineering. 56, 284-289 (2014).</li>
<li>Dang, Z. M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Fundamentals%2C+processes+and+applications+of+high-permittivity+polymer-matrix+composites%5BTitle%5D)+AND+%22Progress+in+Materials+Science%22%5BJournal%5D)">Fundamentals, processes and applications of high-permittivity polymer-matrix composites.</a> Progress in Materials Science. 57 (4), 660-723 (2012).</li>
<li>Wu, P., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Effect+of+coupling+agents+on+the+dielectric+properties+and+energy+storage+of+Ba0.5Sr0.5TiO3%2FP%28VDF-CTFE%29+nanocomposites%5BTitle%5D)+AND+%22AIP+Advances%22%5BJournal%5D)">Effect of coupling agents on the dielectric properties and energy storage of Ba0.5Sr0.5TiO3/P(VDF-CTFE) nanocomposites.</a> AIP Advances. 7 (7), 075210(2017).</li>
<li>Zhang, L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Process+and+microstructure+to+achieve+ultra-high+dielectric+constant+in+ceramic-polymer+composites%5BTitle%5D)+AND+%22Scientific+Reports%22%5BJournal%5D)">Process and microstructure to achieve ultra-high dielectric constant in ceramic-polymer composites.</a> Scientific Reports. 6, 35763(2016).</li>
<li>Lu, X., Tong, Y., Cheng, Z. Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Fabrication+and+characterization+of+free-standing%2C+flexible+and+translucent+BaTiO3-P+%28VDF-CTFE%29+nanocomposite+films%5BTitle%5D)+AND+%22Journal+of+Alloys+and+Compounds%22%5BJournal%5D)">Fabrication and characterization of free-standing, flexible and translucent BaTiO3-P (VDF-CTFE) nanocomposite films.</a> Journal of Alloys and Compounds. 770, 327-334 (2019).</li>
<li>Goyal, R. K., Katkade, S. S., Mule, D. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Dielectric%2C+mechanical+and+thermal+properties+of+polymer%2FBaTiO3+composites+for+embedded+capacitor%5BTitle%5D)+AND+%22Composites+Part+B%3A+Engineering%22%5BJournal%5D)">Dielectric, mechanical and thermal properties of polymer/BaTiO3 composites for embedded capacitor.</a> Composites Part B: Engineering. 44 (1), 128-132 (2013).</li>
<li>Pan, Z., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Fast+discharge+and+highenergy+density+of+nanocomposite+capacitors+using+Ba0.6Sr0.4TiO3nanofibers%5BTitle%5D)+AND+%22Ceramics+International%22%5BJournal%5D)">Fast discharge and highenergy density of nanocomposite capacitors using Ba0.6Sr0.4TiO3nanofibers.</a> Ceramics International. 42 (13), 14667-14674 (2016).</li>
<li>Hu, G., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Preparation+and+dielectric+properties+of+poly%28vinylidene+fluoride%29%2FBa0.6Sr0.4TiO3+composites%5BTitle%5D)+AND+%22Journal+of+Alloys+and+Compounds%22%5BJournal%5D)">Preparation and dielectric properties of poly(vinylidene fluoride)/Ba0.6Sr0.4TiO3 composites.</a> Journal of Alloys and Compounds. 619, 686-692 (2015).</li>
<li>Chen, Y., Chan, H. L. W., Choy, C. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Nanocrystalline+lead+titanate+and+lead+titanate%2Fvinylidene+fluoride-trifluoroethylene+0-3+nanocomposites%5BTitle%5D)+AND+%22Journal+of+the+American+Ceramic+Society%22%5BJournal%5D)">Nanocrystalline lead titanate and lead titanate/vinylidene fluoride-trifluoroethylene 0-3 nanocomposites.</a> Journal of the American Ceramic Society. 81 (5), 1231-1236 (1998).</li>
<li>Singh, P., Borkar, H., Singh, B. P., Singh, V. N., Kumar, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Ferroelectric+polymer-ceramic+composite+thick+films+for+energy+storage+applications%5BTitle%5D)+AND+%22AIP+advances%22%5BJournal%5D)">Ferroelectric polymer-ceramic composite thick films for energy storage applications.</a> AIP advances. 4 (8), 087117(2014).</li>
<li>Dang, Z., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Fundamentals%2C+processes+and+applications+of+high-permittivity+polymer-matrix+composites%5BTitle%5D)+AND+%22Progress+in+Materials+Science%22%5BJournal%5D)">Fundamentals, processes and applications of high-permittivity polymer-matrix composites.</a> Progress in Materials Science. 57 (4), 660-723 (2012).</li>
<li>Arbatti, M., Shan, X. B., Cheng, Z. Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Ceramic-Polymer+Composites+with+High+Dielectric+Constant%5BTitle%5D)+AND+%22Advanced+Materials%22%5BJournal%5D)">Ceramic-Polymer Composites with High Dielectric Constant.</a> Advanced Materials. 19 (10), 1369-1372 (2007).</li>
<li>Fan, B., Liu, Y., He, D., Bai, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Achieving+polydimethylsiloxane%2Fcarbon+nanotube+%28PDMS%2FCNT%29+composites+with+extremely+low+dielectric+loss+and+adjustable+dielectric+constant+by+sandwich+structure%5BTitle%5D)+AND+%22Applied+Physics+Letters%22%5BJournal%5D)">Achieving polydimethylsiloxane/carbon nanotube (PDMS/CNT) composites with extremely low dielectric loss and adjustable dielectric constant by sandwich structure.</a> Applied Physics Letters. 112 (5), 052902(2018).</li>
<li>Liao, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((A+surface-modified+TiO2+nanorod+array%2FP%28VDF-HFP%29+dielectric+capacitor+with+ultra-high+energy+density+and+efficiency%5BTitle%5D)+AND+%22Journal+of+Materials+Chemistry+C%22%5BJournal%5D)">A surface-modified TiO2 nanorod array/P(VDF-HFP) dielectric capacitor with ultra-high energy density and efficiency.</a> Journal of Materials Chemistry C. 5 (48), 12777-12784 (2017).</li>
<li>Mittal, K. L. <a target="_blank" href="http://scholar.google.com/scholar?hl=en&safe=off&q=author%3aMittal%2C+KL+%22Silanes+and+Other+Coupling+Agents%22">Silanes and Other Coupling Agents</a>. 3, CRC Press. (2004).</li>
<li>Zhang, X., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Superior+Energy+Storage+Performances+of+Polymer+Nanocomposites+via+Modification+of+Filler%2FPolymer+Interfaces%5BTitle%5D)+AND+%22Advanced+Materials+Interfaces%22%5BJournal%5D)">Superior Energy Storage Performances of Polymer Nanocomposites via Modification of Filler/Polymer Interfaces.</a> Advanced Materials Interfaces. 5 (11), 1800096(2018).</li>
<li>Yeh, J. M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Thermal+and+optical+properties+of+PMMA-titania+hybrid+materials+prepared+by+sol-gel+approach+with+HEMA+as+coupling+agent%5BTitle%5D)+AND+%22Journal+of+Applied+Polymer+Science%22%5BJournal%5D)">Thermal and optical properties of PMMA-titania hybrid materials prepared by sol-gel approach with HEMA as coupling agent.</a> Journal of Applied Polymer Science. 94 (1), 400-405 (2004).</li>
<li>Yang, C., Song, H. S., Liu, D. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Effect+of+coupling+agents+on+the+dielectric+properties+of+CaCu3Ti4O12%2FPVDF+composites%5BTitle%5D)+AND+%22Composites+Part+B%3A+Engineering%22%5BJournal%5D)">Effect of coupling agents on the dielectric properties of CaCu3Ti4O12/PVDF composites.</a> Composites Part B: Engineering. 50, 180-186 (2013).</li>
<li>Iijima, M., Sato, N., Lenggoro, I. W., Kamiya, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Surface+Modification+of+BaTiO3+Particles+by+Silane+Coupling+Agents+in+Different+Solvents+and+Their+Effect+on+Dielectric+Properties+of+BaTiO3%2FEpoxy+Composites%5BTitle%5D)+AND+%22Colloids+and+Surfaces+A%3A+Physicochemical+and+Engineering+Aspects%22%5BJournal%5D)">Surface Modification of BaTiO3 Particles by Silane Coupling Agents in Different Solvents and Their Effect on Dielectric Properties of BaTiO3/Epoxy Composites.</a> Colloids and Surfaces A: Physicochemical and Engineering Aspects. 352 (1-3), 88-93 (2009).</li>
<li>Zhang, Q., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Enhanced+Dielectric+Tunability+of+Ba0.6Sr0.4TiO3%2FPoly%28vinylidene+fluoride%29+Composites+via+Interface+Modification+by+Silane+Coupling%5BTitle%5D)+AND+%22Agent.+Composites+Science+and+Technology%22%5BJournal%5D)">Enhanced Dielectric Tunability of Ba0.6Sr0.4TiO3/Poly(vinylidene fluoride) Composites via Interface Modification by Silane Coupling.</a> Agent. Composites Science and Technology. 129, 93-100 (2016).</li>
<li>Dang, Z. M., Wang, H. Y., Xu, H. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Influence+of+Silane+Coupling+Agent+on+Morphology+and+Dielectric+Property+in+BaTiO3%2FPolyvinylidene+fluoride+Composites%5BTitle%5D)+AND+%22Applied+Physics+Letters%22%5BJournal%5D)">Influence of Silane Coupling Agent on Morphology and Dielectric Property in BaTiO3/Polyvinylidene fluoride Composites.</a> Applied Physics Letters. 89 (11), 112902(2006).</li>
<li>Tong, Y., Zhang, L., Bass, P., Rolin, T. D., Cheng, Z. Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Influence+of+silane+coupling+agent+on+microstructure+and+properties+of+CCTO-P%28VDF-CTFE%29+composites%5BTitle%5D)+AND+%22Journal+of+Advanced+Dielectrics%22%5BJournal%5D)">Influence of silane coupling agent on microstructure and properties of CCTO-P(VDF-CTFE) composites.</a> Journal of Advanced Dielectrics. 8 (02), 1850008(2018).</li>
<li>Shan, X. <a target="_blank" href="http://scholar.google.com/scholar?hl=en&safe=off&q=author%3aShan%2C+X+%22High+dielectric+constant+0-3+ceramic-polymer+composites%22">High dielectric constant 0-3 ceramic-polymer composites</a>. , Auburn University. (2009).</li>
</ol>

The authors have nothing to disclose.

As discussed above, the method developed by this work could successfully improve the energy-storage performance of ceramic-polymer nanocomposites. To optimize the effect of such method, it is critical to control the amount of coupling agent used in ceramic-surface modification. For ceramic nanoparticles with a diameter of ~200 nm, it was experimentally determined that 2 wt% of KH550 could lead to a maximal energy density. For other composite systems, this conclusion may be used approximately when the fillers with the dia...

The dielectrics applied in electrical energy storage devices are mainly characterized using two important parameters: the dielectric constant (&#949;r) and the breakdown strength (Eb)1,2,3. In general, organic materials such as polypropylene (PP) exhibit a high Eb (~102 MV/m) and a low &#949;r (mostly &#60;5)4,5,6 while inorganic materials, especially ferroelectrics such as BaTiO3, exhibit a high &#949;r (103-104) and a low Eb (~100 MV/m)6,7,8. In some applications, flexibility and the ability to withstand high mechanical impacts are also important for fabricating dielectric capacitors4. Therefore, it is important to develop methods for preparing polymer-based dielectric composites, especially for the development of low-cost methods to create high-performance 0-3 nanocomposites with high &#949;r and Eb9,10,11,12,13,14,15,16,17,18. For this purpose, preparation methods based on ferroelectric polymer matrices such as the polar polymer PVDF and its correlated copolymers are widely accepted due to their higher &#949;r (~10)4,19,20. In these nanocomposites, particles with high er, especially ferroelectric ceramics, have been widely used as fillers6,20,21,22,23,24,25.
When developing methods for manufacturing ceramic-polymer composites, there is a general concern that dielectric properties can be significantly influenced by the distribution of fillers26. The homogeneity of dielectric composites is not only determined by the preparation methods, but also by the wettability between the matrix and fillers27. It has been proven by many studies that the non-uniformity of ceramic-polymer composites can be eliminated by physical processes such as spin-coating28,29 and hot-pressing19,26. However, neither of these two processes change the surface connection between fillers and matrices; therefore, the composites prepared by these methods are still limited in improving &#949;r and Eb19,27. Additionally, from a manufacturing point of view, inconvenient processes are undesirable for many applications because they can lead to much more complex fabrication processes28,29. In this regard, a simple and effective method is needed.
Currently, the most effective method to improve the compatibility of ceramic-polymer nanocomposites is based on the treatment of ceramic nanoparticles, which modifies the surface chemistry between fillers and matrices30,31. Recent studies have shown that coupling agents can be easily coated on ceramic nanoparticles and effectively modify the wettability between fillers and matrices without affecting the casting process32,33,34,35,36. For surface modification, it is widely accepted that for each composite system, there is a suitable amount of coupling agent, which corresponds to a maximal increase in energy storage density37; excess coupling agent in composites may result in a decline in the performance of products36,37,38. For dielectric composites using nano-sized ceramic fillers, it is speculated that the effectiveness of coupling agent mainly depends on the surface area of fillers. However, the critical amount to be used in each nano-sized system is yet to be determined. In short, further research is required to use coupling agents to develop simple processes for manufacturing ceramic-polymer nanocomposites.
In this work, BaTiO3 (BT), the most widely studied ferroelectric material with high dielectric constant, was used as fillers, and the P(VDF-CTFE) 91/9 mol% copolymer (VC91) was used as the polymer matrix for the preparation of ceramic-polymer composites. To modify the surface of the BT nanofillers, the commercially available 3-aminopropyltriethoxysilane (KH550) was purchased and used as a coupling agent. The critical amount of the nanocomposite system was determined through a series of experiment. An easy, low-cost, and widely applicable method is demonstrated to improve the energy density of nano-sized composite systems.

<table><tbody><tr><td>3-Aminopropyltriethoxysilane (KH550)</td><td>Sigma-Aldrich</td><td>440140</td><td>Liquid, Assay: 99%</td></tr><tr><td>95 wt.% ethanol-water</td><td>Sigma-Aldrich</td><td>459836</td><td>Liquid, Assay: 99.5%</td></tr><tr><td>BaTiO&lt;sub&gt;3&lt;/sub&gt; nanoparticles</td><td>US Research Nanomaterials</td><td>US3830</td><td>In a diameter of about 200 nm</td></tr><tr><td>Ferroelectric tester</td><td>Radiant</td><td>Precision-LC100</td><td></td></tr><tr><td>Glass substrates</td><td>Citoglas</td><td>16397</td><td>75 x 25 mm</td></tr><tr><td>Gold coater</td><td>Pelco</td><td>SC-6</td><td></td></tr><tr><td>High voltage supplier</td><td>Trek</td><td>610D</td><td>10 kV</td></tr><tr><td>Impedance analyzer</td><td>Keysight</td><td>4294A</td><td></td></tr><tr><td>N, N dimethylformamide</td><td>Fisher Scientific</td><td>GEN002007</td><td>Liquid</td></tr><tr><td>P(VDF-CTFE) 91/9 mol.% copolymer</td><td></td><td></td><td></td></tr><tr><td>Scanning Electron Microscopy (SEM)</td><td>JEOL</td><td>JSM-7000F</td><td></td></tr><tr><td>Vacuum oven</td><td>Heefei Kejing Materials Technology Co, Ltd</td><td>DZF-6020</td><td></td></tr></tbody></table>

application of a coupling agent to improve the dielectric properties of polymer-based nanocomposites

In this work, an easy, low-cost, and widely applicable method was developed to improve the compatibility between the ceramic fillers and the polymer matrix by adding 3-aminopropyltriethoxysilane (KH550) as a coupling agent during the fabrication process of BaTiO3-P(VDF-CTFE) nanocomposites through solution casting. Results show that the use of KH550 can modify the surface of ceramic nanofillers; therefore, good wettability on the ceramic-polymer interface was achieved, and the enhanced energy storage performances were obtained by a suitable amount of the coupling agent. This method can be used to prepare flexible composites, which is highly desirable for the production of high-performance film capacitors. If an excessive amount of coupling agent is used in the process, the non-attached coupling agent can participate in complex reactions, which leads to a decrease in dielectric constant and an increase in dielectric loss.

The free-standing nanocomposite films with different contents of fillers were successfully fabricated as described in the protocol, and were labeled as xBT-VC91, where x is the volume percentage of BT in the composites. The effect of KH550 (coupling agent) on the morphology and microstructure of these BT-VC91 films was studied by SEM and shown in Figure 1. The SEM images of 30BT-VC91 nanocomposites with 1 and 5 wt% coupling agent are shown in Figure 1a and <stro...

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Application of a Coupling Agent to Improve the Dielectric Properties of Polymer-Based Nanocomposites

Here, we demonstrate a simple and low-cost solution-casting process to improve the compatibility between the filler and the matrix of polymer-based nanocomposites using surface modified BaTiO3 fillers, which can effectively enhance the energy density of the composites.

In this work, an easy, low-cost, and widely applicable method was developed to improve the compatibility between the ceramic fillers and the polymer ...

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5.8K Views.  Taiyuan University of Science and Technology. Here, we demonstrate a simple and low-cost solution-casting process to improve the compatibility between the filler and the matrix of polymer-based nanocomposites using surface modified BaTiO3 fillers, which can effectively enhance the energy density of the composites.

Video: Application of a Coupling Agent to Improve the Dielectric Properties of Polymer-Based Nanocomposites

Formulation of Diblock Polymeric Nanoparticles through Nanoprecipitation Technique

Nanotechnology is a relatively new branch of science that involves harnessing the unique properties of particles that are nanometers in scale (nanoparticles). Nanoparticles can be engineered in a precise fashion where their size, composition and surface chemistry can be carefully controlled. This enables unprecedented freedom to modify some of the fundamental properties of their cargo, such as solubility, diffusivity, biodistribution, release characteristics and immunogenicity. Since their inception, nanoparticles have been utilized in many areas of science and medicine, including drug delivery, imaging, and cell biology1-4. However, it has not been fully utilized outside of "nanotechnology laboratories" due to perceived technical barrier. In this article, we describe a simple method to synthesize a polymer based nanoparticle platform that has a wide range of potential applications. 
The first step is to synthesize a diblock co-polymer that has both a hydrophobic domain and hydrophilic domain. Using PLGA and PEG as model polymers, we described a conjugation reaction using EDC/NHS chemistry5 (Fig 1). We also discuss the polymer purification process. The synthesized diblock co-polymer can self-assemble into nanoparticles in the nanoprecipitation process through hydrophobic-hydrophilic interactions.
The described polymer nanoparticle is very versatile. The hydrophobic core of the nanoparticle can be utilized to carry poorly soluble drugs for drug delivery experiments6. Furthermore, the nanoparticles can overcome the problem of toxic solvents for poorly soluble molecular biology reagents, such as wortmannin, which requires a solvent like DMSO. However, DMSO can be toxic to cells and interfere with the experiment. These poorly soluble drugs and reagents can be effectively delivered using polymer nanoparticles with minimal toxicity. Polymer nanoparticles can also be loaded with fluorescent dye and utilized for intracellular trafficking studies. Lastly, these polymer nanoparticles can be conjugated to targeting ligands through surface PEG. Such targeted nanoparticles can be utilized to label specific epitopes on or in cells7-10.

This article describes a nanoprecipitation method to synthesize polymer-based nanoparticles using diblock co-polymers. We will discuss the synthesis of diblock co-polymers, the nanoprecipitation technique, and potential applications.

Nanotechnology is a relatively new branch of science that involves harnessing the unique properties of particles that are nanometers in scale ...

Bioengineering

Using Polystyrene-block-poly(acrylic acid)-coated Metal Nanoparticles as Monomers for Their Homo- and Co-polymerization

We present a template-free method for &#8220;polymerizing&#8221; nanoparticles into long chains without side branches. A variety of nanoparticles are encapsulated in polystyrene-block-poly(acrylic acid) (PSPAA) shells and then used as monomers for their self-assembly. Spherical PSPAA micelles upon acid treatment are known to assemble into cylindrical micelles. Exploiting this tendency, the core-shell nanoparticles are induced to aggregate, coalesce, and then transform into long chains. When more than one type of nanoparticles are used, random and block &#8220;copolymers&#8221; of nanoparticles can be obtained. Detailed procedures are reported for the PSPAA encapsulation of nanoparticles, homo- and co-polymerization of the core-shell nanoparticles, separation and purification of the resulting nanoparticle chains. Transformations of single-line chains into double- and triple-line chains are also presented. The synergy between the polymer shell and the embedded nanoparticles leads to an unusual chain-growth polymerization mode, giving long nanoparticle chains that are distinct from the products of the traditional step-growth aggregation process.

Using Polystyrene-block-polyacrylic acid-coated Metal Nanoparticles as Monomers for Their Homo- and Co-polymerization

We report protocols for &#8220;polymerizing&#8221; various types of polymer-encapsulated metal nanoparticles into long chains of &#8220;homo-&#8220; and &#8220;co-polymers&#8221;.

We present a template-free method for &#8220;polymerizing&#8221; nanoparticles into long chains without side branches. A variety of nanoparticles are ...

Chemistry

Functionalization and Dispersion of Carbon Nanomaterials Using an Environmentally Friendly Ultrasonicated Ozonolysis Process

Functionalization of carbon nanomaterials is often a critical step that facilitates their integration into larger material systems and devices. In the as-received form, carbon nanomaterials, such as carbon nanotubes (CNTs) or graphene nanoplatelets (GNPs), may contain large agglomerates. Both agglomerates and impurities will diminish the benefits of the unique electrical and mechanical properties offered when CNTs or GNPs are incorporated into polymers or composite material systems. Whilst a variety of methods exist to functionalize carbon nanomaterials and to create stable dispersions, many the processes use harsh chemicals, organic solvents, or surfactants, which are environmentally unfriendly and may increase the processing burden when isolating the nanomaterials for subsequent use. The current research details the use of an alternative, environmentally friendly technique for functionalizing CNTs and GNPs. It produces stable, aqueous dispersions free of harmful chemicals. Both CNTs and GNPs can be added to water at concentrations up to 5 g/L and can be recirculated through a high-powered ultrasonic cell. The simultaneous injection of ozone into the cell progressively oxidizes the carbon nanomaterials, and the combined ultrasonication breaks down agglomerates and immediately exposes fresh material for functionalization. The prepared dispersions are ideally suited for the deposition of thin films onto solid substrates using electrophoretic deposition (EPD). CNTs and GNPs from the aqueous dispersions can be readily used to coat carbon- and glass-reinforcing fibers using EPD for the preparation of hierarchical composite materials.

Here, a novel method for the functionalization and stable dispersion of carbon nanomaterials in aqueous environments is described. Ozone is injected directly into an aqueous dispersion of carbon nanomaterial that is continuously recirculated through a high-powered ultrasonic cell.

Functionalization of carbon nanomaterials is often a critical step that facilitates their integration into larger material systems and devices. In the ...

Environment

Electroactive Polymer Nanoparticles Exhibiting Photothermal Properties

A method for the synthesis of electroactive polymers is demonstrated, starting with the synthesis of extended conjugation monomers using a three-step process that finishes with Negishi coupling. Negishi coupling is a cross-coupling process in which a chemical precursor is first lithiated, followed by transmetallation with ZnCl2. The resultant organozinc compound can be coupled to a dibrominated aromatic precursor to give the conjugated monomer. Polymer films can be prepared via electropolymerization of the monomer and characterized using cyclic voltammetry and ultraviolet-visible-near infrared (UV-Vis-NIR) spectroscopy. Nanoparticles (NPs) are prepared via emulsion polymerization of the monomer using a two-surfactant system to yield an aqueous dispersion of the polymer NPs. The NPs are characterized using dynamic light scattering, electron microscopy, and UV-Vis-NIR-spectroscopy. Cytocompatibility of NPs is investigated using the cell viability assay. Finally, the NP suspensions are irradiated with a NIR laser to determine their effectiveness as potential materials for photothermal therapy (PTT).

A protocol is presented for the synthesis and preparation of nanoparticles consisting of electroactive polymers.

A method for the synthesis of electroactive polymers is demonstrated, starting with the synthesis of extended conjugation monomers using a three-step ...

Advanced Compositional Analysis of Nanoparticle-polymer Composites Using Direct Fluorescence Imaging

The fabrication of polymer-nanoparticle composites is extremely important in the development of many functional materials. Identifying the precise composition of these materials is essential, especially in the design of surface catalysts, where the surface concentration of the active component determines the activity of the material. Antimicrobial materials which utilize nanoparticles are a particular focus of this technology. Recently swell encapsulation has emerged as a technique for inserting antimicrobial nanoparticles into a host polymer matrix. Swell encapsulation provides the advantage of localizing the incorporation to the external surfaces of materials, which act as the active sites of these materials. However, quantification of this nanoparticle uptake is challenging. Previous studies explore the link between antimicrobial activity and surface concentration of the active component, but this is not directly visualized. Here we show a reliable method to monitor the incorporation of nanoparticles into a polymer host matrix via swell encapsulation. We show that the surface concentration of CdSe/ZnS nanoparticles can be accurately visualized through cross-sectional fluorescence imaging. Using this method, we can quantify the uptake of nanoparticles via swell encapsulation and measure the surface concentration of encapsulated particles, which is key in optimizing the activity of functional materials.

Here we present a reliable method to monitor the incorporation of nanoparticles into a polymer host matrix via swell encapsulation. We show that the surface concentration of cadmium selenide quantum dots can be accurately visualized through cross-sectional fluorescence imaging.

The fabrication of polymer-nanoparticle composites is extremely important in the development of many functional materials. Identifying the precise ...

Nanosponge Tunability in Size and Crosslinking Density

We describe a protocol for the synthesis of linear polyesters containing pendant epoxide functionality and their incorporation into a nanosponge with controlled dimensions. This approach begins with synthesis of a functionalized lactone which is key to the pendant functionalization of the resulting polymer. Valerolactone (VL) and allyl-valerolactone (AVL) are then copolymerized using ring-opening polymerization. Post-polymerization modification is then used to install an epoxide moiety on some or all of the pendant allyl groups. Epoxy-amine chemistry is employed to form nanoparticles in a dilute solution of both polymer and small molecule diamine crosslinker based on the desired nanosponge size and crosslinking density. Nanosponge sizes can be characterized by transmission electron microscopy (TEM) imaging to determine the dimension and distribution. This method provides a pathway by which highly tunable polyesters can create tunable nanoparticles, which can be used for small molecule drug encapsulation. Due to the nature of the backbone, these particles are hydrolytically and enzymatically degradable for a controlled release of a wide range of hydrophobic small molecules.

This article describes a process for tuning the size and crosslinking density of covalently crosslinked nanoparticles from linear polyesters containing pendant functionality. By tailoring synthesis parameters (polymer molecular weight, pendant functionality incorporation, and crosslinker equivalents), a desired nanoparticle size and crosslinking density can be achieved for drug delivery applications.

We describe a protocol for the synthesis of linear polyesters containing pendant epoxide functionality and their incorporation into a nanosponge with ...

The Effect of Construction and Demolition Waste Plastic Fractions on Wood-Polymer Composite Properties

Construction and demolition waste (CDW), including valuable materials such as plastics, have a remarkable influence on the waste sector. In order for plastic materials to be re-utilized, they must be identified and separated according to their polymer composition. In this study, the identification of these materials was performed using near-infrared spectroscopy (NIR), which identified material based on their physical-chemical properties. Advantages of the NIR method are a low environmental impact and rapid measurement (within a few seconds) in the spectral range of 1600-2400 nm without special sample preparation. Limitations include its inability to analyze dark materials. The identified polymers were utilized as a component for wood-polymer composite (WPC) that consists of a polymer matrix, low cost fillers, and additives. The components were first compounded with an agglomeration apparatus, followed by production by extrusion. In the agglomeration process, the aim was to compound all materials to produce uniformly distributed and granulated materials as pellets. During the agglomeration process, the polymer (matrix) was melted and fillers and other additives were then mixed into the melted polymer, being ready for the extrusion process. In the extrusion method, heat and shear forces were applied to a material within the barrel of a conical counter-rotating twin-screw type extruder, which reduces the risk of burning the materials and lower shear mixing. The heated and sheared mixture was then conveyed through a die to give the product the desired shape. The above-described protocol proved the potential for re-utilization of CDW materials. Functional properties must be verified according to the standardized tests, such as flexural, tensile, and impact strength tests for the material.

Secondary material streams have been shown to include potential raw materials for production. Presented here is a protocol in which CDW-plastic waste as a raw material is identified, followed by various processing steps (agglomeration, extrusion). As a result, a composite material was produced, and mechanical properties were analyzed.

Construction and demolition waste (CDW), including valuable materials such as plastics, have a remarkable influence on the waste sector. In order for ...

Preparation of Monodomain Liquid Crystal Elastomers and Liquid Crystal Elastomer Nanocomposites

LCEs are shape-responsive materials with fully reversible shape change and potential applications in medicine, tissue engineering, artificial muscles, and as soft robots. Here, we demonstrate the preparation of shape-responsive liquid crystal elastomers (LCEs) and LCE nanocomposites along with characterization of their shape-responsiveness, mechanical properties, and microstructure. Two types of LCEs &#8212; polysiloxane-based and epoxy-based &#8212; are synthesized, aligned, and characterized. Polysiloxane-based LCEs are prepared through two crosslinking steps, the second under an applied load, resulting in monodomain LCEs. Polysiloxane LCE nanocomposites are prepared through the addition of conductive carbon black nanoparticles, both throughout the bulk of the LCE and to the LCE surface. Epoxy-based LCEs are prepared through a reversible esterification reaction. Epoxy-based LCEs are aligned through the application of a uniaxial load at elevated (160 &#176;C) temperatures. Aligned LCEs and LCE nanocomposites are characterized with respect to reversible strain, mechanical stiffness, and liquid crystal ordering using a combination of imaging, two-dimensional X-ray diffraction measurements, differential scanning calorimetry, and dynamic mechanical analysis. LCEs and LCE nanocomposites can be stimulated with heat and/or electrical potential to controllably generate strains in cell culture media, and we demonstrate the application of LCEs as shape-responsive substrates for cell culture using a custom-made apparatus.

We demonstrate the preparation of siloxane-based and epoxy-based liquid crystal elastomers (LCEs) and LCE nanocomposites. The LCEs are characterized with respect to reversible strain, liquid crystal ordering, and stiffness. As a potential application, we demonstrate their use as shape-responsive substrates in a custom device for active cell culture.

LCEs are shape-responsive materials with fully reversible shape change and potential applications in medicine, tissue engineering, artificial muscles, and ...

Synthesis of Stimuli-responsive Nanogels using Aqueous One-step Crosslinking and Co-nanopolymerization

Nanogels consisting of crosslinked-polymeric nanoparticles have been developed for the delivery of numerous chemical and biological therapeutics, owing to their versatile bottom-up synthesis and biocompatibility. While various methods have been employed for nanogel synthesis to date, very few have achieved it without the use of harsh organic solvents or high temperatures that can damage the integrity of the biological payload. In contrast, the methodology presented here accomplishes the synthesis of sub-100 nm sized, protein-loaded nanogels using mild reaction conditions. Here, we present a method for the non-covalent encapsulation of protein-based payloads within nano-gels that were synthesized using an aqueous-based, single-step, crosslinking copolymerization technique. In this technique, we initially electrostatically bind a protein-based payload to a cationic quaternary ammonium monomer and simultaneously cross-link and co-polymerize it using ammonium persulfate and N,N,N&#39;,N&#39;-tetramethylethylenediamine to form nanogels that entrap the protein payload. The size and polydispersity index of the nanogels is determined using dynamic light scattering (DLS), while the surface morphology is assessed by transmission electron microscopy (TEM). The mass of protein entrapped within nanogels is determined by calculating the encapsulation efficiency. Furthermore, the controlled-release ability of the nanogels via the gradual degradation of redox-responsive structural elements is also assessed in bioreduction assays. We provide examples of nanoparticle optimization data to demonstrate all caveats of nanogel synthesis and characterization using this technique. In general, uniformly sized nanogels were obtained with an average size of 57 nm and a polydispersity index value of 0.093. A high encapsulation efficiency of 76% was achieved. Furthermore, the nanogels exhibited controlled release of up to 86% of the encapsulated protein by gradual degradation of novel redox-responsive components in the presence of glutathione over 48 h.

Nanogels are an excellent and versatile nanoparticle platform for the delivery of biologics. Stimuli-responsive poly(ethylene) glycol-based polymeric nano-gels, capable of encapsulating protein-based payloads, were synthesized using a one-step cross-linking co-nanopolymerization strategy in aqueous conditions. The optimal fabrication and characterization of these novel nanoparticles are presented here.

Nanogels consisting of crosslinked-polymeric nanoparticles have been developed for the delivery of numerous chemical and biological therapeutics, owing to ...

Vapor Phase Deposition of Electroactive Poly(3,4-ethylenedioxythiophene) onto Electrospun Commodity Polymer Nanofibers

This study investigates the preparation of polyacrylonitrile (PAN) nanofibers through electrospinning to create highly porous and strong materials for applications in water purification, electrocatalysis, and biomedicine. The uniformly white PAN nanofiber mats were cut into 2 cm x 2 cm coupons to ensure consistency. After electrospinning, these nanofibers were coated with an electroactive polymer (EAP) using chemical vapor deposition, with iron (III) chloride (FeCl3) serving as an oxidant for polymerizing 3,4-ethylenedioxythiophene (EDOT) into poly(3,4-ethylenedioxythiophene) (PEDOT). The study examined the impact of different FeCl3 concentrations on PEDOT deposition on the PAN coupons. PEDOT deposition led to an increase in coupon weight. Scanning electron microscopy (SEM) revealed increases in the diameter of the nanofibers treated with increasing FeCl3 oxidant concentration, although higher FeCl3&#160;concentrations caused inter-fiber bridging, implying a concomitant decrease in inter-fiber spacing. Energy dispersive X-ray spectroscopy (EDS) was used to confirm the presence of Fe, Cl, and S in the nanofibers, with sulfur content rising with FeCl3&#160;concentration used, suggesting increased PEDOT deposition efficiency with increasing oxidant concentration. Mechanical testing showed that PEDOT-coated PAN fibers had improved tensile strength and toughness in the hydrated state compared to pure PAN nanofibers. These results highlight the crucial role of FeCl3&#160;concentration in influencing the morphology and properties of PAN-PEDOT composites, enhancing their suitability for applications such as water purification, tissue engineering, biosensing, catalysis, and energy storage.

This paper describes a simple technique for coating electrospun PAN nanofibers with electroactive polymers using vapor deposition. The effects of the oxidant FeCl&#8323; on the deposition of poly(3,4-ethylenedioxythiophene) coatings on PAN were investigated to understand and optimize polymer growth, fiber diameter, and overall mechanical strength of the nanofiber mats.

This study investigates the preparation of polyacrylonitrile (PAN) nanofibers through electrospinning to create highly porous and strong materials for ...