Synthesis of a bio‐inspired catechol/phosphorylcholine surface modifier and characterization of its surface properties

Biocompatible and blood‐compatible surface modification is urgently needed for stainless steel (SUS)‐based human implant devices to avoid inflammation and biofouling. To this end, the use of polymeric surface modifiers, whose surface properties are specifically tailored, is a promising approach since this approach minimizes the impact on device's mechanical properties. However, adhesion between the device and surface modifier is relatively weak, since van der Waals forces are employed, leading to low device durability. To address this issue, this work functionalized poly(ɛ‐caprolactone)‐b‐[poly(α‐chloride‐ɛ‐caprolactone)‐b‐poly(2‐methacryloyloxyethyl phosphorylcholine)]₂ (PCL‐b‐(PCL‐Cl‐b‐PMPC)₂) with catechol groups via a nucleophilic substitution, whereby the catechol functionalization was optimized. The resultant surface modifier showed strong adhesion toward SUS surfaces, forming a smooth and uniform hydrophilic polymeric film that reduced SUS fouling (i.e., protein). Notably, no significant changes of adhesion between the SUS and thin films (thin film) were observed after immersion for 45 days in a pH 7.4 phosphate buffer solution. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 38–49     

Unsaturated hyperbranched polyester as a surface modifier of CaCO3 and enhanced effect on mechanical properties of HDPE/CaCO3 composites

The unsaturated hyperbranched polyester (UH20) based on Boltorn™ H20 (H20) end‐capped with methacrylate groups and carboxylic acid groups was introduced to treat calcium carbonate (CaCO₃) as a new type of surface modifier by a wet‐coating technique. The interaction between CaCO₃ and modifier was proven to be due to the ionic character by FT‐IR after the extraction with acetone. The maximum amount of tightly bonded UH20 modifier was determined to be around 9% by thermogravimetric analysis (TGA). The incorporation of CaCO₃ coated with UH20 into high‐density polyethylene (HDPE) decreased the mechanical performance of HDPE/CaCO₃ composite in comparison with CaCO₃ coated with stearic acid. In the presence of a small amount of dicumyl peroxide (DCP), a greatly improvement of the notched impact strength as well the tensile strength of HDPE/CaCO₃ coated with UH20 composite was obtained. An enhanced effect in the mechanical performance of the composite between CaCO₃ coated with UH20 and HDPE matrix in the existence of DCP was suggested. Moreover, the morphological structures of impact fracture surface of the HDPE/CaCO₃ composites were studied by scanning electron microscopy (SEM) to confirm the possible mechanism for explaining the improvement of mechanical properties of the composite. Copyright © 2005 John Wiley & Sons, Ltd.     

Structural and mechanical behavior of polypropylene/ maleated styrene‐(ethylene‐co‐butylene)‐styrene/sisal fiber composites prepared by injection molding

Hybrid composites consisting of isotactic poly(propylene) (PP), sisal fiber (SF), and maleic anhydride grafted styrene‐(ethylene‐co‐butylene)‐styrene copolymer (MA‐SEBS) were prepared by melt compounding, followed by injection molding. The melt‐compounding torque behavior, thermal properties, morphology, crystal structure, and mechanical behavior of the PP/MA‐SEBS/SF composites were systematically investigated. The torque test, thermogravimetric analysis, differential scanning calorimetric, and scanning electron microscopic results all indicated that MA‐SEBS was an effective compatibilizer for the PP/SF composites, and there was a synergism between MA‐SEBS and PP/SF in the thermal stability of the PP/MA‐SEBS/SF composites. Wide‐angle X‐ray diffraction analysis indicated that the α form and β form of the PP crystals coexisted in the PP/MA‐SEBS/SF composites. With the incorporation of MA‐SEBS, the relative amount of β‐form PP crystals decreased significantly. Mechanical tests showed that the tensile strength and impact toughness of the PP/SF composites were generally improved by the incorporation of MA‐SEBS. The instrumented drop‐weight dart‐impact test was also used to examine the impact‐fracture behavior of these composites. The results revealed that the maximum impact force (F_max), impact‐fracture energy (E_T), total impact duration (t_r), crack‐initiation time (t_init), and crack‐propagation time (t_prop) of the composites all tended to increase with an increasing MA‐SEBS content. From these results, the incorporation of MA‐SEBS into PP/SF composites can retard both the crack initiation and propagation phases of the impact‐fracture process. These prolonged the crack initiation and propagation time and increased the energy consumption during impact fracture, thereby leading to toughening of PP/MA‐SEBS/SF composites. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1214–1222, 2002     

Effects of elastomer on morphology,flammability and rheological properties of HIPS/PS‐encapsulated Mg(OH)2 composites

The effects of elastomer type on morphology, flammability and rheological properties of high‐impact polystyrene/Mg(OH)₂ based on encapsulated by polystyrene have been investigated. The ternary composites characterized by cone calorimetry, horizontal burning rate, limiting oxygen index (LOI), rheology and SEM. Morphology was controlled using poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] triblock copolymer (SEBS) or the corresponding maleinated SEBS (SEBS‐g‐MA). As revealed by SEM observations, composites of HIPS/SEBS/Mg(OH)₂ exhibit separation of the filler and elastomer and good adhesion between SEBS and the filler, whereas composites of HIPS/SEBS‐g‐MA/Mg(OH)₂ exhibit encapsulation of the filler by SEBS‐g‐MA. The flame retardant and rheological properties of ternary composites were strongly dependent on microstructure. The rheological test showed that the composites with encapsulation structure exhibit a stronger solid‐like response at low frequency than those of the composites with separate dispersion structure. The combustion tests showed that the composites with encapsulation structure showed higher flame retardant properties than those of separate dispersion structure at optimum use level of SEBS‐g‐MA. However, with the increase of the content of SEBS‐g‐MA, the flame retardancy of the composite declined somewhat which can be explained that the SEBS‐g‐MA coating acts as a heat and mass transfer barrier due to the formation of encapsulation structure. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2023–2030, 2007     

Novel fibrous composites based on electrospun PSF and PVDF ultrathin fibers reinforced with inorganic nanoparticles: Evaluation as oil spill sorbents

Oil spill accidents and oily wastewaters induce a negative impact to the environment and human health. Therefore, the developing of new sorbent materials to combat promptly such type of pollution is of great interest. In this work, poly(vinylidene fluoride) and polysulfone ultrathin fibers reinforced with Halloysite nanoclay and CoFe₂O₄ were developed via electrospinning method as composite sorbent materials. Fibrous composites were characterized by scanning and transmission electron microscopy. The magnetic property and the wetting behavior were ascertained by magnetometric and contact angle measurements, respectively. Results showed that the morphology of fibers was homogeneous, and the inorganic particles were properly dispersed within the polymeric matrix. Finally, sorbents were tested for sorption of oily liquids. Produced materials revealed the sorption capacities ranging from 3.70 to 10.01 g/g for poly(vinylidene fluoride)‐based composites, and from 15.69 to 28.21 g/g for polysulfone‐based composites, depending on the nature of tested oil.     

Preparation and enhanced properties of poly(propylene)/ silica‐grafted‐hyperbranched polyester nanocomposites

A series of poly(propylene) silica‐grafted‐hyperbranched polyester nanocomposites by grafting the modified hyperbranched polyester (Boltorn? H20), possessing theoretically 50% end carboxylic groups and 50% end hydroxyl groups, which endcapped with octadecyl isocyanate (C19), onto the surface of SiO₂ particles (30 nm) through 3‐glycidoxy‐propyltrimethoxysilane (GPTS) was prepared. The effect of silica‐grafted‐modified Boltorn? H20 on the mechanical properties of polypropylene (PP) was investigated by tensile and impact tests. The morphological structure of impact fracture surface and thermal behavior of the composites were determined by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC), respectively. The melt viscosity of composites was investigated by melt flow index (MFI). The obtained results showed that: (1) the modified Boltorn? H20 was successfully grafted onto the SiO₂ surface confirmed by FT‐IR and X‐ray photoelectron spectroscopy (XPS) analysis; (2) the incorporation of silica‐grafted‐modified Boltorn? H20 (3–5 wt% SiO₂) greatly enhanced the notched impact strength as well the tensile strength of the composites; (3) the incorporation of silica‐grafted‐modified Boltorn? H20 had no influence on the melting temperature and crystallinity of PP phase; (4) the MFI of PP composites increased when the silica‐grafted‐modified Boltorn? H20 particles were added compared with PP/SiO₂ or PP/SiO₂‐GPTS composites. Copyright © 2004 John Wiley & Sons, Ltd.     

Correlation of morphological parameters and mechanical performance of polyamide‐612/poly (ethylene–octene) elastomer blends

Blends of polyamide‐612 (PA‐612) and maleic anhydride grafted poly (ethylene–octene) elastomer (POE‐g‐MA) as an impact modifier have been prepared in the composition range of 0–35 wt. % of POE‐g‐MA and subsequently investigated for their structural, thermal, mechanical, dynamic mechanical properties and morphological attributes. X‐ray diffraction studies revealed a decrease in crystallinity whereas the thermal properties such as onset to degradation temperature and crystallization temperature remained broadly unaffected. Nearly three‐fold increase in the impact strength is registered accompanied by substantial increase in tensile failure strain, though tensile modulus (E) and tensile yield strength (σ _y) decreased with increase in impact modifier content. Dynamic mechanical analysis exhibited a singularity response in the loss factor in the temperature range of ~10°C–50°C. Micromechanical aspects were analyzed using conventional theoretical models for low strain mechanical response (E) such as rule of mixtures and foam model and for high strain mechanical response (σ _y) such as Nikolais–Narkis model and porosity model. Impact toughness and strain‐at‐break of the investigated composition were successfully correlated to the domain size (D_n) of the dispersed phase and their inter‐particle distances (τ). Scanning electron microscopy showed the coalescence of domains of the dispersed phase at higher POE content and thus reiterates the crucial role of inter‐particle distance in controlling the toughening mechanism of POE blended PA‐612. Copyright © 2013 John Wiley & Sons, Ltd.     

Stopped‐flow polymerizations of ethene and propene in the presence of the catalyst system rac‐Me2Si(2‐methyl‐4‐phenyl‐1‐indenyl)2ZrCl2/methylaluminoxane

The kinetics of ethene and propene polymerization at 20–60°C in the presence of the homogeneous catalyst system rac‐Me₂Si(2‐methyl‐4‐phenyl‐1‐indenyl)₂ZrCl₂/methylaluminoxane was investigated by means of stopped‐flow techniques. The specific rate of chain propagation, measured at the very short reaction times typical of this method, turned out to be ≈10² times higher for ethene than for propene; this suggests that diffusion limitations through the poly(ethylene) precipitating at longer reaction times may be responsible for the fact that the two monomers polymerize instead at comparable rates under “standard” conditions. It was also found that the concentration of active sites is significantly lower than the analytical Zr concentration.     

Noncovalent functionalization of multiwalled carbon nanotubes using graft copolymer with naphthalene and its application as a reinforcing filler for poly(styrene‐co‐acrylonitrile)

A new compatibilizer, poly(vinyl benzyloxy ethyl naphthalene)‐graft‐poly(methyl methacrylate), for poly(styrene‐co‐acrylonirile) (SAN)/multi‐walled carbon nanotubes (MWCNTs) composites was synthesized. It has been identified that naphthalene unit in backbone of compatibilizer interacts with MWCNTs via π? π interaction and that the PMMA graft of the compatibilizer is miscible with the SAN matrix. When a small amount of compatibilizer was added to SAN/MWCNT composites, MWCNTs were more homogeneously dispersed in SAN matrix than the case without compatibilizer, indicating that the compatibilizer improves the compatibility between SAN and MWCNTs. As a consequence, mechanical and electrical properties of the composites with compatibilizer were largely improved as compared with those of composites without compatibilizer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4184–4191, 2010     

Structural Aspects of Palladium and Platinum Complexes With Chiral Diphosphinoferrocenes Relevant to the Regio‐ and Stereoselective Copolymerization of CO with Propene

A series of chiral diphosphinoferrocene ligands 3a – i , derived from josiphos (=(2R)‐1‐[(1R)‐1‐(dicyclohexylphosphino)ethyl]‐2‐(diphenylphosphino)ferrocene, formerly called {(R)‐1‐[(S)‐2‐(diphenylphosphino)ferrocenyl]ethyl}dicycloxexylphosphine) where the electronic properties of the ligand are systematically varied, were prepared. X‐Ray studies of five of these new ligands confirmed that these compounds display very similar conformations in the solid state and that no structural criteria could be found indicating the modified electronic properties. These ligands find application in the Pd‐catalyzed highly regio‐ and stereoselective CO/propene copolymerization reaction, where the electronic properties of the ligand show a great impact on the catalyst activity. Coordination‐chemical aspects of these diphosphinoferrocenes relevant to the CO/propene copolymerization reaction were addressed by the preparation and characterization of Pd‐ and Pt‐complexes of the general formula [PdCl₂(P−P)] ( 5 ), [PdMe₂(P−P)] ( 6 ), [PdClMe(P−P)] ( 7 ), [PdMe(MeCN)(P−P)]PF₆ ( 8 ), and [PtClMe(P−P)] ( 9 ) (P−P=chiral diphosphinoferrocene ligand ( 3a – h ), four of which were characterized by X‐ray crystallography.     

Morphology and fracture behavior of toughening‐modified poly(vinyl chloride)/organophilic montmorillonite composites

Toughening‐modified poly(vinyl chloride) (PVC)/organophilic montmorillonite (OMMT) composites with an impact‐modifier resin (Blendex 338) were prepared by melt intercalation, and their microstructures were investigated with wide‐angle X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy. The mechanical properties of the PVC composites were examined in terms of the content of Blendex and OMMT, and the fracture toughness was analyzed with a modified essential work of fracture model. Intercalated structures were found in the PVC/OMMT composites with or without Blendex. Either Blendex or OMMT could improve the elongation at break and notched impact strength of PVC at proper contents. With the addition of 30 phr or more of Blendex, supertough behavior was observed for PVC/Blendex blends, and their notched impact strength was increased more than 3319% compared with that of pristine PVC. Furthermore, the addition of OMMT greatly improved both the toughness and strength of PVC/Blendex blends, and the toughening effect of OMMT on PVC/Blendex blends was much larger than that on pristine PVC. Blendex and OMMT synergistically improved the mechanical properties of PVC. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 286–295, 2004     

Stable second‐order nonlinear optical poly(amide–imide)/inorganic materials via simultaneous sequential self‐repetitive reaction and sol–gel process

A series of thermally stable organic/inorganic second‐order nonlinear optical (NLO) composites via sequential self‐repetitive reaction (SSRR) and sol–gel process has been developed. This SSRR is based on carbodiimide (CDI) chemistry. The difunctional azo chromophores (2,4‐diamino‐4′‐(4‐ nitrophenyl‐diazenyl)azobenzene (DNDA)) was reacted with excessive amount of 4, 4′‐methylene‐ diphenylisocyanate (MDI) to form poly‐CDI, and subsequently trimellitic anhydride (TMA) was added to obtain poly(N‐acylurea). The organic/inorganic composites containing prepolymer of phenyltriethoxysilane (PTEOS) and poly(N‐acylurea) in different weight ratios (10:90, 30:70, 50:50, 70:30, 90:10 wt%) were prepared, respectively. The moderate glass transition temperature (T_g) characteristic of the poly(N‐acylurea) allows the NLO‐active polymer to achieve high poling efficiency. After in situ poling and curing process, the T_gs of the composites were elevated, and higher than that of the pristine poly(amide–imide) sample. Electro‐optical (EO) coefficients (r₃₃) of about 5.5 ～ 18.0 pm/V at 830 nm were obtained. Excellent temporal stability at 100°C, and waveguide characteristics (3.1–4.2 dB/cm at 830 nm) were also obtained for these composites. Copyright © 2008 John Wiley & Sons, Ltd.     

Surface modification of multiwall carbon nanotubes and its effect on mechanical and through‐plane electrical resistivity of PEMFC bipolar plate nanocomposites

In this work, we showed how the functionalization of multiwall carbon nanotubes (MWCNT) by nitric acid (HNO₃) and their predispersion into poly (butylene terephthalate) (PBT) improved the through‐plane electrical conductivity and mechanical properties of co‐continuous morphology polyvinylidene fluoride (PVDF)/poly (ethylene terephthalate) (PET)/carbon black (CB)/graphite (GR)/MWCNT nanocomposites. First, when MWCNT were functionalized with HNO₃ then premixed with PBT, they showed no aggregations inside the PBT matrix due to their improved interfacial interactions and chemical compatibility with the PBT matrix. Then, when PBT/(HNO₃‐functionalized MWCNT) mixture was added in small quantities to (PET/PVDF)/(CB/GR) composites, it decreased significantly their through‐plane resistivity and enhanced their impact and flexural properties. Its synergistic effect also led to the best proton exchange membrane fuel cell bipolar plate prototypes (smoother surface, without any cracks).     

Dispersion of silica nanoparticles bearing perfluorohexyl units into fluorinated copolymers

This study aims at determining the compatibility behavior of nanoparticles surface with fluorinated matrices to obtain a homogenous dispersion and better composites properties. First, modified silica nanoparticles by C₆F₁₃I and C₆F₁₃‐C₂H₄‐SH led to various fluorinated silica of different massic concentrations and grafting rates. The dispersion of these nanoparticles (in 5 wt %) into molten poly(VDF‐co‐HFP) and poly(TFE‐co‐HFP) matrices were studied as well as the hydrophobic, mechanical, and thermal properties of both fluorinated copolymers and resulting composites. In both series, the storage modulus of nanocomposites increased while the melting (T_m) and decomposition (T_10%) temperatures varied with the polymer matrix. They increased for poly(VDF‐co‐HFP) composites (T_m= 134 to 144 °C and T_10%= 441 to 464 °C) but decreased for poly(TFE‐co‐HFP) nanocomposites (T_m= 276 to 268 °C and T_10%= 488 to 477 °C). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1512–1522     

Polylactide (PLA) and Highly Filled PLA - Calcium Sulfate Composites with Improved Impact Properties

Summary: Starting from gypsum as by-product of lactic acid fabrication process, novel high performance composites have been produced by melt-blending PLA and this filler after a previous specific dehydration performed at 500 °C for min. 1h. Due to PLA sensitivity towards hydrolysis, the utilization of β-anhydrite II (AII) as filler is a prerequisite. Characterized by attractive mechanical and thermal properties due to good filler dispersion throughout the polyester matrix, these composites are interesting in biodegradable rigid packaging or technical applications. Interestingly, tensile strength of PLA – AII composites proved remarkably high, e.g. higher than 35 MPa at 50 wt-% filler content. However a decrease of impact properties has been recorded. To increase the toughness of these composites while preserving high stiffness an impact modifier based on ethylene copolymer has been mixed with both the polymer matrix and AII by melt-compounding. The effectiveness of the impact modifier was confirmed in both neat PLA and AII-based composites. Addition of 5-10 wt-% impact modifier into highly filled composites (30 to 40 wt-% filler) leads to an attractively threefold increase of impact strength with respect to the compositions without modifier, remarkable thermo-mechanical performances and good filler dispersion.     

Synthesis and properties of sulfur‐contained poly(silylene arylacetylene)s

Poly(silylene arylacetylene) (PSA) is a kind of poly(arylacetylene) silicon‐containing resins with excellent heat resistance and good mechanical performances. In this article, the sulfur atom is introduced into the main chain of the PSA molecule to obtain a sulfur‐containing poly(silylene arylacetylene), named S‐PSA. By Williamson and Sonogashira reactions, bis(4‐ethynylphenyl)sulfide and bis(4‐ethynylphenyl)sulfone were synthesized. Thereafter, through Grignard reagent way, the poly(silylene ethynylene phenylene sulfide phenylene ethynylene) (PSESE) and poly(silylene ethynylene phenylene sulfone phenylene ethynylene) (PSESO₂E) were synthesized from bis(4‐ethynylphenyl)sulfide, bis(4‐ethynylphenyl)sulfone, and methylphenyl dichlorosilane. Poly(silylene ethynylene phenylene sulfoxide phenylene ethynylene) (PSESOE) was synthesized by the oxidation of PSESE. The structures and properties of these resins were characterized and the mechanical properties of the T300 reinforced composites were tested. The results show that the novel S‐PSA resins have excellent heat resistance and good mechanical properties, and could be used as resin matrices for high‐performance composites in high‐tech fields. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2324–2332     

Interfacial effect on confined crystallization of poly(ethylene oxide)/silica composites

The impact of nanoconfinement introduced by nanoparticles on polymer crystallization has attracted extensive attention because it plays an important role in the ultimate properties of polymer nanocomposites. In this study, interfacial and spatial confinement effects of silica (SiO₂) nanoparticles on the crystallization behaviors of poly(ethylene oxide) (PEO)/SiO₂ composites were systematically investigated by changing the size and concentration of SiO₂ in PEO matrix. The composites with high silica loadings exhibit two crystallization peaks of PEO as determined by differential scanning calorimetry. The first peak at 7–43 °C is related to the bulk PEO, while the second peak at ?20 to ?30 °C is attributed to the restricted PEO segments. Three‐layer (amorphous, interfacial, and bulk) model is proposed to interpret the confined crystallization of PEO/SiO₂ composites, which is supported by the results of thermogravimetric analysis and solid‐state ¹H nuclear magnetic resonance. In amorphous layer, most PEO segments are directly adsorbed on SiO₂ surface via hydrogen bonding. The interfacial PEO layer, which is nonuniform, is composed of crystallizable loops and tails extending from amorphous layer. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 414–423     

Polypropene product innovation by reactor granule technology

Continuous fine tuning of both chemistry and architecture of heterogeneous, isospecific MgCl₂/TiCl₄ catalyst systems for propene polymerization has led to a significant improvement in their performances in terms of activity, stereoselectivity, and capability to control both molecular parameters and morphology of the resulting polymers. As a result, a number of improved/innovative propene‐based products has recently been developed that clearly outperform the previously available materials. In particular, a family of reactor‐grade polymers has been synthesized including homopolymers and heterophasic copolymers offering, respectively, an unprecedented relationship between fluidity and stiffness and between stiffness and impact strenght, and supersoft polypropene alloys that could not have been achieved even via mechanical blending.     

Copolymerization of vinylcyclohexane with ethene and propene using zirconocene catalysts

Vinylcyclohexane (VCH) was copolymerized with ethene and propene using methylaluminoxane‐activated metallocene catalysts. The catalyst precursor for the ethene copolymerization was rac‐ethylenebis(indenyl)ZrCl₂ ( 1 ). Propene copolymerizations were further studied with C_s‐symmetric isopropylidene(cyclopentadienyl)(fluorenyl)ZrCl₂ ( 2 ), C₁‐symmetric ethylene(1‐indenyl‐2‐phenyl‐2‐fluorenyl)ZrCl₂ ( 3 ), and “meso”‐dimethylsilyl[3‐benzylindenyl)(2‐methylbenz[e]indenyl)]ZrCl₂ ( 4 ). Catalyst 1 produced a random ethene–VCH copolymer with very high activity and moderate VCH incorporation. The highest comonomer content in the copolymer was 3.5 mol %. Catalysts 1 and 4 produced poly(propene‐co‐vinylcyclohexane) with moderate to good activities [up to 4900 and 15,400 kg of polymer/(mol of catalyst × h) for 1 and 4 , respectively] under similar reaction conditions but with fairly low comonomer contents (up to 1.0 and 2.0% for 1 and 4 , respectively). Catalysts 2 and 3 , both bearing a fluorenyl moiety, gave propene–VCH copolymers with only negligible amounts of the comonomer. The homopolymerization of VCH was performed with 1 as a reference, and low‐molar‐mass isotactic polyvinylcyclohexane with a low activity was obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6569–6574, 2006     

Enhanced dielectric performance and energy storage of PVDF‐HFP‐based composites induced by surface charged Al2O3

In order to enhance dielectric properties and energy storage density of poly(vinylidene fluoride‐hexafluoro propylene) (PVDF‐HFP), surface charged gas‐phase Al₂O₃ nanoparticles (GP‐Al₂O₃, with positive surface charges, ε’ ≈ 10) are selected as fillers to fabricate PVDF‐HFP‐based composites via simple physical blending and hot‐molding techniques. The results show that GP‐Al₂O₃ are dispersed homogeneously in the PVDF‐HFP matrix and the existence of nanoscale interface layer (matrix‐filler) is investigated by SAXS. The dielectric constant of the composites filled with 10 wt % GP‐Al₂O₃ is 100.5 at 1 Hz, which is 5.6 times higher than that of pure PVDF‐HFP. The maximum energy storage density of the composite is 4.06 J cm^?3 at an electrical field of 900 kV mm^?1 with GP‐Al₂O₃ content of 1 wt %. Experimental results show that GP‐Al₂O₃ could induce uniform fillers’ distribution and increase the concentration of electroactive β‐phase as well as enhance interfacial polarization in the matrix, which resulted in enhancements of dielectric constant and energy storage density of the PVDF‐HFP composites. This work demonstrates that surface charged inorganic‐oxide nanoparticles exhibit promising potential in fabricating ferroelectric polymer composites with relatively high dielectric constant and energy storage. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 574–583