Enhanced dielectric and ferroelectric properties induced by Ag @ Pb(Zr,Ti)O3 in poly(vinyl alcohol) matrix composites: A solution casting approach

The present research work focused on the dielectric and electrical properties of silver (Ag) doped Pb(Zr,Ti)O₃ (PZT) particles embedded in a matrix of poly(vinyl alcohol) (PVA) via solution casting technique. The structural analysis confirmed the presence of Ag particles and the microstructural study revealed that both Ag and PZT particles were successfully homogenized over the polymer matrix. The Ag–PZT–PVA composites showed enhanced dielectric properties over a wide range of frequency and the dielectric constant value of such composites was significantly increased to 366 (100 Hz) at 1.1 wt % filler loading. The percolation threshold of the Ag–PZT–PVA composites was found to be 0.9 wt %. The experimental result well fitted to the percolation theory. The enhancement of dielectric constant of the resulting composite systems might be attributed to the increment of conductivity of the interlayer between PZT and PVA due to the presence of Ag particles, which improved the space charge polarization and Maxwell–Wagner–Sillars (MWS) polarization effects. Furthermore, the remnant polarization of the unpoled Ag–PZT–PVA composites (2P_r ～1.48 µC/cm² for 1.1.wt % of Ag–PZT) has also improved, which is favorable for enhanced ferroelectric properties of the composites. The present findings of the composites might be exploited in the potential application of high performance energy storage devices. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45583.     

Preparation and properties of β‐phase graphene oxide/PVDF composite films

We report preparation of graphene oxide (GO) from expanded graphite (EG) via a modified Hummers method. GO/PVDF composites films were obtained using solvent N, N‐Dimethylformamide (DMF) and cosolvent comprising deionized water/DMF combination. X‐ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) analyses revealed that the main crystal structure of the composite films is β‐phase, and use cosolvent method tends to favor the formation of β‐phase. Scanning electron microscopy (SEM) was used to investigate the microstructure of composite films. Storage modulus and loss modulus were measured by Dynamic mechanical analysis (DMA). Broadband dielectric spectrum tests showed an increase in the dielectric constant of the GO/PVDF composite films with the rising content of GO, and by cosolvent method could improve the dielectric constant while reducing the dielectric loss. Our method that uses GO as an additive and deionized water/DMF as the cosolvent provides a promising and low‐cost pathway to obtain high dielectric materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41577.     

COOHMWCNTs‐induced BiFeO3‐poly(vinylidene fluoride) (PVDF) composites with enhanced dielectric and ferroelectric properties

In this work, flexible three phase composite films were prepared with surface functionalized multi‐walled carbon nanotubes (f‐MWCNTs) and bismuth ferrite (BiFeO₃;BFO) particles embedded into the poly(vinylidene fluoride) (PVDF) matrix via solution casting technique. The properties and the microstructure of prepared composites were investigated using an impedance analyzer and field emission scanning electron microscope. The micro‐structural study showed that the f‐MWCNTs and BFO particles were dispersed homogeneously within the PVDF matrix, nicely seated on the floor of the f‐MWCNTs separately. The dielectric measurement result shows that the resultant composites with excellent dielectric constant (≈96) and relatively lower dielectric loss (<0.23 at 100 Hz). Furthermore, the percolation theory is explored to explain the dielectric properties of the resultant composites. It says that the percolation threshold of f_MWCNTs = 0.9 wt % and the enhancement of the dielectric constant of the composite was also discussed. In addition, the remnant polarization of the un‐poled PVDF‐BFO‐f‐MWCNTs composites (2P_r ～1.34 µC/cm² for 1.1 wt % of f‐MWCNTs) is also improved. These three phase composites provide a new insight to fabricate flexible and enhanced dielectric properties as a promising application in modern electrical and electronic devices. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46002.     

Formation and characterization of perfluorocyclobutyl polymer thin films

Perfluorocyclobutyl (PFCB) polymers are a new class of materials that show promise as selective layer materials in the development of composite membranes for gas separations, such as carbon dioxide/methane (α_{pure gas} = 38.6) and oxygen/nitrogen (α_{pure gas} = 4.8) separations. In many of the flat sheet applications, a thin film of the selective layer that is free of major defects must be coated onto a support membrane. A focus of this study was to elucidate the impacts of solvents, polymer concentration, and dip‐coating withdrawal speed on PFCB thin film thickness and uniformity. An extension was proposed to the Landau–Levich model to estimate the polymer film thickness. The results show that the extended model fits the thickness‐withdrawal speed data well above about 55 mm/min, but, at lower withdrawal speeds, the data deviated from the model. This deviation could be explained by the phenomenon of polymer surface excess. Static surface excesses of polymer solutions were estimated by applying the Gibbs adsorption equation using measured surface tension data. Prepared films were characterized by ellipsometry. Refractive index was found to increase with decreasing film thickness below about 50 nm, indicating densification of ultrathin films prepared from PFCB solutions below the overlap concentration. Atomic force microscopy was used to characterize surface morphologies. Films prepared from tetrahydrofuran and chloroform yielded uniform nanolayers. However, films prepared using acetone as solvent yielded a partial dewetting pattern, which could be explained by a surface depletion layer of pure solvent between the bulk PFCB/acetone solution and the substrate. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Characteristic analysis of biaxially stretched PVDF thin films

By use of biaxial stretching process of poly(vinylidene fluoride) fabrication to gain high piezoelectricity is the focus in this article. The influence of different stretch ratio and temperature are investigated and compared to uniaxial stretching process. The Fourier transform infrared spectroscopy and X‐ray diffraction are used to observe the β‐phase fraction and the degree of crystallinity. The piezoelectric coefficients (d₃₃, d₃₁) and the sensitivity are also measured. All the above characteristic examinations show the same consequences that equi‐biaxial stretching process employed with same stretch ratio in both axial directions of poly(vinylidene fluoride) fabrication is the focus in this article. And heating temperature would have adequate piezoelectricity approximate to uniaxial stretching. In observation of surface morphology by using scanning electron microscopy, uniformity in biaxial direction is gained. However, biaxial stretching with higher stretch ratio of R = 4 × 4 would produce porosity and crack. Via atomic force microscopy, biaxial stretching with higher stretch ratio attains better surface chain orientation and smoothness. To sum up, the biaxial stretching approach has the advantage of low stretch ratio requirement to preserve good fabrication quality. Set up with stretch ratio in‐between R = 3 × 3 and R = 4 × 4 at 80 °C is suggested to use in biaxial stretching. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46677.     

Polymeric nanocapsules containing methylcyclohexane for improving thermally induced debonding of thin adhesive films

The thin adhesive film with tunable interfacial adhesion can be applied in a broad range of display applications, from optically clear films to flexible devices. We have fabricated adhesive films including evaporable polymeric nanocapsules which can form thermally induced bubble gaps at the interface. These nanocapsules consisted of a poly(methyl methacrylate) core and a polyethyleneimine shell, and were impregnated with methylcyclohexane as a vaporization material. The evaporated core materials facilitated the desorption of thin adhesive film through bubble formation on the adhesive interface after thermal treatment, resulting in improved detachment of the adhesive layer. The optimization of the bubble gaps was performed to adjust the adhesive strength by varying the duration and temperature of thermal treatment, as well as the quenching temperature. The evaporable adhesive film with nanocapsule concentration of 1.0 wt % resulted in high transmittance of 94.9%, with the best adhesive strength reduction of 57.6% obtained after thermal treatment. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46586.     

Polarization and space charge performance in PVDF with MPB composition BCZT doped composite films

The morphotropic phase boundary composition 47(Ba_0.7Ca_0.3)TiO₃–0.53Ba(Zr_0.2Ti_0.8)O₃ (calcium barium zirconate titanate, BCZT) were doped in poly(vinylidene fluoride) matrix by solution casting method. The effect of BCZT particles on polarization characteristics of composite films were investigated through dielectric spectra, hysteresis, and thermally stimulated discharge current measurements. It reveals that relative dielectric constant, remnant polarization, and energy storage density gradually increase and reach the maximum value with 39 at 100 Hz, 1.17 μC/cm², and 3.69 J/cm³ at the concentration of 20 vol % BCZT. The Gaussian method was employed to decompose thermally stimulated discharge current composite peaks and an approximate model was used to analyze the activation energy levels of these films. The results indicated that the introduction of BCZT is effective for the charge carrier traps and activation energy distribution in the relaxation process of composite films. The decreased molecular movements, and increased interfaces formed between the BCZT grains and the poly(vinylidene fluoride) matrix may be responsible for these performances. And a new relaxation peak appeared at about 370 K in composites when BCZT concentration exceeded 20 vol %, which was considered to be caused by the ferroelectric‐paraelectric phase transition of BCZT. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45362.     

Hydrogen-bonding assembly of heteropolyacid and poly(vinyl alcohol) for strong,flexible, and transparent UV-protective films

Although many preparation approaches have been developed, it remains a huge challenge to achieve ultraviolet (UV)-protection films that combine high transparency, excellent UV-shielding, and mechanical properties. Herein, we demonstrate a facile and eco-friendly process for fabricating strong, flexible, and transparent UV-protective poly(vinyl alcohol) (PVA) films by exploiting silicomolybdic acid (SiMoA) as UV absorber and reinforcing phase. Fourier-transform infrared analysis confirms the formation of strong hydrogen-bonding interactions between PVA and SiMoA. The glass-transition temperature, mechanical properties, and UV-shielding stability of the UV-protective PVA composite films obviously increase with increasing the content of SiMoA. By incorporation of only 2 wt % SiMoA, the UV-protective PVA composite film can block more than 90% of UV light in the entire UV regions and retain high visible light transparency (up to 95%). Simultaneously, the UV-protective PVA composite film presents excellent mechanical properties with a tensile strength of 65.2 MPa and an elongation at break of 172.6%, which are 72.0 and 69.5% higher than that of pristine PVA films. This work provides a simple but effective approach for creating strong, flexible, and transparent UV-blocking polymeric materials via hydrogen-bonding assembly, which are expected to have wide application prospects in UV-protection field. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48813.     

Structural,ferroelectric, and optical properties of Pr-NBT-xCTO relaxor ferroelectric thin films

Sol-gel method was used to prepare the Pr³⁺ ions-doped (1-x)Na_0.5Bi_0.5TiO₃-xCaTiO₃ (Pr-NBT-xCTO) (x?=?0, 0.04, 0.06, 0.08, 0.1, 0.12, and 0.16) thin films on Pt/Ti/SiO₂/Si and fused silicon substrates. The structure phase of thin films was evolving from rhombohedral (R3c) to orthorhombic (Pnma) with increasing CTO content. Owing to the morphotropic phase boundary (MPB), the improved ferroelectric and dielectric properties were obtained at x?=?0.06–0.1. The MPB was formed from the concomitant phase of rhombohedral (R3c) and orthorhombic (Pnma). The Pr-NBT-0.08CTO thin film showed the best ferroelectric and dielectric properties, as well as strong relaxor behavior (the diffusion factor is γ?=?1.79). In addition, all the films exhibited strong red emission as excited by UV light, and wide optical band-gap (3.44–3.47?eV), which might be influenced by grain size and structural variation. Our results indicate that Pr-NBT-xCTO thin films may have potential applications in ferroelectric-luminescence multifunctional optoelectronic devices.     

Fabrication of highly monodisperse CeO2@poly(methyl silsesquioxane) microspheres and their application in UV‐shielding films

Highly monodisperse CeO₂@poly(methyl silsesquioxane) (PMSQ) microspheres were successfully prepared by a facile chemical precipitation technique. The structures and properties of CeO₂@PMSQ were analyzed by Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy techniques. We confirmed that the PMSQ microspheres were uniformly coated by CeO₂ nanoparticles, with about an 8 nm crystallite diameter. Then, CeO₂@PMSQ was incorporated into a poly(vinyl alcohol) (PVA) matrix to fabricate PVA/CeO₂@PMSQ composite films by the casting of homogeneous solutions. The thermal and optical properties of the composite films were investigated by thermogravimetric analysis and UV–visible spectroscopy. The results show the high UV‐shielding efficiency of the composites: for a film containing 2.5 wt % CeO₂@PMSQ microspheres, about 80% UV light at wavelengths between 200 and 360 nm was absorbed, whereas the optical transparency in the visible region still remained very high. The addition of CeO2@PMSQ microspheres improved the thermal stability of the PVA films. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45065.     

Effect of block copolymer containing ionic liquid moiety on interfacial polarization in PLA/PCL blends

Compared with poly(?‐caprolactone)‐b‐poly(ethylene glycol) block copolymer (BC), a systematic study of the effect of the concentration of the compatibilizer, poly(?‐caprolactone)‐b‐poly(ethylene glycol) BC containing ionic liquid moiety (BCIL), on the interfacial properties of a phase separating blend of poly(l ‐lactic acid)/poly(?‐caprolactone) (PLA/PCL) was performed. BCIL copolymer as a compatibilizer for immiscible PLA/PCL blend can reinforce the interactions between the two polymeric phases by the IL electrostatic interaction at interphase, and the particle size of PCL decreases because of interfacial reinforced‐compatibilization of IL moiety. Ion mobility of IL moiety at interphase and PCL phase for PLA/PCL/BCIL blend can induce interfacial blocking of charge carriers, and IL moiety segregating mainly at the interface can decrease the relaxation rate and increase the dielectric strength of interfacial polarization. Our results provide a methodology to characterize and tune the morphology and blocking of charge carriers with the aim of tailoring the dielectric interfacial properties of blends. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46161.     

Dual xanthan gum/poly(vinyl acetate) or alkyl‐functionalized poly(vinyl alcohol) films as models for advanced coatings

Double‐layer films, prepared by casting films of xanthan gum (XG), and subsequently poly(vinyl acetate) (PVAc) onto the former, are reported. The resulting XG/PVAc films provide high protection as coatings to a bleaching agent, 6‐(phthalimido)peroxyhexanoic acid, in liquid detergents, due to the combined roles of the outer PVAc layer as water‐barrier and the inner XG layer as water‐sink. PVAc films cast from either homogeneous solutions in acetone or aqueous dispersions were used; the stabilities exerted by the former were markedly superior. For comparison, poly(vinyl alcohol) (PVA) was also used as outer wall material, resulting in much lower protection due to its hydrophilicity. Functionalization (silylation or acetalyzation) of PVA films is also suggested as a means to decrease the surface hydrophilicity of the material. The dual hydrophilic–hydrophobic films presented herein serve as models for advanced coatings in (micro)encapsulation processes, owing to the straightforward study of their morphology and transport phenomena. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40870.     

High dielectric constant epoxy nanocomposites containing ZnO quantum dots decorated carbon nanotube

Zinc oxide (ZnO) quantum dot (QD) decorated multi-walled carbon nanotube (MWCNT) hybrid was utilized in the fabrication of high dielectric constant epoxy nanocomposites. Because of the shielding effect of ZnO QD, the well-dispersed epoxy hybrid nanocomposites exhibit frequency insensitive high dielectric constant as well as greatly reduced dielectric loss. With only 1.5 wt% of MWCNT addition, the epoxy/MWCNT-ZnO nanocomposite possesses dielectric constant as high as 31 and dielectric loss as low as 0.01 at 1 kHz. In addition, the epoxy nanocomposite exhibits greatly enhanced tensile properties. The role of ZnO QD decorated MWCNT in the preparation and property improvement of multi-functional polymer nanocomposites is discussed.     

Synthesis and ferroelectric investigations of poly(vinylidene fluoride‐co‐hexafluoropropylene)‐Mg(NO3)2 films

The free‐standing, flexible, and ferroelectric films of poly(vinylidenefluoride‐co‐hexafluoropropylene) [P(VDF‐HFP)] were prepared by spin coating method. The ferroelectric phase of the films was enhanced by adding magnesium nitrate Mg(NO₃)₂ in different wt % as the additive during the film fabrication. The effects on the structural, compositional, morphological, ferroelectric, dielectric, and leakage current behaviors of the films due to the addition of salt were analyzed. Based on the X‐ray diffraction (XRD) patterns and Fourier Transform Infrared (FTIR) spectra, it is confirmed that the addition of Mg(NO₃)₂ promotes the electroactive β phase that induces the ferroelectric property. The fiber‐like topography of the films exhibits a nodule‐like structure, and the roughness of the films increases by the addition of Mg(NO₃)₂. The ferroelectric studies show the higher polarization values for the composite films than that of the plain P(VDF‐HFP) film. The Piezo‐response force microscope images also confirm the domain switching behavior of the samples. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44008.     

Deformation-induced bonding of polymer films below the glass transition temperature

Bonding between polymers through interdiffusion of macromolecules is a well-known mechanism of polymer adhesion. A new polymer bonding mechanism in the solid state, taking place at ambient temperatures well below the glass transition value (T_g), has been recently reported; in this mechanism, bulk plastic compression of polymer films held in contact led to adhesion over timescales of the order of a fraction of a second. In this study, we prepared various blends of plasticized polymer films with desirable ductility from amorphous and semicrystalline powders of hydroxypropyl methylcellulose and polyvinyl alcohol derivatives; then, we observed the bonding of these polymers at ambient temperatures, up to 80 K below T_g, purely through mechanical deformation. The deformation-induced bonding of the polymer films studied in this work led to interfacial fracture toughnesses in the range of 1.0–21.0 J/m² when bulk plastic strains between 3% and 30% were imposed across the films. Scanning electron microscopy observation of the debonded interfaces also confirmed that bonding was caused by deformation-induced macromolecular mobilization and interpenetration. These results expand the range of applicability of sub-T_g, solid-state, deformation-induced bonding processes.     

Encapsulated graphenes through ultrasonically initiated in situ polymerization: A route to high dielectric permittivity,low loss materials with low percolation threshold

To improve dielectric performance of polystyrene (PS) without sacrificing its flexibility and processability, PS encapsulated graphene sheets (PSG) were synthesized by ultrasonically initiated in situ polymerization and was incorporated into PS matrix as fillers. The structure and properties of the obtained PSG were investigated by Fourier transform infrared, transmission electron microscopy, scanning electron microscope, and atom force microscopies. The results showed that the in situ formed PS layers attached on the surface of graphene and there were strong interfacial interactions between them. In virtue of this core‐shell architecture and intrinsic properties of PSG, PS/PSG nanocomposites exhibited improved dielectric performance and a typical percolation transition with very low percolation threshold of 0.2 wt %. Compared with pure PS, significantly increased dielectric permittivity and a low loss tangent were observed for the composites. These composites might be potential flexible dielectric materials for use in high‐frequency capacitors with low loss. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44628.     

Friction‐induced electroactive β polymorph of poly(vinylidene fluoride)

Poly(vinylidene fluoride) (PVDF) has been widely used in electric devices due to electroactive β polymorph. In this article, we probe the formation of β phase under friction by spectroscopy and thermal analysis. During continuous friction, entire sliding of PVDF is identified with two regimes, i.e., running‐in and steady‐state. At initial running‐in period, friction surfaces are dominated by plastic strain, which leads to striking formation of β phase from α polymorph (α→β). Subsequently, melting‐flow domains almost cover friction surfaces at steady‐state. Thus, formation of β crystal is correspondingly induced by shear crystallization. Nevertheless, β‐crystal content at steady‐state is lower than that at running‐in. With sliding proceeding, moreover, β‐crystal content exhibits a gradually decreasing tendency, attributed to rising surface temperature. Besides, the friction‐induced β phase is further confirmed by evaluation of wear debris. Overall, friction plays a crucial role as to the formation of β phase. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46395.     

Selective localization of organophilic clay Cloisite 30B in biodegradable poly(lactic acid)/poly(3-hydroxybutyrate) blends

The influence of selective localization of the nanoclay Cloisite 30B on the morphological, thermal and thermo-mechanical properties of biodegradable poly(lactic acid)/poly(hydroxybutyrate) blends was evaluated in this work. For this, different compounds were obtained by adding the filler in a single phase or mixed with the two matrices simultaneously by melting processing. The simultaneous processing leads to a better dispersion of nanoparticles on the blend and generates a more homogeneous polymer interface, but the properties do not increase in relation to those that were processed in separate steps. For the blends obtained in separated steps, the polymeric domains and, consequently, the superficial tension between phases are better controlled by a nanolayer. Thus, the results obtained in this work indicate that better control of the polymeric interfaces can generate a more significant effect on the thermal and thermo-mechanical properties of nanostructured blends than just a good dispersion of the fillers.     

Insight of electrical behavior in ferroelectric‐semiconductor polymer nanocomposite films of PVDF/ZnSe and PVDF/Cu:ZnSe

Nanocomposite thin films (NCTF) of low‐dimensional ZnSe and copper doped ZnSe integrated poly(vinylidene fluoride) (PVDF) polymer were developed via simple solution casting method. Herein, ZnSe and Cu:ZnSe nanoparticles were synthesized through the chemical reduction technique. The obtained low‐dimensional nanoparticles and NCTFs were characterized by XRD, SEM/EDS, TEM, and FTIR analysis. Room temperature dielectric and ferroelectric characteristics of PVDF/ZnSe flexible NCTF exhibited superior dielectric and ferroelectric behavior with a high coercive field of 15.6 V. Whereas, the dielectric and ferroelectric characteristics were greatly diminished in the PVDF/Cu:ZnSe flexible NCTF was due to the conducting behavior of copper ions at the interface of the polymer network. These results indicated that the PVDF/ZnSe flexible NCTF will be a potential candidate for advanced electrical applications and device fabrication. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44983.     

Experimental and theoretical dielectric studies of PVDF/PZT nanocomposite thin films

Poly(vinylidene fluoride)/lead zirconate titanate nanocomposite thin films (PVDF/PZT-NPs) were successfully prepared by mixing fine Pb(Zr_0.52,Ti_0.48)O₃ nanoparticles (PZT-NPs) into a PVDF solution under ultrasonication. The mixture was spin coated onto glass substrate and then cured at 110 °C. X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) were used to characterize the structure and properties of the obtained thin-film nanocomposites. The dielectric properties of the PVDF/PZT-NPs were analyzed in detail with respect to frequency. In comparison with pure poly (vinylidene fluoride), the dielectric constant of the nanocomposite (15 vol.% PZT-NPs) was significantly increased, whereas the loss tangent was unchanged in the frequency range of 100 Hz to 30 MHz. The nanocomposites exhibited good dielectric stability over a wide frequency range. Different theoretical approaches were employed to predict the effective dielectric constants of the thin film nanocomposite systems, and the estimated results were compared with the experimental data.