Influence of ferrite nanoparticle type and content on the crystallization kinetics and electroactive phase nucleation of poly(vinylidene fluoride)

This work reports on the nucleation of the β-phase of poly(vinylidene fluoride) (PVDF) by incorporating CoFe(2)O(4) and NiFe(2)O(4) nanoparticles, leading in this way to the preparation of magnetoelectric composites. The fraction of filler nanoparticles needed to produce the same β- to α-phase ratio in crystallized PVDF is 1 order of magnitude lower in the cobalt ferrite nanoparticles. The interaction between nanoparticles and PVDF chains induce the all-trans conformation in PVDF segments, and this structure then propagates in crystal growth. The nucleation kinetics is enhanced by the presence of nanoparticles, as corroborated by the increasing number of spherulites with increasing nanoparticle content and by the variations of the Avrami's exponent. Further, the decrease of the crystalline fraction of PVDF with increasing nanoparticle content indicates that an important fraction of polymer chains are confined in interphases with the filler particle.     

Simple synthesis of palladium nanoparticles, β-phase formation, and the control of chain and dipole orientations in palladium-doped poly(vinylidene fluoride) thin films

Palladium nanoparticles (Pd-NP's) are prepared by a simple one-step procedure when poly(vinylidene fluoride) (PVDF) is used as a polymer stabilizer. High-quality Pd-NP-doped PVDF thin films are fabricated where the heat-controlled spin-coating technique is adopted. The effect of Pd-NP's on the crystal modifications and lamellae orientation in PVDF films is investigated using Fourier transform infrared-grazing incidence reflection absorption spectroscopy. The electroactive β phase and edge-on crystalline lamellae are found to be formed preferentially in Pd-NP-doped PVDF films. As a result, Pd-NP-doped PVDF ultrathin films gave a very good discernible contrast between the written and erased data bits, which suggests that they can be used as a scanning-probe-microscopy-based ferroelectric memory device or a ferroelectric gate field-effect transistor memory device in the future.     

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     

Effect of poly(ethylene glycol) on the dielectric properties of poly(vinylidene fluoride)/BiFeO<Subscript>3</Subscript>/poly(ethylene glycol) composite films for electronic applications

In the present work a series of poly(vinylidene fluoride)/BiFeO₃/poly(ethylene glycol) composite films were prepared by solvent casting method with poly(vinylidene fluoride) as polymer matrix, bismuth ferrite as ceramic filler and poly(ethylene glycol) as binding agent as well as enhancer. The structural analysis of the composite films by X-ray diffraction confirms that the composites have a distorted rhombohedral structure. The micro-structural analysis shows that the use of poly(ethylene glycol)in the composite films enhances the homogeneity as well as compatibility of BiFeO₃ particles within the poly(vinylidene fluoride) matrix. The dielectric and electrical study done by impedance analyzer reveals that with an increase in poly(ethylene glycol) concentration, there is a subsequent increase in dielectric constant as well as AC electrical conductivity. Finally, the ferroelectric behavior of the composite confirms that the ferroelectric properties of the composites are enhanced by the addition of BiFeO₃ with an increase in poly(ethylene glycol) concentrations. These preliminary results give an idea for possible applications of this type of composites in the field of electronic applications.     

Preparation of size-controlled, highly populated, stable, and nearly monodispersed Ag nanoparticles in an organic medium from a simple interfacial redox process using a conducting polymer

The reducing property of an organically soluble conducting polymer (poly(o-methoxyaniline), POMA) is used to prepare monodisperse, size-controlled, highly populated, and highly stable silver nanoparticles in an organic medium through an interfacial redox process with an aqueous AgNO3 solution. The transition of emeraldine base (EB) to the pernigraniline base (PB) form of POMA occurs during nanoparticle formation, and the nitrogen atoms of POMA(PB) stabilize Ag nanoparticles by coordination to the adsorbed Ag(+) on the nanoparticle surface. The conductivity of the nanocomposite is on the order of 10(-11) S/cm, indicating that no doping of POMA occurs under the preparation conditions. The nanoparticles are free of excess oxidant and external stabilizer particles. The POMA (EB) concentration tailors the size of nanoparticles, and at its higher concentration (0.01% POMA with 0.01 N AgNO3), very dense Ag nanoparticles (6 x 10(15) particles/m(2)) of almost uniform size and shape are produced. The rate constant and Avrami exponent values of the nanoparticle formation are measured from the time-dependent UV-vis spectra using the Avrami equation. The Avrami exponent (n) values are close to 1, indicating 2D athermal nucleation with the circular shape of the nuclei having diffusion-controlled growth. The rate constant values are almost independent of AgNO3 concentration but are strongly dependent on POMA concentration. The higher rate constant with increasing POMA(EB) concentration has been attributed for the lowering of nanoparticle size due to increased nucleation density.     

Nanoprecipitation for ultrafiltration membranes

Polymer nanoparticles are readily obtainable by rapidly mixing a dilute polymer solution and a poor solvent. The nanoparticles of poly(vinylphenol), poly(vinylidene fluoride), and emeraldine base polyaniline prepared by nanoprecipitation become sticky when their diameters decrease down to a few tens of nanometers, and such polymer nanoparticles spontaneously assemble into rigid fractal networks of the nanoparticles. By filtering these fibrous nanoparticle networks on a microfiltration membrane, ultrafiltration membranes with a thin free‐standing filter cake layer made of nanoparticles are obtainable. The nanoparticle membranes are robust at least up to the applied pressure of 2 MPa and can separate 99% of 10 nm Au nanoparticles from the aqueous dispersion at the flux of more than 1835 L m^?2 h^?1 even at very low pressure difference of 0.08 MPa. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 615–620     

Crystallization behavior and electroactive properties of PVDF,P(VDF-TrFE) and their blend films

PVDF, poly(vinylidene fluoride), as a semi-crystalline polymer, has interesting electroactive properties but usual melt and solution processing techniques result in its thermodynamically favored non-polar α-phase. By comparison, poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE), PT for short, directly crystallizes in the polar β-phase under the same conditions as PVDF. In this study, blend thin films comprising PVDF and P(VDF-TrFE) were prepared by solvent casting method. The difference in the crystallization behavior is comprehensively investigated between the polymers: PVDF, P(VDF-TrFE), and the resulting blend films. It is found that replacement of the fluoride atom in TrFE monomer induces a strong steric hindrance that may alter the crystallization process to become more favorable for nucleation of the PVDF β-phase. To figure out the effect of TrFE content on the crystallization behavior and electroactive properties, films with different blend ratios of PVDF and P(VDF-TrFE) were prepared. We found that the PVDF films exhibit higher crystallization activation energy (ΔE) as PT content increases. The atomic force microscopy (AFM) in the piezoresponse force microscopy (PFM) mode illustrated that P5T5 films with equal contents of PVDF and P(VDF-TrFE) induced the highest d₃₃ values.     

In Situ Formation of a Uniform Distribution of Silver Nanoparticles in PVDF: Kinetics of Formation and Resulting Properties

Hybrid organic/silver nanoparticle thermoplastic films have been prepared using a single step process where the silver nanoparticles were formed during a cure cycle applied to the film. Figure 1 is a TEM demonstrating the ability of our technique to produce silver nanoparticles in the semi-crystalline polymer Poly(vinylidene fluoride) (PVDF). The current laboratory focus is on characterizing kinetics and particularly the diameter growth and inter-particle distance as a function of time and temperature using the techniques of small-angle X-ray scattering (SAXS), differential scanning calorimetry (DSC), and X-ray diffraction (XRD). Using the Beaucage model, the SAXS data demonstrates that the particle size reaches equilibrium after approximately 70 minutes of curing at 240 °C. This result is also observed in the XRD results where the half width of the diffraction peaks becomes smaller quickly during the initial hour. In a parallel experiment using DSC, the exothermic heat flow increases rapidly during the first hour but does not reach completion until almost 150 minutes.     

Effect of MMT,SiO2, CaCO3, and PTFE nanoparticles on the morphology and crystallization of poly(vinylidene fluoride)

The crystallization and melting behaviors of poly (vinylidene fluoride) (PVDF) with small amount of nanoparticles (1 wt %), such as montmorillonite (MMT), SiO₂, CaCO₃, or polytetrafluoroethylene (PTFE), directly prepared by melt‐mixing method were investigated by scanning electron microscopy (SEM), polarizing optical microscopy, Fourier transform infrared spectroscopy, wide angle X‐ray diffraction (WAXD), and differential scanning calorimetry (DSC). The nanoparticle structure and the interactions between PVDF molecule and nanoparticle surface predominated the crystallization behavior and morphology of the PVDF. Small amount addition of these four types of nanoparticles would not affect the original crystalline phase obtained in the neat PVDF sample (α phase), but accelerated the crystallization rate because of the nucleation effect. In these four blend systems, MMT or PTFE nanoparticles could be well applied for PVDF nanocomposite preparation because of stronger interactions between particle surface and PVDF molecules. The nucleation enhancement and the growth rate of the spherulites were decreased in the order SiO₂ > CaCO₃ > PTFE > MMT. The melting and recrystallization of PVDF was found in MMT addition sample, because of the special ways of ordering of the PVDF chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Correlation between rheological,electrical, and microstructure characteristics in polyethylene/aluminum nanocomposites

Polyethylene (PE)/aluminum (Al) nanocomposites with various filler contents were prepared by a solution compounding method. We investigated the influence of the surface modification of Al nanoparticles on the microstructure and physical properties of the nanocomposites. The silane coupling agent octyl‐trimethoxysilane was shown to significantly increase interfacial compatibility between the polymer phase and Al nanoparticles. Rheological percolation threshold values were determined by analyzing the improvement in storage modulus at low frequencies depending on the Al loadings. Lower percolation threshold values were obtained for the composites prepared with the original nanoparticles than those prepared with the silane‐modified Al nanoparticles. A strong correlation between the time and concentration dependences of dc conductivity and rheological properties was observed in the different nanocomposite systems. The rheological threshold of the composites is smaller than the percolation threshold of electrical conductivity for both of the nanocomposite systems. The difference in percolation threshold is understood in terms of the smaller particle–particle distance required for electrical conduction when compared with that required to impede polymer mobility. It was directly shown by SEM characterization that the nanoparticle surface modification yielded better filler dispersion, as is consistent with our rheological and electrical analysis. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2143–2154, 2008     

Extrusion of poly(vinylidene fluoride) recycled filaments: Effect of the processing cycles on the degree of crystallinity and electroactive phase content

This study analyses the possibility of reprocessing used poly(vinylidene fluoride), PVDF, maintaining the main properties critical for its use in piezoelectric sensor/actuator applications. The influence of multiple reprocessing cycles of PVDF on crystallinity and ß-phase content fundamental for its electroactive behaviour, was studied. Nine reprocessing cycles were completed and it was found that the material preserved the characteristics required for its use as piezoelectric polymer without significant degradation.     

Modeling interband transitions in silver nanoparticle-fluoropolymer composites

The interband transition contributions to the optical properties of silver nanoparticles in fluoropolymer matrices are investigated. For the materials in this study, nanoparticle synthesis within the existing polymer matrix is accomplished using an infusion process that consists of diffusing an organometallic precursor gas into the free volume of the fluoropolymer and decomposing the precursor followed by metal nanoparticle nucleation and growth. The resulting polymer matrix nanocomposite has optical properties that are dominated by the response of the nanoparticles owing to the broadbanded transparency of the fluoropolymer matrix. The optical properties of these composites are compared to Maxwell-Garnett and Mie theory with results indicating that interband transitions excited in the silver nanoparticles affect the optical absorption over a range of frequencies including the surface plasmon resonance. It is shown that calculations of the optical absorption spectrum using published data for the silver dielectric function do not accurately describe the measured material response and that a classical model for bound and free electron behavior can best be used to represent the dielectric function of silver.     

Preparation and Storage of Silver Nanoparticles in Aqueons Polymers

以水溶性聚合物为保护剂,采用化学还原法制备了银纳米粒子,分别利用透射电子显微镜、紫外可见光谱、同步光散射光谱等手段对其进行了表征,并探索了制备银纳米粒子的最佳实验条件。通过将银纳米粒子-聚合物溶液进行脱水,得到含有银纳米粒子的固态聚合物膜。将固态聚合物膜重新溶解于水,其水溶液的紫外可见光谱与脱水前的溶液进行了比较,发现两者性质并无明显差异。因此,将银纳米粒子分散固定在聚合物膜中是一种崭新而有效的银纳米粒子制备和存储方法。     

Dialysis Nanoprecipitation of Polystyrene Nanoparticles

Using a facile dialysis nanoprecipitation method, nanoparticles of several hundred nanometers have been successfully generated from a “traditional,” non‐biodegradable polymer, that is, polystyrene. The effect of initial polymer concentration inside the dialysis membrane, as well as the polymer/solvent system and the ionic strength (electrolyte concentration) of the dialysis solution, on nanoparticle size is examined. A nucleation‐aggregation mechanism has been provided to explain the observed trends. Furthermore, we determine the zeta potential as a function of ionic strength for the generated nanoparticles and show that anionic charging may be present in the system.     

Structure and properties of nanocomposites based on zinc sulfide and poly(vinylidene fluoride)

The structure and properties of nanocomposites based on zinc sulfide and poly(vinylidene fluoride) were studied. The nanocomposite material was prepared by the matrix isolation technique: ZnS nanoparticles are formed by chemical reactions in a poly(vinylidene fluoride) powder of particle size 0.5–1.0 μm.     

Electrochemical nucleation of gold nanoparticles in a polymer film at a liquid-liquid interface

Simultaneous nucleation of gold nanoparticles and polymerization of tyramine has been carried out at an immiscible electrolyte interface. By transferring the gold ion of tetraoctylammoniumtetracloroaurate (TOAAuCl(4)) from the organic to the aqueous phase, a fast homogeneous electron transfer from the tyramine monomer reduces the gold ion. Electropolymerization then proceeds, and gold nanoparticles form. The newly formed nanoparticles act as nucleation sites for the deposition of the oligomers/polymer (and possibly vice versa). This results in gold nanoparticles stabilized in a polytyramine matrix. The size of the nanoparticles is controlled by the concentration of oligomers/polymer in solution. The polymer nanoparticle composite film was analyzed with TEM, XPS, and AFM.     

Fabrication of highly porous poly (ɛ-caprolactone) fibers for novel tissue scaffold via water-bath electrospinning

A non-toxic route was used for the preparation of silver nanoparticles using tryptophan (Trp) as reducing/stabilizing agent in the presence of cetyltrimethyl ammonium bromide (CTAB). Role of water soluble neutral polymer poly(vinylpyrrolidone) (PVP) has been studied on the growth of yellow colour silver nanoparticle formation. The synthesized nanostructures were characterized by UV–Visible absorption spectroscopy, transmission electron microscopy (TEM) by observing the size and distribution of silver nanoparticles. As the reaction proceeded, particles grew up to about 10 and 20 nm in the presence and absence of PVP, respectively, as determined by TEM. The formed nanoparticles showed the highest absorption plasmon band at 425 nm. Rate of silver sol formation increases with the [Trp], [CTAB] and [PVP], reaching a limiting value and then decreases with the increase in concentrations of these reagents. It was observed that nanoparticles are spherical, aggregated and poly dispersed in the absence and presence of PVP, respectively. On the basis of kinetic data, a suitable mechanism is proposed and discussed for the silver sol formation.     

Submillimeter infrared spectroscopy of fluorinated polymers - phase transition study

Submillimeter infrared technique is used to study the phase transitions in poly(vinylidene fluoride) homopolymer and copolymers with trifluorethylene. During the phase transition form II to form I, induced by copolymerization, electrical or mechanical stresses, the spectra show an important increasing of the submillimeter absorption. This behavior is explained by changes of the polarizability at phase transition.     

Penetration of pores in membranes by plasma polymer forming species

Penetration of low‐temperature plasma polymer forming species through a microporous polycarbonate membrane was indicated by advancing contact angle measurement and scanning electron microscopoy of the membrane surface. No penetration of plasma polymer forming species was found in nylon and poly(vinylidene fluoride) membranes. This is attributed to the tortuous pore shapes of the nylon and poly‐(vinylidene fluoride) membranes compared to the straight cylindrical pore shape of the polycarbonate membrane.     

Water transport in aluminium oxide-poly(ethylene-co-butyl acrylate) nanocomposites

Polymer composites with metal oxide nanoparticles are emerging materials for use as insulation in electrical applications. However, the extensive interfacial surfaces and the presence of polar groups on the particle surfaces make these composites susceptible to water sorption. Water sorption kinetics were studied at 23 °C and different relative humidities (18–90%) for composites based on poly(ethylene-co-butyl acrylate) and aluminium oxide (?12 wt.%); the latter being in three different forms: uncoated and coated with either octyltriethoxysilane or aminopropyltriethoxysilane. The equilibrium water uptake increased linearly with increasing overall concentration of polar groups on the nanoparticle surfaces. Composites with well-dispersed nanoparticles showed Fickian diffusion (constant diffusivity and invariant boundary conditions) with a diffusivity that decreased with increasing filler content; the maximum factorial decrease in diffusivity was 300 with reference to that of the pristine polymer. This effect was most pronounced for composites with accessible polar groups on the particle surfaces, suggesting that water saturation of the composites is retarded by dual water sorption. Composites that contained a sizeable fraction of large nanoparticle agglomerates showed a two-stage sorption process: a rapid process associated with the saturation of the matrix phase and a slow diffusion process due to water sorption by the large nanoparticle agglomerates.