Processing Conditions and Aging Effect on the Morphology of PZT Electrospun Nanofibers, and Dielectric Properties of the Resulting 3–3 PZT/Polymer Composite

Lead zirconate titanate (PZT) nanofibers are obtained by electrospinning a sol–gel based solution and polyvinyl pyrrolidone (PVP) polymer, and by subsequent sintering of the electrospun precursor fibers. The average diameter of the precursor PZT/PVP green fibers has increased with the aging of the precursor solution along with an increase in the viscosity. Bead-free uniform green PZT/PVP fibers were collected at about an ∼230 nm average fiber diameter using a 28 wt% PVP ratio solution with a viscosity of 290 mPa. Shrinkage of 40% was recorded on the fiber diameter after sintering. The X-ray diffraction pattern of the annealed PZT fibers exhibits no preferred orientation and a perovskite phase. Preparation of 3–3 nanocomposites by the infusion of polyvinylester into the nanofiber mat facilitates successful handling of the fragile mats and enables measurements of the dielectric properties. The dielectric constant of the PZT/polyvinylester nanocomposite of about 10% fiber volume fraction was found to be fairly stable and vary from 72 to 62 within the measurement range. The dielectric loss of the composite is below 0.08 at low frequencies and reaches a stable value of 0.04 for most of the measured frequencies.     

Poly(lactic acid)/poly(vinyl pyrrolidone) membranes produced by solution blow spinning: Structure,thermal, spectroscopic,and microbial barrier properties

Submicrometric and nanometric poly(lactic acid)/poly(vinyl pyrrolidone) (PLA/PVP) fibrous membranes containing 0, 5, 10, 15, and 20 wt % PVP, with or without 20 wt % Copaiba oil (Copaifera sp.), were produced by solution blow spinning (SBS), using polymer injection rate of 120 μL min^?1, gas pressure of 2.4 kPa, working distance of 20 cm, and collector rotation of 200 rpm. The morphological, thermal, and spectroscopic properties of these membranes were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetry (TG), and Fourier transform infrared spectroscopy (FTIR). A method for the evaluation of membrane microbial barrier properties based on resazurin colorimetric method was proposed. Results showed that the addition of both PVP and Copaiba oil produced thicker fibers; otherwise, there was no effect on morphology. Thermal analyses (TG and DSC) indicated the immiscible nature of polymer blends produced, also confirmed by the spectroscopic studies. Antimicrobial barrier properties were related to the antimicrobial effect of Copaiba oil, combined with it hydrophobic nature. The hydrophilic nature of PVP favored degradation of fiber mats, impairing barrier property when higher concentrations of PVP were added. Results indicate that produced spun mats can potentially be used in applications such as wound dressing. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44802.     

Magnetic electrospun fluorescent polyvinylpyrrolidone nanocomposite fibers

Magnetic nanoparticles (MNPs) were synthesized from facile thermodecomposition of iron pentacarbonyl and the subsequent silica coating on the MNP surface was achieved via a modified Stöber process to obtain the core–shell composite structured particles (MNPs-SiO₂). MNPs-SiO₂ were then incorporated into polyvinylpyrrolidone (PVP) to form nanocomposite fibers via an electrospinning process with optimized operational parameters such as polymer concentration, applied electrical voltage, feed rate and tip-to-collector distance. All these parameters show an unusual effect on the produced fiber diameter. Contrary to the conventional observation, i.e., increasing the applied voltage and feed rate or decreasing the distance could increase the fiber diameter; a reduced average fiber diameter was observed in this study and could be explained from the stretching and contraction force balance within the fiber during electrospinning. The size of the resulting PVP fibers is correlated to the corresponding rheological behaviors of the PVP solutions with different concentrations. The MNPs-SiO₂/PVP nanocomposite fibers exhibit a similar thermal decomposition temperature (386.3 °C) as that (387.8 °C) of pure PVP. Meanwhile, unique fluorescent and magnetic properties have been incorporated simultaneously in the nanocomposite fibers with the addition of small amount of MNPs-SiO₂ nanoparticles.     

Significant thermal property and hydrogen bonding strength increase in poly(vinylphenol-co-vinylpyrrolidone) copolymer

A series of poly(vinylphenol-co-vinylpyrrolidone) (PVPh-co-PVP) copolymers were prepared by free radical copolymerization of acetoxystyrene with vinylpyrrolidone (PAS-co-PVP), followed by selective removal of the acetyl protective group. These copolymers were investigated by solid state nuclear magnetic resonance (NMR) and thermal gravimetric analyzer (TGA) to compare with previous results on differential scanning calorimetry (DSC) and Fourier-Transform infrared spectroscopy (FTIR) analyses. The spin-lattice relaxation time in the rotating frame (T_1ρ(H)) of the PVPh-co-PVP is greater than the corresponding PVPh/PVP blend, indicating that the polymer mobility is more restricted and high rigid character of the former. At the same time, the thermal decomposition temperature of homopolymer, copolymer and polymer blend is the order of PVPh-co-PVP copolymer>PVPh/PVP blend>pure PVP homopolymer>PAS-co-PVP copolymer and this order is consistent with previous studies on DSC, FTIR and NMR analyses. In order to understand the mechanism of significant glass transition temperature increase of the PVPh-co-PVP copolymer, the degree of hydrolysis was controlled by varying time of reaction of the PAS-co-PVP copolymer.     

Thermal behavior of poly(acrylic acid)–poly(vinyl pyrrolidone) and poly(acrylic acid)–metal–poly(vinyl pyrrolidone) complexes

Thermal analysis (TGA and DTA) of samples of PAA, PVP, PAA–PVP complexes, containing different weight fractions of PAA and ternary polymer–metal–polymer complexes, were studied. The activation energy parameters for the thermal degradation were also calculated. The study of the effect of FeCl₃, NiCl₂, and Ni(NO₃)₂ on the TGA and DTA curves of the complexes showed that the decompositions are dependent on the concentrations and the nature of the metal ions. The DTA traces of PAA–PVP complex containing FeCl₃, NiCl₂, and Ni(NO₃)₂ showed that the treatment of the complex with these metal ions causes considerable changes in the thermal decomposition of PAA–PVP complex. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4049–4057, 2006     

Semi‐interpenetrating polymer networks based on polyurethane and polyvinylpyrrolidone. II. Dielectric relaxation and thermal behaviour

Semi‐interpenetrating polymer networks (semi‐IPNs) based on crosslinked polyurethane (PU) and linear polyvinylpyrrolidone (PVP) were synthezised, and their thermal and dynamic mechanical properties and dielectric relaxation behavior were studied to provide insight into their structure, especially according to their composition. The differential scanning calorimetry results showed the glass transitions of the pure components: one glass‐transition temperature (T_g) for PU and two transitions for PVP. Such glass transitions were also present in the semi‐IPNs, whatever their composition. The viscoelastic properties of the semi‐IPNs reflected their thermal behavior; it was shown that the semi‐IPNs presented three distinct dynamic mechanical relaxations related to these three T_g values. Although the temperature position of the PU maximum tan δ of the α‐relaxation was invariable, on the contrary the situation for the two maxima observed for PVP was more complex. Only the maximum of the highest temperature relaxation was shifted to lower temperatures with decreasing PVP content in the semi‐IPNs. In this study, we investigated the molecular mobility of the IPNs by means of dielectric relaxation spectroscopy; six relaxation processes were observed and indexed according the increase in the temperature range: the secondary β‐relaxations related to PU and PVP chains, an α‐relaxation due to the glass–rubber transition of the PU component, two α‐relaxations associated to the glass–rubber transitions of the PVP material, and an ionic conductivity relaxation due to the space charge polarization of PU. The temperature position of the α‐relaxation of PU was invariable in semi‐IPNs, as observed dynamic mechanical analysis measurements. However, the upper α‐relaxation process of PVP shifted to higher temperatures with increasing PVP content in the semi‐IPNs. We concluded that the investigated semi‐IPNs were two‐phase systems with incomplete phase separation and that the content of PVP in the IPNs governed the structure and corresponding properties of such systems through physical interactions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1191–1201, 2003     

Preparation of sub-micron PZT particles with the sol–gel technique

This paper describes the production of Pb_1.0Zr_0.9Ti_0.1 ceramic powder, by using metal organic precursors as starting materials. In this study polyvinylpyrrolidone, PVP, was used to create a PZT–PVP sol and then also added as a secondary stage to control the particle size of the powder.Two different sol–gel routes were used to create PZT powder. Both routes gave similar primary particle sizes in the range, 30–70 nm, but different agglomerate formations. Perovskite PZT powder was created with both routes.     

Fabrication and characterization of PEI/PVP‐based carbon hollow fiber membranes for CO2/CH4 and CO2/N2 separation

Carbon hollow fiber membranes derived from polymer blend of polyetherimide and polyvinylpyrrolidone (PVP) were extensively prepared through stabilization under air atmosphere followed by carbonization under N₂ atmosphere. The effects of the PVP compositions on the thermal behavior, structure, and gas permeation properties were investigated thoroughly by means of differential scanning calorimetry, thermogravimetric analysis, X‐ray diffraction, and pure gas permeation apparatus. The experimental results indicate that the transport mechanism of small gas molecules of N₂, CO₂, and CH₄ is dominated by the molecular sieving effect. The gas permeation properties of the prepared carbon membranes have a strong dependency on PVP composition. The carbon membranes prepared from polymer blends with 6 wt % PVP demonstrated the highest CO₂/CH₄ and CO₂/N₂ selectivities of 55.33 and 41.50, respectively. © 2011 American Institute of Chemical Engineers AIChE J, 58: 3167–3175, 2012     

Influence of electrospinning parameters on poly(hydroxybutyrate) electrospun membranes fiber size and distribution

Poly(hydroxybutyrate) (PHB) obtained from sugar cane waste was dissolved in a blend of chloroform and dimethylformamide (DMF) and electrospun at 40°C. By adding DMF to the solution, the electrospinning process for the PHB polymer becomes more stable, allowing complete polymer crystallization during the jet travelling between the tip and the grounded collector. The influence of processing parameters on fiber size and distribution was systematically studied. It was observed that an increase of tip inner diameter promotes a decrease of the fiber average size and a broader distribution. Conversely, an increase of the electric field and flow rate produces an increase of fiber diameter until a maximum of ～2.0 µm but for electric fields higher than 1.5 kV cm^?1, a decrease of the fiber diameter was observed. Polymer crystalline phase seems to be independent of the processing conditions and a crystallinity degree of 53% was found. Moreover, thermal degradation of the as‐spun membrane occurs in single step degradation with activation energy of 91 kJ mol^?1. Furthermore, MC‐3T3‐E1 cell adhesion was not inhibited by the fiber mats preparation, indicating their potential use for biomedical applications. POLYM. ENG. SCI., 54:1608–1617, 2014. © 2013 Society of Plastics Engineers     

Flexible and thermally stable SiC fiber mats derived from electrospun boron-doped polyaluminocarbosilane precursors

Polymer-derived SiC fibers are critical structural and functional materials for high-temperature applications, whose service performance can be further improved by introduction of certain heterogeneous elements. Herein, flexible and thermal stable SiC fiber mats were prepared from boron-doped polyaluminocarbosilane (PACS) precursor by electro-spinning, curing and pyrolysis. Two boron-containing compounds o-carborane (oCB) and phenylboronic acid (PBA) were used as the boron sources and their effects on the properties and structure of the SiC fiber mats were investigated. The introduced oCB and PBA had obviously improved the ceramic yield of the cured fiber mats and the flexibility of the SiC fiber mats. However, PBA introduced more boron, but also more oxygen, which leaded to formation of more amorphous SiC_xO_y phases. Although only a small amount of boron was introduced by oCB, a more significant improvement in the thermal stability of the SiC fiber mat was obtained. This work provided a practical approach for fabrication of flexible and thermally stable SiC fiber mats.     

A study on polymer blend electrolyte based on PVA/PVP with proton salt

Proton-conducting polymer blend electrolytes based on PVA–PVP–NH₄NO₃ were prepared for different compositions by solution cast technique. The prepared films are investigated by different techniques. The XRD study reveals the amorphous nature of the polymer electrolyte. The FTIR and laser Raman studies confirm the complex formation between the polymer and salt. DSC measurements show decrease in T _g with increasing salt concentration. The ionic conductivity of the prepared polymer electrolyte was found by ac impedance spectroscopy analysis. The maximum ionic conductivity was found to be 1.41 × 10^?3 S cm^?1 at ambient temperature for the composition of 50PVA:50PVP:30 wt% NH₄NO₃ with low-activation energy 0.29 eV. The conductivity temperature plots are found to follow an Arrhenius nature. The dielectric behavior was analyzed using dielectric permittivity (ε*) and the relaxation frequency (τ) was calculated from the loss tangent spectra (tan δ). Using this maximum ionic conducting polymer blend electrolyte, the primary proton battery with configuration Zn + ZnSO₄·7H₂O/50PVA:50PVP:30 wt% NH₄NO₃/PbO₂ + V₂O₅ was fabricated and their discharge characteristics studied.     

Thermomechanical Modeling of Laser‐Induced Structural Relaxation and Deformation of Glass: Volume Changes in Fused Silica at High Temperatures

A fully coupled thermomechanical model of the nanoscale deformation in amorphous SiO₂ due to laser heating is presented. Direct measurement of the transient, nonuniform temperature profiles was used to first validate a nonlinear thermal transport model. Densification due to structural relaxation above the glass transition point was modeled using the Tool‐Narayanaswamy (TN) formulation for the evolution of structural relaxation times and fictive temperature. TN relaxation parameters were derived from spatially resolved confocal Raman scattering measurements of Si–O–Si stretching mode frequencies. Together, these thermal and microstructural data were used to simulate fictive temperatures which are shown to scale nearly linearly with density, consistent with previous measurements from Shelby et al. Volumetric relaxation coupled with thermal expansion occurring in the liquid‐like and solid‐like glassy states lead to residual stresses and permanent deformation which could be quantified. However, experimental surface deformation profiles between 1700 and 2000 K could only be reconciled with our simulation by assuming a roughly 2 × larger liquid thermal expansion for a‐SiO₂ with a temperature of maximum density ~150 K higher than previously estimated by Bruckner et al. Calculated stress fields agreed well with recent laser‐induced critical fracture measurements, demonstrating accurate material response prediction under processing conditions of practical interest.     

Thermal and dynamic mechanical behavior of bionanocomposites: Fumed silica nanoparticles dispersed in poly(vinyl pyrrolidone), chitosan,and poly(vinyl alcohol)

Various bionanocomposites were prepared by dispersing fumed silica (SiO₂) nanoparticles in biocompatible polymers like poly(vinyl pyrrolidone) (PVP), chitosan (Chi), or poly(vinyl alcohol) (PVA). For the bionanocomposites preparation, a solvent evaporation method was followed. SEM micrographs verified fine dispersion of silica nanoparticles in all used polymer matrices of composites with low silica content. Sufficient interactions between the functional groups of the polymers and the surface hydroxyl groups of SiO₂ were revealed by FTIR measurements. These interactions favored fine dispersion of silica. Mechanical properties such as tensile strength and Young's modulus substantially increased with increasing the silica content in the bionanocomposites. Thermogravimetric analysis (TGA) showed that the polymer matrices were stabilized against thermal decomposition with the addition of fumed silica due to shielding effect, because for all bionanocomposites the temperature, corresponding to the maximum decomposition rate, progressively shifted to higher values with increasing the silica content. Finally, dynamic thermomechanical analysis (DMA) tests showed that for Chi/SiO₂ and PVA/SiO₂ nanocomposites the temperature of β‐relaxation observed in tanδ curves, corresponding to the glass transition temperature T_g, shifted to higher values with increasing the SiO₂ content. This fact indicates that because of the reported interactions, a nanoparticle/matrix interphase was formed in the surroundings of the filler, where the macromolecules showed limited segmental mobility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal degradation of a phenolic resin,vegetable fibers,and derived composites

The thermal degradation behavior of resol, several vegetable fibers (two types of cotton fibers, sisal and sugar cane bagasse) and derived polymer composites have been investigated using thermogravimetric analysis (TGA). The initial thermal degradation temperature T_ONSET, the temperature at the maximum degradation rate TD_M, and the char left at 500°C corresponding to the crosslinked resol were higher than the values measured for the fibers and their composites. Thus, the addition of the fibers reduced the thermal resistance of the phenolic thermoset. The polymer and the fiber‐composites showed a complex degradation involving different thermal decomposition processes. For that reason, the DTG curves were deconvoluted and a phenomenological kinetic expression was found for each individual peak. The overall thermal decomposition curve was recalculated adding each degradation process weighted according to its contribution to the total weight loss. An increase in the activation energy corresponding to the cellulose degradation was observed in the composites, highlighting the protective action of the resin encapsulating the fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Predicting poly(vinyl pyrrolidone)'s solubility parameter and systematic investigation of the parameters of electrospinning with response surface methodology

The solubility parameters were used to choose the solvent for poly(vinyl pyrrolidone) (PVP) in electrospinning. In this study, a novel method for predicting the contribution value of the pyrrolidone group (a typical part of the PVP molecular structure) was proposed. The solubility parameters of PVP were calculated by this method, and accordingly, ethanol was chosen as the solvent for PVP. What is more, response surface methodology was used to facilitate a systematic investigation on the influence of the PVP solution concentration, feed rate, distance between the tip and collector, and operating voltage on the fiber diameter and morphology in electrospinning. The predicted fiber diameters by the response regression model, and the experimental values were in close proximity. The solution concentration and feed rate both had significant effects on the PVP fiber diameter, and there was some interaction between the solution concentration and the feed rate in this system. In addition, this study provided a train of thought for the electrospinning of polymer fibers with controllable and predictable fiber diameters. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40304.     

Effect of topology on the adhesive forces between electrospun polymer fibers using a T‐peel test

Electrospinning provides an effective methodology to obtain high aspect ratio polymer fibers for biomimetic applications. In this article, we evaluate the effect of topology on adhesion between aligned fibers. Polycaprolactone is electrospun using two different setups: (i) a tip collector and (ii) a flat collector. The tip collector enables the fibers to self‐align. When a fiber reaches the tip collector, the next fiber is repelled by the charge they carry, forcing the fibers to deposit in a parallel arrangement. The flat collector allows the fibers to deposit at random. The adhesion between the fiber mats is measured using a T‐peel test. Adhesion strength (758.7 ± 211.7 kPa) changes marginally with the peeling rate and applied pressure on the membranes. Aligned fibers exhibit higher adhesion strength between the membranes in comparison to randomly oriented nonwovens (613.1 ± 79.9 kPa). The estimated Johnson–Kendall–Roberts contact energy (83.1 ± 32.5 mJ/m²) is consistent with the range of van der Waals adhesion forces. This work shows how the adhesion between two polymer membranes can be modulated by surface topology, based on a T‐peel testing setup. POLYM. ENG. SCI., 53:2219–2227, 2013. © 2013 Society of Plastics Engineers     

Thermal behaviour of TiO2-encapsulating polymers

Comparing the thermal properties of TiO₂ encapsulating polystyrene and poly(methyl methacrylate) with those of TiO₂ dispersion polymers it was found that the encapsulating polymers have two thermal relaxation regions. The activation energy of those thermal relaxation regions was determined using the Wunderlich method and it was found that the values are similar to the activation energy for the dynamic dispersion. It is suggested that the low-temperature thermal relaxation is caused by the local change of conformation of molecular chains, while the high-temperature thermal relaxation is similar to that of the normal glass transition temperature including the interaction with TiO₂. In addition, the thermal behaviour near the degradation point in different atmospheres indicates that the encapsulating polymer has a specific structure for adsorbing a large amount of oxygen.     

Semiinterpenetrating polymer networks based on polyurethane and polyvinylpyrrolidone. I. Thermodynamic state and dynamic mechanical analysis

Semiinterpenetrating polymer networks (semi‐IPNs) based on polyurethane (PU) and polyvinylpyrrolidone (PVP) have been synthesized, and their thermodynamic characteristics, thermal properties, and dynamical mechanical properties have been studied to have an insight in their structure as a function of their composition. First, the free energies of mixing of the two polymers in semi‐IPNs based on crosslinked PU and PVP have been determined by the vapor sorption method. It was established that these constituent polymers are not miscible in the semi‐IPNs. The differential scanning calorimetry results evidence the T_g of polyurethane and two T_g for PVP. The dynamic mechanical behavior of the semi‐IPNs has been investigated and is in accordance with their thermal behavior. It was shown that the semi‐IPNs present three distinct relaxations. If the temperature position of PU maximum tan δ is invariable, on the contrary, the situation for the two maxima observed for PVP is more complex. Only the maximum of the highest temperature relaxation is shifted to lower temperature with changing of the semi‐IPNs composition. It was concluded that investigated semi‐IPNs are two‐phase systems with incomplete phase separation. The phase composition was calculated using viscoelastic properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 852–862, 2001     

Improvement of carbon nanotube dispersion in electrospun polyacrylonitrile fiber through plasma surface modification

In this study, surfaces of multiwalled carbon nanotubes (CNTs) were functionalized with poly(hexafluorobutyl acrylate) (PHFBA) thin film using a rotating-bed plasma-enhanced chemical vapor deposition (PECVD) method without imparting any defects on their surfaces. Polyacrylonitrile (PAN) electrospun polymer fiber mats and composite fiber mats with CNTs and functionalized CNTs (f-CNTs) were prepared. The wettability and chemical and morphological properties of the synthesized fiber mats were investigated, and the dispersion of CNTs and f-CNTs in the polymer matrix was compared according to the contact angle results of electrospun polymer mats. According to the chemical and morphological characterization results, PHFBA-coated CNTs were dispersed more uniformly in the polymer matrix than the uncoated CNTs. The f-CNTs/PAN composite fiber mat exhibits a lower surface energy than the pristine CNTs/PAN fiber mat. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47768.     

Morphology enhancement of TiO2/PVP composite nanofibers based on solution viscosity and processing parameters of electrospinning method

In this work, different sol solutions with various titanium tetraisopropoxide (TIP)/glacial acetic acid ratios in 2‐propanol with 5 wt % poly(vinyl pyrrolidone) (PVP) (M_w = 360,000 g/mol) were prepared and electrospun. Composition of the prepared sols and as‐spun TiO₂/PVP nanofibers were determined by Fourier transform infrared and Raman spectroscopy methods. Morphology of the electrospun TiO₂/PVP nanofibers was studied by scanning electron microscopy and transmission electron microscopy (TEM) techniques. Rheometry measurements of the sol solutions showed decrease of viscosity upon the addition of TIP to the polymer solutions with constant polymer and acid concentrations. The sol solution having the lowest viscosity (at shear rate 10 s^?1) but the highest TIP/glacial acetic acid ratio showed beaded nanofibers morphology when electrospun under 10 and 12 kV applied voltage while injection rate, needle tip to collector distance, and needle gauge were kept constant. However, smooth electrospun TiO₂/PVP composite nanofibers with the average nanofibers diameters (148 ± 79 nm) were achieved under the same condition when applied voltage increased to 15 kV. TEM micrographs of the electrospun TiO₂/PVP nanofiber showed that the TiO₂ particles with continuous structure are formed at the middle of the nanofiber and distributed along its axis. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46337.