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Considerable effort has been devoted to improving the properties of PVDF (polyvinylidene fluoride), arguably the most technologically important piezoelectric polymer. Electrospinning has been found to be a particularly effective method of producing PVDF nanofibers with superior piezoelectric properties due to the resulting exceptionally high fraction of the piezoelectrically active crystalline β‐phase. It is typically assumed that the high external electric fields applied during electrospinning enhance the formation of this β‐phase, with the confused literature offering various unsatisfactory mechanistic explanations. However, by comparing PVDF nanofibers produced by two different processes (electrospinning and blowspinning), we show that the electric field is entirely unnecessary; indeed, the crystallization dynamics are principally driven by the applied mechanical stress, as evidenced by structurally identical 200 nm diameter PVDF fibers produced with and without external electric fields.

The properties of mixtures of poly(lactic acid) (PLA) and poly(ethylene oxide) (PEO) were studied in polymer solutions by dilute solution viscometry, and in-solution blow-spun nanofibers were studied by microscopy (scanning electron and transmission electron microscopy) and thermal and spectral analysis. Three mixtures of PLA and PEO (3:1, 1:1, and 1:3) were solution-blended in chloroform. Dilute solvent viscometry indicated that the 3:1 mixture of PLA and PEO had a higher miscibility coefficient value than the other mixtures. The neat polymers and mixtures were solution-blow-spun into nanofibers. The fiber diameters were smallest in the neat polymers. Transmission electron micrographs revealed a core/sheath structure for the sample mixtures. X-ray analysis indi- cated that the crystallinity was positively correlated with the PEO content. Fibers from the mixtures had contact angle measurements similar to those of the neat PEO. Fourier transform infrared and Raman spectroscopy of the mixtures indicated interactions between ester and ether groups, which were attributed to dipole-dipole interactions between the ester groups of PLA and the ether groups of PEO. V C 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 129: 3672-3681, 2013

Mixed rutile-anatase TiO2 nanoparticles were synthesized by hydrothermal treatment under acidic conditions and incor- porated into poly(vinyl alcohol) (PVA). These nanocomposites were electrospun to produce nanofibers of PVA/TiO2, which were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The photocatalytic degradation of Rhodamine B and degradation of the polymer by UV-C lamps were also investigated. The results showed that TiO2 nanoparticles did not change the morphology and thermal behavior of the nanofiber polymer, but were effective in modifying the UV absorption of PVA without reducing its stability. V C 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 127: 4463-4469, 2013

This article studied the applicability of poly(- acrylamide) and methylcellulose (PAAm-MC) hydrogels as potential delivery vehicle for the controlled-extended release of ammonium sulfate (NH4)2SO4 and potassium phosphate (KH2PO4) fertilizers. PAAm-MC hydrogels with different ac- rylamide (AAm) and MC concentrations were prepared by a free radical polymerization method. The adsorption and de- sorption kinetics of fertilizers were determined using conduc- tivity measurements based on previously built analytical curve. The addition of MC in the PAAm chains increased the quantities of (NH4)2SO4 and KH2PO4 loaded and extended the time and quantities of fertilizers released. Coherently, both loading and releasing processes were strongly influ- enced by hydrophilic properties of hydrogels (AAm/MC mass proportion). The best sorption (124.0 mg KH2PO4/g hydrogel and 58.0 mg (NH4)2SO4/g hydrogel) and desorp- tion (54.9 mg KH2PO4/g hydrogel and 49.5 mg (NH4)2SO4/g hydrogel) properties were observed for 6.0% AAm-1.0% MC hydrogels (AAm/MC mass proportion equal 6), indicating that these hydrogels are potentially viable to be used in con- trolled-extended release of fertilizers systems. V C 2011 Wiley

Nano and submicrometric fibers of poly(D,L-lactide) (PDLLA or PLA) were spun from solutions using a solution blow spinning (SBS) apparatus. Fiber morphology and diameter were investigated by scanning electron microscopy as a function of polymer concentration, feed rate, and air pressure. A more systematic understanding of the SBS process parameters was obtained, and a quantitative relationship between these parameters and average fiber diameter was established by design of experiments and response surface methodology. It was observed that polymer concentration played an important role in fiber diameter, which ranges from 70 to 2000 nm, and its distribution. Lower polymer concentration tended to increase the formation of bead-on-string structures, whereas smooth fibers were formed at higher concentrations. Fiber diameter tended to increase with polymer concentration and decrease with feed rate. Based on these results, optimal conditions could be obtained for solution-blow spun fibers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.

Hydrogels with potential technological applications has been prepared using polyacrylamide (PAAm) and methylcellulose (MC) polymers by free radical polymerization reaction. The spectroscopic, morphological, swelling, and kinetic properties were investigated by solid state 13C VACP-MAS nuclear magnetic resonance (NMR), fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), water uptake (WU) measurements, respectively. FTIR and NMR analysis confirmed the formation of semi-IPN structured hydrogel. Data from WU and SEM revealed that the addition of MC into the solution-forming hydrogel leads to increase in average pore size and hydrophilicity. By varying of AAm, MC, pH and ionic-strength of swelling medium, it was possible to obtain hydrogels with hydrophilic properties controlled and optimized. The water uptake mechanism is dependent of the AAm concentration, which can follow the Fickian diffusion and anomalous transport process. In this way, PAAm-MC hydrogels are promising materials for technological applications, such as agricultural field. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

This work evaluates the use of cotton cellulose nanofibers (CCN) as a reinforcing agent to prepare thermoplastic corn starch (TPS) matrix plasticized with 30 wt % of glycerol. The nanocomposites were filled with 0.5–5.0 wt % of CCN on a dry-starch basis. The dried nanofibers were resuspended through the use of an ultrasonicator and then introduced in the fixed water formulation for obtaining TPS. The nanocomposites were compounded in a corotating twin-screw extruder. Scanning transmission electron microscopy (STEM), field emission gun (FEG), X-ray diffraction (XRD) and thermogravimetric analysis (TGA), in air atmosphere, were used to characterize nanofibers, neat TPS, and nanocomposites. The results showed that the nanofibers had needlelike structure with an average length of about 135 ± 50 nm and an average diameter of about 14 ± 4 nm. The addition of CCN was effective to enhance the mechanical properties of neat TPS in compositions above 2.5 wt %, although some agglomeration could be observed. The resulting nanocomposites showed good structural stability, because the amylopectin transcrystallization phenomena on the surface of nanofibers had not occurred. Only a slight decrease in the crystallinity index and a minor increase in the water absorption in relation to neat TPS were observed. An increase in the thermal stability of TPS nanocomposites with respect to neat TPS was verified, but it was independent of the CCN content. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

This research studied the characteristics of poly(acrylamide) and methylcellulose (PAAm-MC) hydrogels as a novel adsorbent material for removal of pesticide paraquat, from aqueous solution, with potential applications in curbing environmental risk from such herbicides. PAAm-MC hydrogels with different acrylamide (AAm) and MC concentrations were prepared by a free-radical polymerization method. The capability of the hydrogels in removing paraquat dichloride from aqueous solution was determined using UV–Vis analysis. The scanning electron microscopy method was used to study the morphological properties of the hydrogels, and swelling degree (Q) of the hydrogels was also measured. The entrapped MC in PAAm chains provoked significant changes in morphological, hydrophilic, and adsorption properties of the PAAm-MC hydrogels. The adsorption capacity of hydrogels was strongly influenced by AAm, MC, and paraquat concentrations with the highest adsorption capacity (qeq = 14.3 mg g−1) was observed for hydrogels synthesized with 6.0% AAm with 0.75% MC swollen in 45.7 mg L−1 of paraquat solution. Freundlich model performed better than Langmuir model in describing the adsorption isotherm of PAAm-MC/paraquat system, implying a heterogeneous surface. These results suggest that PAAm-MC hydrogels are potentially viable absorbents for removal of paraquat pesticide from aqueous solution and cleaning water contaminated with dyes, heavy metals, and others pesticides. © 2009 Wiley Periodicals, Inc. Journal of Appl Polym Sci, 2009

A solution blow spinning technique was developed using elements of both electrospinning and melt blowing technologies as an alternative method for making non-woven webs of micro- and nanofibers with diameters comparable with those made by the electrospinning process with the advantage of having a fiber production rate (measured by the polymer injection rate) several times higher. The diameters of fibers produced ranged from 40 nm for poly(lactic acid) to several micrometers for poly(methyl methacrylate). This solution blow spinning method uses a syringe pump to deliver a polymer solution to an apparatus consisting of concentric nozzles whereby the polymer solution is pumped through the inner nozzle while a constant, high velocity gas flow is sustained through the outer nozzle. Analysis of the process showed that pressure difference and shearing at the gas/solution interface jettisoned multiple strands of polymer solution towards a collector. During flight, the solvent component of the strands rapidly evaporates forming a web of micro and nanofibers. The effect of injection rate, gas flow pressure, polymer concentration, working distance, and protrusion distance of the inner nozzle was investigated. Polymer type and concentration had a greater effect on fiber diameter than the other parameters tested. Injection rate, gas flow pressure, and working distance affected fiber production rate and/or fiber morphology. Fibers were easily formed into yarns of micro- and nanofibers or non-woven films that could be applied directly onto biological tissue or collected in sheets on a rotating drum. Indeed, virtually any type of target could be used for fiber collection.

This work reports a systematic comparative study of the technological properties of natural lattices and rubbers extracted from Hancornia speciosa Gomes and Hevea brasiliensis [(Willd. ex Adr. de Juss.) Muell.-Arg.] (clone RRIM 600) trees from 11 collections in Brazil throughout 2004. Natural rubber latex particle sizes and distributions were quite similar with an average diameter around 1 μm. Molecular weight, Wallace plasticity, and Mooney viscosity values were approximately the same for both rubbers. Fourier transform infrared spectroscopy peaks characteristic of natural rubber were observed for both Hancornia and Hevea. The measured differences in technological properties included lower values for Hancornia dry rubber content, % ash, % nitrogen, and plasticity retention index but higher value for acetone extract. Interestingly, nitrogen and protein content were much lower in Hancornia, suggesting that it may have important applications in nonallergic rubber uses. This represents the first report of lacticifer-produced low-protein natural rubber. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

UNESP Depto de Fisica e Quimica Sao Paulo State University, Ilha Solteira, Sao Paulo 15.385-000

Blends of starch and zein plasticized with glycerol were prepared by melting in a batch mixer at 160°C. Glycerol was used as plasticizer in contents ranging from 20 to 40 wt % with respect to the starch/zein matrix. These blends were characterized by mechanical tests, dynamic me- chanical analysis, and optical microscopy. In tensile tests, the Young's modulus and ultimate tensile strength in- creased with increasing zein content for all compositions, whereas elongation at break decreased sharply with increas- ing zein content up to 20%, and it remained nearly constant at higher contents of zein, which increased the stiffness of the blends. On the other hand, increase in the glycerol content caused a decrease in mechanical resistance of the blends. Storage modulus increased with increasing zein con- tent and the tan curves showed that the blends exhibited two distinct glass transitions, one for each component, indi- cating a two-phase system, confirming the morphological evidence of micrographs that displayed two separate phases. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4133- 4139, 2006

Blend films (free-standing) containing 20% in volume of polyaniline (PANI) in 80% of natural rubber (NR) were fabricated by casting in three different ways: (1) adding PANI-EB (emeraldine base) dissolved in N-methyl-2-pyrrolidone (NMP) to the latex (NRL), (2) adding PANI-EB dissolved in m-cresol to NR dissolved in xylol (NRD), (3) overlaying the surface of a pure NR cast film with a PANI layer grown by in situ polymerization (NRO). All the films were immersed into HCl solution to achieve the primary doping (protonation) of PANI before the characterization. The main goal here was to investigate the elastomeric and electrical conductivity properties for each blend, which may be applied as pressure and deformation sensors in the future. The characterization was carried out by optical microscopy, dc conductivity, vibrational spectroscopy (infrared absorption and Raman scattering), thermogravimetry analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and tensile stress–strain curves. The results suggest that the NRL blend is the most suitable in terms of mechanical and electrical properties required for applications in pressure and deformation sensors: a gain of conductivity without losing the elastomeric property of the rubber. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1498–1503, 2005

Conductive composites from poly(vinylidene fluoride) (PVDF) and a novel thermally stable conductive additive made via in situ deposition of polyaniline or polypyrrole on carbon black particles were produced by a melting process. Electrical conductivity in the order of 10−2 S/cm could be achieved with low contents of the conductive filler. Thermogravimetric analysis (TGA) showed that there is no appreciable degradation of the composites at temperatures as high as 300°C. Moreover, the addition of the conducting polymer-modified carbon black additive is advantageous to the melt processing of the composites, reducing the melt viscosity in comparison to the addition of pure carbon black. Composites containing the β-phase of PVDF could be obtained via quenching from the melt, as indicated by X-Ray diffraction analysis. The type and amount of the additive and the quenching rate influence the formation of β-phase in the PVDF composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 553–557, 2004

Curing of a novolac-type phenolic resin was studied by DSC. The kinetic analysis was performed by means of the dynamic Ozawa method at heating rates of 5, 10, 15, and 20°C/min. This analysis was used to determine the kinetic parameters of the curing process. The activation energy was found to be 144 kJ/mol. It was found that the Ozawa exponent values decreased with increasing reaction temperature from 3.5 to 1, suggesting a change in the reaction mechanism from microgel growth to diffusion-controlled reaction. The reaction rate constant was found to range from 123.0 to 33.6 (°C/min)n. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1678–1682, 2003

Sisal fibers were benzylated under different conditions and were characterized with infrared spectroscopy, X-ray diffraction, thermal analysis, and scanning electron microscopy. The benzylation reaction was monitored by the mass gain as a function of the reaction time. In the first stage, there was a mass loss associated with the loss of lignin and polyoses from the raw fiber, which was accompanied by an increase in mass due to benzyl incorporation. When fiber delignification was carried out before benzylation, the mass gain curves of the benzylation reaction presented no initial mass loss and a much higher mass gain. Benzylation promoted several morphological changes: (1) the loss of the parenchyma cells, (2) the defibrillation of the technical fibers into ultimate fibers, (3) the microdefibrillation of the ultimate fibers, and (4) benzyl incorporation. The crystallinity of the fibers decreased with benzylation, as observed by X-ray diffraction. The thermal stability of the fibers varied according to the treatment used. Other changes promoted in the fibers by chemical modification were examined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2957–2965, 2003

The world tendency toward using recycled materials demands new products from vegetable resources and waste polymers. In this work, composites made from powdered tire rubber (average particle size: 320 μm) and sisal fiber were prepared by hot-press molding and investigated by means of dynamic mechanical thermal analysis and tensile properties. The effects of fiber length and content, chemical treatments, and temperature on dynamic mechanical and tensile properties of such composites were studied. The results showed that mercerization/acetylation treatment of the fibers improves composite performance. Under the conditions investigated the optimum fiber length obtained for the tire rubber matrix was 10 mm. Storage and loss moduli both increased with increasing fiber content. The results of this study are encouraging, demonstrating that the use of tire rubber and sisal fiber in composites offers promising potential for nonstructural applications. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 670–677, 2004

The real (e′) and imaginary (e″) components of the complex permittivity of blends of PVDF [poly(vinylidene fluoride)] with POMA [poly(o-methoxyaniline)] doped with toluenosulfonic acid (TSA) containing 1, 2.5, and 5 wt % POMA–TSA were determined in the frequency interval between 102 and 3 × 106 Hz and in the temperature range from −120 up to 120°C. It was observed that the values of e′ and e″ had a greater increase with the POMA–TSA content and with a temperature in the region of frequencies below 10 kHz. This effect decreased with frequency and it was attributed to interfacial polarization. This polarization was caused by the blend heterogeneity, formed by conductive POMA–TSA agglomerates dispersed in an insulating matrix of PVDF. The equation of Maxwell–Garnett, modified by Cohen, was used to evaluate the permittivity and conductivity behavior of POMA–TSA in the blends. A strong decrease was observed in POMA–TSA conductivity in the blend, which was bigger the lower the POMA–TSA content in the blend. This decrease could have been caused either by the POMA dedoping during the blend preparation process or by its dispersion into the insulating matrix. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 752–758, 2003

Chopped sisal fibers and finely powdered high-density polyethylene were surface functionalized using dichlorosilane (DS) under radio frequency (RF)-plasma conditions and characterized by electron spectroscopy for chemical analysis (ESCA) and fluorescence labeling techniques. A high-capacity (10 L), rotating, 13.56 MHz, electrodeless plasma installation, specially designed to allow the uniform surface modification of powdery and particulate matter of irregular shape, was used. A three-factor fractional experimental design was employed to evaluate the effect of RF-power, pressure, and reaction time on the ESCA-based relative atomic composition of plasma-treated samples. It was demonstrated that SiHxCly functionalities are present on plasma-exposed surfaces and these functionalization reactions can be controlled by selecting proper plasma parameters. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2145–2154, 2002

Self-assembled films of poly(o-ethoxyaniline)—POEA alternated with sulfonated lignin (SL)—were successfully produced, and their kinetics of formation and growth investigated for different dopants (hydrochloric acid, methanesulfonic acid, p-toluenesulfonic acid, and camphorsulfonic acid). These films were characterized by ultraviolet-visible spectroscopy, atomic force microscopy, surface potential, and electrical resistance measurements. It has been observed that the bulkiest dopants led to a greater time for the polymer deposition and greater amount of material adsorbed. This can be explained by the lower mobility and lower solvation of the bulkiest dopant counterions, which led to a higher screening effect of the charges present in the POEA chains and therefore to a more compact molecular conformation. The morphology of the POEA films were also greatly affected by the type of dopant used, being rougher for the bulkiest dopants. The POEA films also exhibited different electrical responses upon ethylene exposure depending on the dopant, indicating a promising use for gas sensor applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1309–1316, 2002

Mechanical blends of ethylene–vinyl acetate copolymer and polyaniline doped with dodecyl benzene sulfonic acid (PAni–DBSA) were prepared in a two-roll mill at 50°C and in a Haake internal mixer at 150°C. The effects of the blend composition and processing conditions on the electrical conductivity and mechanical properties were investigated. These blends exhibited high levels of electrical conductivity at a small amount of PAni complex. Blends prepared in a two-roll mill displayed conductivity values as high as 1 S/cm and a higher protonation degree than the pure PAni–DBSA, as indicated by X-ray photoelectron spectroscopy. Two different insulator–conductor transition points were observed in these blends. The mechanical performance decreased as the amount of PAni–DBSA increased, indicating blend incompatibility and a plasticizing effect of the DBSA. The morphology of the blends were studied by scanning electron microscopy. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 114–123, 2001

Universidade de Sao Paulo Ciencia e Engenharia de Materiais Area Interunidades, Sao Carlos, SP

A pectin-based hydrogel was used as a remover of Cu2+ and Pb2+ ions from water and wastewater and in the release of phosphate, potassium, and urea. The swelling studies in either aqueous or saline solutions were analyzed at different pressures, and the prediction of profile of water and solute transports was further analyzed on basis of transport process by diffusion in swellable polymer networks. The hydrogel composed of 0.10 g mL−1 final polymer concentration showed an excellent absorption capacity for removal of Cu2+ and Pb2+ from the solution: 120 mg Cu2+ and 130 mg Pb2+ per g hydrogel, both at pH 5.5. The hydrogel help to conserve water in a pressure range in which a variety of horticultural plants can absorb it. The release process of urea, phosphate, and potassium from the hydrogels is controlled by non-Fickian mechanism with a tendency to macromolecular relaxation. This type of hydrogel is an interesting system for applications in which the efficient use of water is required and release of fertilizers for agriculture. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Unripe coconut fibers were used as fillers in a biodegradable polymer matrix of starch/ethylene vinyl alcohol (EVOH)/glycerol. The effects of fiber content on the mechanical, thermal, and structural properties were evaluated. The addition of coconut fiber into starch/EVOH/glycerol blends reduced the ductile behavior of the matrix by making the composites more brittle. At low fiber content, blends were more flexible, with higher tensile strength than at higher fiber levels. The temperature at the maximum degradation rate slightly shifted to lower values as fiber content increased. Comparing blends with and without fibers, there was no drastic change in melt temperature of the matrix with increase of fiber content, indicating that fibers did not lead to significant changes in crystalline structure. The micrographs of the tensile fractured specimens showed a large number of holes resulting from fiber pull-out from the matrix, indicating poor adhesion between fiber and matrix. Although starch alone degraded readily, starch/EVOH/glycerol blends exhibited much slower degradation in compost. Composites produced 24.4–28.8% less CO2 compared with starch in a closed-circuit respirometer. Addition of increasing amount of fiber in starch/EVOH/glycerol composite had no impact on its biodegradation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009