Surface-coated fly ash reinforced biodegradable poly(vinyl alcohol) composite films: part 2-analysis and characterization

Composite films of poly(vinyl alcohol) (PVA) reinforced with 5, 10, 15, 20 and 25 wt.% surface-coated fly ash by surfactant, sodium lauryl sulphate (SLS-FA) along with 1 wt.% cross-linking agent, glutaraldehyde (GLA) were prepared by aqueous casting method. The tensile strengths of the composite films were increased proportionally with the addition of SLS-FA. The maximum 75% higher strength of the composite with 20 wt.% was achieved compared to that of neat PVA. The modulus of the composites was also increased proportionally with SLS-FA and the maximum 218% reached in composite with 20 wt.%, but the strain at break was decreased with addition of SLS-FA. Changes in FTIR spectra reflect the chemical and/or physical bonding in the ternary PVA, SLS-FA and GLA component systems. In the study of surface morphology, the connectivity was visualized in SEM images along with interstitial voids. The films with SLS-FA show 53% smoother surface calculated with AFM compared to unmodified FA composite films.     

Ionic desorption in valence- and core-excited poly(vinyl chloride)

Photon stimulated ion desorption (PSID) studies have been performed in poly(vinyl chloride) (PVC) using synchrotron radiation, encompassing the valence and core electron (Cl 2p and C 1s) energy ranges. Data acquisition was performed at the Brazilian synchrotron light source (LNLS), operating in a multi-bunch mode and using a time-of-flight mass spectrometer (TOF-MS). A pulsed high voltage applied to the sample was used as a trigger for the TOF-MS experiments. Ionic desorption from PVC shows strong selectivity in the formation of chlorine ions around the Cl 2p-edge while very similar fragmentation patterns are observed for the other energies studied.     

Preparation and characterization of a novel antistatic poly(vinyl chloride)/quaternary ammonium based ion-conductive acrylate copolymer composites

Antistatic poly(vinyl chloride)/quaternary ammonium salt based ion-conductive acrylate copolymer (PVC/QASI) composites were successfully prepared in a Haake torque rheometer. The surface resistivity of the PVC/QASI composites could be reduced to 10⁷ Ω sq^?1 order of magnitude when the QASI content reached 20 phr (parts per hundreds of resin). The surface resistivity of the composites was slightly sensitive to the relative humidity (RH), showing a good antistatic ability under an RH of 12%. Mechanical properties tests, differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) were also used to investigate the tensile strength, elongation at break, thermal properties, and morphology of the PVC/QASI composites, respectively.     

Thermally stimulated transformation of the structure of cobalt complexes in polyvinyl alcohol-cobalt(II) chloride systems

We present the kinetic and temperature dependences of the optical absorption of thermochromic films of polyvinyl alcohol with added CoCl₂. Based on the data obtained, we have analyzed the possibility that tetrahedral cobalt complexes are formed from octahedral complexes. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 6, pp. 826–829, November–December, 2007.     

The use of a temperature programmable brabender mixing head for the evaluation of the processing characteristics of poly(vinyl chloride)

A technique is described for determining the temperature-torque profile of a PVC compound in a Brabender Plasticorder mixing chamber from room temperature to the temperature at which degradation occurs. Within this temperature range many PVC compounds show three characteristic peaks in the torque temperature trace. It is suggested that these three peaks are associated with the breakdown of the PVC powder particles (Stage III, 100 to 150 μm), micro-granules (Stage II, 0.5 to 2 μm), and primary particles (Stage I, 10 nm), respectively. The positions and shapes of these peaks are functions of the compound being investigated and as such can be used to characterize the processing behavior of the compound.

The greater part of the work has been carried out using suspension polymers but application of the technique to mass and emulsion polymers suggests that the conclusions are applicable to all polymers which possess a particulate substructure.     

Molecular and optical modifications in poly(vinyl chloride) due to N-phenylmaleimide additives and gamma irradiation

The effects of N-phenylmaleimide (NPMI) concentration and gamma dose on the molecular and optical properties of poly(vinyl chloride) (PVC) have been studied. The results reveal an improvement in the intrinsic viscosity of PVC in the presence of an organic material. The effective concentration that enhanced the intrinsic viscosity, from 1.02 to 1.28, was found to be 10 mmol NPMI per 100 g PVC. The effect of gamma irradiation on the PVC polymer stabilized with this concentration of NPMI has been studied. Samples from the 0.01 g NPMI/1 g PVC were irradiated with gamma doses in the range 5–180 kGy. It is found that irradiation in the dose range 120–180 kGy enhances the intrinsic viscosity of the samples. In addition, the transmission of these irradiated samples in the wavelength range 200–2500 nm, as well as any color changes was studied. The color intensity (Δ E) was greatly increased with the increasing gamma dose, and was accompanied by darkness with a significant increase in the yellow color component.     

Analysis of X-ray and electron-beam diffraction patterns from poly(dipropyl siloxane)

The crystalline polysiloxane (—R2SiO—)n. where R= n-propyl, has been characterized through high-resolution X-ray diffraction patterns of the polycrystalline material and selected-area electron-beam diffraction patterns of single crystals. The smallest unit cell consistent with the diffraction data is tetragonal, with dimensions a = 9.52 ? 0.01 and c = 9.40 ± 0.05 . The probable space group is P41 (or P43).     

Modification of cycloolefin copolymer and poly(vinyl chloride) surfaces by superimposition of nano- and microstructures

Cycloolefin copolymer (COC) and poly(vinyl chloride) (PVC) surfaces were patterned with nanopillars or with microbumps on which nanopillars were superimposed. The area of patterned surfaces was several square centimeters. Patterning was achieved by applying nanoporous anodized aluminum oxide (AAO) membrane as a mask in injection molding or imprinting. Nanostructures superimposed on microstructures were achieved by patterning the AAO mask with microstructures before anodization. Micro- and nanometer-sized structures could then be transferred simultaneously to polymer surfaces. Structures were characterized by SEM, AFM, and contact profilometry. The effect of different-sized structures on properties of the polymer surface was studied by contact angle measurements. Relative to the smooth surface, the increase in water contact angle on a COC surface with nanostructures superimposed on microstructures was up to 50°.     

Inactivation of Escherichia coli and properties of medical poly(vinyl chloride) in remote-oxygen plasma

This paper reports the germicidal effect (GE) of Escherichia coli on the surface of medical poly(vinyl chloride) (PVC) in remote-oxygen plasma. The concentration of active species in plasma is determined by means of double Langmuir electron probe and electron-spin resonance (ESR) diagnosis. Moreover, surface properties of sterilized PVC are characterized by the water contact angle measurement, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The distribution of electrons, ions, and radicals in plasma reactor is different. High-purity radicals are obtained at 40 cm from the induction coil which is called remote-plasma zone. By remote-oxygen-plasma sterilization, GE value reach 4.12 under the conditions of treatment time of 60 s, plasma RF power of 100 W and oxygen flux of 60 cm³/min. Compared with direct-oxygen-plasma sterilization, remote plasma can enhance the hydrophilic property and limit the degradation of the PVC surface. After remote-plasma sterilization, PVC surface energy is increased more than twice, which mainly resulted from the increase of surface polar force , and hydrogen bonding force . Moreover, remote-plasma sterilization can increase oxygenated functional groups on PVC surface. Experimental results show that remote plasma can inactivate E. coli on the medical PVC substrate effectively. Furthermore, it can optimize the surface properties.     

Dielectric relaxation and ac conductivity behavior of carboxyl functionalized multiwalled carbon nanotubes/poly (vinyl alcohol) composites

We study the dielectric relaxation and ac conductivity behavior of MWCNT-COOH/Polyvinyl alcohol nanocomposite films in the temperature (T) range 303–423 K and in the frequency (f) range 0.1 Hz–1 MHz. The dielectric constant increases with an increase in temperature and also with an increase in MWCNT-COOH loading into the polymer matrix, as a result of interfacial polarization. The permittivity data were found to fit well with the modified Cole-Cole equation. Temperature dependent values of the relaxation times, free charge carrier conductivity and space charge carrier conductivity were extracted from the equation. An observed increment in the ac conductivity for the nanocomposites was analysed by a Jonscher power law which suggests that the correlated barrier hopping is the dominant charge transport mechanism for the nanocomposite films. The electric modulus study revealed deviations from ideal Debye-type behavior which are explained by considering a generalized susceptibility function. XRD and DSC results show an increase in the degree of crystallinity.     

Hydrolysis etching of crystalline and amorphous poly(ethylene terephthalate): Influence of molecular weight and microstructure

The degradation of samples of amorphous and semicrystalline PET with different molecular weights by means of hydrolysis at 180°C has been investigated by measuring the weight loss and the x-ray crystallinity as a function of etching time. It is shown that during the first hours of etching, a concurrent crystallization of the amorphous samples takes place. It is found that weight loss values of amorphous samples after long etching times are higher than the weight loss of the crystallized materials. Results also indicate that weight loss depends to some extent on the initial degree of crystallinity of the material. It is emphasized that the lateral size of the crystallites is a major parameter in determining the total amount of etched material. Analysis of results further confirms that mainly the amorphous regions lying outside of the lamellar stacks are removed by hydrolysis. However, the crystals formed during annealing of the amorphous samples at 180°C are less perfect and the lamellar stacks in these samples are more affected by the hydrolysis attack than in the previously crystallized PET samples.     

Rheological,thermal, and mechanical properties of poly(ethylene naphthalate)/poly(ethylene terephthalate) blends

Structural, Theological, thermal, and mechanical properties of blends of poly(ethylene naphthalate) (PEN) and poly(ethylene terephthalate) (PET) obtained by melt blending were investigated using capillary rheometry, differential scanning calorimetry (DSC), scanning electron microscopic (SEM) observation, tensile testing. X-ray diffraction, and ¹H nuclear magnetic resonance (NMR) measurements. The melt Theological behavior of the PEN/PET blends was very similar to that of the two parent polymers. The melt viscosity of the blends was between that of PEN and that of PET. Thermal properties and NMR measurement of the blends revealed that PEN is partially miscible with PET in the as molded blends, indicating that an interchange reaction occurs to some extent on melt processing. The blend of 50/50 PEN/PET was more difficult to crystallize compared with blends of other PEN/PET ratios. The blends, once melted during DSC measurements, almost never showed cold crystallization and subsequent melting and definitely exhibited a single glass transition temperature between those of PEN and PET during a reheating run. Improvement of the miscibility between PEN and PET with melting is mostly due to an increase in transesterification. The tensile modulus of the PEN/PET blend strands had a low value, reflecting amorphous structures of the blends, while tensile strength at the yield point increased linearly with increasing PEN content.     

Surface-coated fly ash used as filler in biodegradable poly(vinyl alcohol) composite films: Part 1—The modification process

The surfaces of fly ash (FA) particles were modified by surfactant, sodium lauryl sulphate (SLS) and used in fabrication of composite films with polyvinyl alcohol (PVA). Both unmodified fly ash (FA) and modified fly ash (SLS-FA) samples were examined using a range of analytical tools including X-ray fluorescence spectroscopy (XRF), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). The distribution patterns of SLS-FA particles were shifted to the higher regions compared to FA by adding 1.2-4.2 μm in the ranges between 2 and 25 μm, whereas the modification process reduced the size of the particles over 25 μm due to grinding during the activation process. The increased 1.2-4.2 μm in average can be considered the thickness of the surfactant on the SLS-FA surface. On the oxides based chemical analysis by XRF, the compositions were almost unchanged. SEM and TEM were visualised the irregular sizes morphology mostly spherical of the particles, although it is impossible to capture the images of exactly same particles in modified and unmodified forms. The composite films reinforced with SLS-FA showed 33% higher strength than those of FA filled films. The enhancement of tensile strength attributed from the level of physical bonding between SLS-FA and PVA surfaces.     

Influence of lithium potassium zirconate nanoparticles on the electrical properties and structural characteristics of poly(vinyl alcohol) films

We investigated the influence of lithium potassium zirconate (LiKZrO₃) nanoparticles on the electrical properties and structural characteristics of poly(vinyl alcohol) (PVA) films. PVA/LiKZrO₃ nanocomposite films were prepared by casting of aqueous solutions with varying LiKZrO₃ content (0.5, 1.0, and 2.0 wt.%). The dielectric constant (ε′), dielectric loss (ε″), AC conductivity (σ_ac), dielectric loss tangent (tan δ), and electric modulus (M′ and M″) of the nanocomposite films were measured over a range of frequencies at ambient temperature. The results show increases in σ_ac and M′ with frequency, whereas ε′, ε″, and tan δ decreased with increasing frequency. The films were also characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and X-ray diffraction (XRD) techniques. DSC and XRD revealed the nature of LiKZrO₃ nanoparticle interaction with the PVA matrix. TGA analysis revealed an increase in thermal stability of the nanocomposites with increasing nanoparticle concentration. Scanning electron microscopy confirmed uniform dispersion of LiKZrO₃ nanoparticles in the PVA matrix.     

Effects of molecular weight and polydispersity of poly (3-hexylthiophene) in bulk heterojunction polymer solar cells

This paper reports the effect of the molecular weight (MW) and polydispersity (PD) of poly (3-hexylthiophene) (P3HT) in bulk heterojunction polymer solar cells (BHJ-SCs). The P3HT with low MW and broad PD exhibited higher crystallinity compared to that with high MW and narrow PD. Due to the improved crystallinity, the BHJ-SCs based on P3HT with low MW and broad PD showed performance with a power conversion efficiency of 3.8% with short-circuit currents of −9.90 mA/cm².     

Formation of linear polyenes in poly(vinyl alcohol) films catalyzed by phosphotungstic acid,aluminum chloride,and hydrochloric acid

Formation of linear polyenes–(CH=CH)_n–via acid-catalyzed thermal dehydration of polyvinyl alcohol in 9- to 40-µm-thick films of this polymer containing hydrochloric acid, aluminum chloride, and phosphotungstic acid as dehydration catalysts was studied by electronic absorption spectroscopy. The concentration of long-chain (n ≥ 8) polyenes in films containing phosphotungstic acid is found to monotonically increase with the duration of thermal treatment of films, although the kinetics of this process is independent of film thickness. In films containing hydrochloric acid and aluminum chloride, the formation rate of polyenes with n ≥ 8 rapidly drops as film thickness decreases and the annealing time increases. As a result, at a film thickness of less than 10–12 µm, long-chain polyenes are not formed at all in these films no matter how long thermal duration is. The reason for this behavior is that hydrochloric acid catalyzing polymer dehydration in these films evaporates from the films during thermal treatment, the evaporation rate inversely depending on film thickness.     

Isotactic poly(p-fluorostyrene): Conformation and molecular packing analysis

The chain conformation and molecular packing of isotactic poly(p-fluorostyrene) have been examined using calculations made with semiempirical potential energy functions. Isolated chain conformational energies indicate no difference in conformation for the fluoropolymer from the conformation for isotactic polystyrene. The energy for packing poly(p-fluorostyrene) chains into a crystalline array as 3₁ or 4₁ helices was also compared with the energies for packing polystyrene in both of these helical forms. While not being the lowest energy mode of packing for poly(p-fluorostyrene), the packing of 4₁-helices does yield a local energy minimum. Such packing of 4₁ helical polystrene chains is considerably less energetically feasible. The results indicate the causes for the experimentally observed difference in the crystalline conformations of the two isotactic polymers as being due to intermolecular influences.     

Analysis of ferroelectric switching in sodium nitrite:poly(vinyl alcohol) nanocomposite films

The Fourier transform infrared (FTIR) spectra and switching current response in sodium nitrite:poly(vinyl alcohol) nanocomposite films have been studied as a function of composition of NaNO₂. The switching current data fitted well to infinite-grain model (IGM) in the region t<t _s and to finite-grain model (FGM) in the region t≥t _s . The microscopic parameters like the dimensionality, the domain wall velocity, and the nucleation rate have been evaluated which provide more physical insight of the switching phenomena in the composite films. The polarization current and nucleation rate are optimum in 50 wt.% composite film and have been discussed in terms of grain size and strain variations with the composition. The effect of applied field and pulse width variation on the switching behavior of 50 wt.% composition has also been studied. The exponential field dependence of the domain wall velocity and the nucleation rate indicate that nucleation mechanism is responsible for switching phenomena in the composite films. The writing pulse width affects significantly on the switching behavior of the composite films.     

Quantum diffusion in polaron model of poly(dG)-poly(dC) and poly(dA)-poly(dT) DNA polymers

We numerically investigate quantum diffusion of an electron in a model of poly(dG)-poly(dC) and poly(dA)-poly(dT) DNA polymers with fluctuation of the parameters due to the impact of colored noise. The randomness is introduced by fluctuations of distance between two consecutive bases along the stacked base pairs. We demonstrate that in the model the decay time of the correlation can control the spread of the electronic wavepacket. Furthermore it is shown that in a motional narrowing regime the averaging over fluctuation causes ballistic propagation of the wavepacket, and in the adiabatic regime the electronic states are affected by localization.     

Effect of electron beam irradiation on the structural,thermal and optical properties of poly(vinyl alcohol) thin film

Poly(vinyl alcohol) (PVA) polymer was prepared using the casting technique. The obtained PVA thin films have been irradiated with electron beam doses ranging from 20 to 300 kGy. The resultant effect of electron beam irradiation on the structural properties of PVA has been investigated using X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR), while the thermal properties have been investigated using thermo-gravimetric analysis and differential thermal analysis (DTA). The onset temperature of decomposition T ₀ and activation energy of thermal decomposition E _a were calculated, results indicate that the PVA thin film decomposes in one main weight loss stage. Also, the electron beam irradiation in dose range 95–210 kGy led to a more compact structure of the PVA polymer, which resulted in an improvement in its thermal stability with an increase in the activation energy of thermal decomposition. The variation of transition temperatures with electron beam dose has been determined using DTA. The PVA thermograms were characterized by the appearance of an endothermic peak due to melting. In addition, the transmission of the PVA samples and any color changes were studied. The color intensity Δ E was greatly increased with increasing electron beam dose, and was accompanied by a significant increase in the blue color component.