Compensation effect observed in thermally stimulated depolarization currents analysis of polymers

Thermally stimulated depolarization currents (TSDC) and differential scanning calorimetry (DSC) are performed on thermoplastic polyesters and dimethacrylate resins over temperature ranges covering the α and β relaxation regions. The noncooperative β relaxation is characterized by a continuous variation of activation energies as a function of temperature and follows the activated states equation with a zero activation entropy. The cooperative α relaxation shows a prominent maximum of the activation energies at the glass transition temperature. Compensation behavior is often observed by TSDC for many polymers in the glass transition temperature range. We show that this behavior is not systematic and that it appears for the α relaxation if the increase of the apparent activation enthalpy is strong and if the width of the glass transition is weak. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2716–2723, 1999     

Open- and short-circuit thermally stimulated currents in ethyl cellulose

Thermally stimulated currents (TSCs) in short-circuit and open-circuit configuration for ethyl cellulose samples (≈40 µm thick) have been studied as a function of polarizing field (25–100kV/cm) and polarizing temperature (323–353K). The thermograms have been found to be characterized by two prominent peaks located around 70 ± 10°C and 140 ± 10°C and the appearance of anomalous current in the high temperature region of the short-circuit TSC thermograms. The observed behaviour has been explained in terms of the existence of heterocharge due to dipole orientation and ionic homocharge drift, together with the injection of charge carriers from electrodes and their subsequent localization in surface and bulk traps.     

Transient and thermally stimulated depolarization currents in polyvinyl formal films

Transient currents in double-sided vacuum aluminized polyvinyl formal (PVF) film samples of thickness 40 μm were investigated in the charge and discharge modes at different temperatures and fileds. The results observed suggest that the transient currents are governed by charge injection processes leading to space charge effects. Comparative studies of the isochronal characteristics (i.e. current–temperature plots at fixed times) with the thermally stimulated discharge current (TSDC) indicated a strong resemblance between the two techniques. These studies suggest that the simultaneous mechanism of movement of charges through microscopic distances coupled with dipolar orientation may be responsible for the TSDC peak observed at 100°C.     

Preparation and characterization of poly(vinyl alcohol) and gelatin blend films

Poly(vinyl alcohol) (PVA) is a water-soluble polymer that has been studied intensively because of several interesting physical properties that are useful in technical applications, including biochemical and medical applications. In this article, we report the effects of the addition of gelatin on the optical, microstructural, thermal, and electrical properties of PVA. Pure and PVA/gelatin blend films were prepared with the solution-casting method. These films were further investigated with Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), ultraviolet–visible (UV–vis) spectroscopy, and dielectric measurements. The FTIR spectrum shows a strong chemical interaction between PVA and gelatin molecules with the formation of new peaks. These peaks are due to the presence of gelatin in the blend films. The DSC results indicate that the addition of gelatin to PVA changes the thermal behavior, such as the melting temperature of PVA, and this shows that the blends are compatible with each other. This also shows that the interaction of gelatin and PVA molecules changes the crystallite parameters and the degree of crystallinity, and this supports the XRD results. The UV–vis optical study also reflects the formation of the complex and its effect on the microstructure of the blend film. Moreover, the addition of gelatin also gives rise to changes in the electrical properties of PVA/gelatin blend films. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Transient currents in poly(vinyl alcohol)–poly(vinyl pyrrolidone) polymer blend films

Transient currents (charging and discharging currents) in poly(vinyl alcohol) (PVA)–poly(vinyl pyrrolidone) (PVP) polymer blend films were measured over the temperature range 30–150°C at field strengths of 2.32–23.2 × 10⁶ Vm^?1. Polymer films were prepared by the isothermal immersion technique. Activation energies were evaluated from quasi-steady-state currents. A single relaxation peak was observed both from isochronal currents and low frequency dielectric relaxation. Activation energies evaluated from these two methods are found to be in fairly good agreement. The polarization is considered to be due to space charge origin along with some contribution from dipolar groups. The maximum loss was observed in Sample I (PVA: PVP = 25:75), suggesting maximum heterogeneity in this blend ratio.     

Alpha relaxation study in poly(vinyl chloride)/poly(ethyl methacrylate) blends using thermally stimulated currents

Thermoelectrets of poly(vinyl chloride) (PVC) and poly(ethyl methacrylate) (PEMA) blends were prepared using the conventional thermal poling method. α‐Relaxation in this polyblend was investigated using thermally stimulated depolarization currents (TSDC). The global spectra of the polyblends revealed that the two polymers are not completely compatible. An Eyring relationship was verified through the linear relation between the activation enthalpy ΔH and the activation entropy ΔS. In addition, the thermal sampling (TS) data were used to determine the compensation parameters such as compensation temperature T_c and compensation time (τ_c). These parameters were used to calculate the density of disorder (DOD) for all samples, which was found to be close to 32%. © 2000 Society of Chemical Industry     

Molecular motions in poly(vinyl acetate) revisited. A thermally stimulated current study

The dipolar relaxation mechanisms in poly(vinyl acetate) have been studied in detail using the technique of thermally stimulated currents. The papers published in the literature about this subject are very contradictory, particularly with respect to the assignment of the observed discharges to the corresponding motions at the molecular level. This work aims at clarifying these problems. We detected and characterised three different relaxation mechanisms: (1) a low temperature one (around ?140°C) which was attributed to local internal rotations in the acetate side-groups; (2) a relaxation whose maximum occurs at 42°C, which corresponds to the glass transition relaxation, and shows a compensation behaviour; (3) an upper glass transition relaxation whose maximum appears at 87°C and was attributed to a liquid-liquid transition. These assignments have been made on the basis of the analysis of the behaviour of the samples when submitted to different thermal and electrical treatments.     

Effect of graphene loading on thermomechanical properties of poly(vinyl alcohol)/starch blend

Polymer nanocomposites based on poly(vinyl alcohol) (PVA)/starch blend and graphene were prepared by solution mixing and casting. Glycerol was used as a plasticizer and added in the starch dispersion. The uniform dispersion of graphene in water was achieved by using an Ultrasonicator Probe. The composites were characterized by FTIR, tensile properties, X‐ray diffraction (XRD), thermal analysis, and FE‐SEM studies. FTIR studies indicated probable hydrogen bonding interaction between the oxygen containing groups on graphene surface and the –OH groups in PVA and starch. Mechanical properties results showed that the optimum loading of graphene was 0.5 wt % in the blend. XRD studies indicated uniform dispersion of graphene in PVA/starch matrix upto 0.5 wt % loadings and further increase caused agglomeration. Thermal studies showed that the thermal stability of PVA increased and the crystallinity decreased in the presence of starch and graphene. FE‐SEM studies showed that incorporation of graphene increased the ductility of the composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41827.     

Studies on dielectric relaxation and ac conductivity of cellulose acetate hydrogen phthalate–poly (vinyl pyrrolidone) blend

The dielectric constant, dielectric loss, and ac conductivity of polyblends of cellulose acetate hydrogen phthalate (CAP) and poly (vinyl pyrrolidone) (PVP) of different compositions were measured in the temperature range of 300–430 K and in the frequency range of 50 Hz–100 kHz. In the blends, the dielectric constant as well as the dielectric loss as a function of the temperature display a single peak corresponding to the glass transition temperature (T_g) in the region between the T_g values of the pure polymers. The T_g values observed agree well with those values obtained from DSC. Dielectric studies show that CAP forms a miscible blend with PVP. Ac conductivity values were calculated from the dielectric data and the conduction mechanism is discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1702–1708, 2002     

Controlled release of naproxen from sodium alginate and poly(vinyl alcohol)/sodium alginate blend beads crosslinked with glutaraldehyde

In this study, polymeric beads of sodium alginate (NaAlg) and its blend with poly(vinyl alcohol) (PVA) were prepared by crosslinking with glutaraldehyde (2.5% v/v) and hydrochloric acid (3% v/v) for the release of naproxen sodium (NS). The prepared beads were characterized with Fourier transform infrared spectroscopy, and pictures of the beads were determined with an optic microscope. The release studies were carried out at three pH values (1.2, 6.8, and 7.4) for 2 h. The effects of the preparation conditions, including the PVA/NaAlg (w/w) ratio, drug/polymer (w/w) ratio, and time of exposure to the crosslinker, on the release of NS were investigated for 10 h at 37°C. The release of NS decreased with the PVA/NaAlg (w/w) ratio and drug/polymer ratio increasing. At the end of 10 h, the highest release of NS was found to be 84% for the 1/2 PVA/NaAlg (w/w) ratio. The swelling measurements of the beads supported the release results. The release kinetics were described with Fickian and non‐Fickian approaches. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation,characterization, electrical and antibacterial properties of sericin/poly(vinyl alcohol)/poly(vinyl pyrrolidone) composites

In this study, we focused on the fabrication of poly(vinyl alcohol) (PVA)/poly(vinyl pyrrolidone) (PVP)/sericin composites via a simple solution‐blending method. The composites were characterized by Fourier transform infrared (FTIR) spectroscopy, UV spectroscopy, X‐ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry, thermogravimetric analysis (TGA), and measurements of the conductivity, tensile strength, and antibacterial activity against Staphylococcus aureus. The results of FTIR and UV spectroscopy implied the occurrence of hydrogen bonding between sericin and the PVA/PVP blend. The structure and morphology, studied by XRD and SEM, revealed that the sericin particles were well dispersed and arranged in an orderly fashion in the blend. The glass‐transition temperature (T_g) of the composite was higher than that of the pure blend, and the T_g value shifted toward higher temperatures when the volume fraction of sericin increased. TGA indicated that sericin retarded the thermal degradation; this depended on the filler concentration. The mechanical and electrical properties, such as the tensile strength, alternating‐current electrical conductivity, dielectric constant, and dielectric loss of the composites, were higher than those of the pure blend, and these properties were enhanced when the concentration of sericin was increased up to 10 wt % filler content, whereas the elongation at break of the composite decreased with the addition of sericin particles. The antibacterial properties of the composite showed that sericin had a significant inhibitory effect against S. aureus. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43535.     

Preparation and thermal properties of hybrid nanocomposites of poly(methyl methacrylate)/octavinyl polyhedral oligomeric silsesquioxane blends

A series of poly(methyl methacrylate) (PMMA)/octavinyl polyhedral oligomeric silsesquioxane (POSS) blends were prepared by the solution‐blending method and characterized with Fourier transform infrared, X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analysis techniques. The glass‐transition temperature (T_g) of the PMMA–POSS blends showed a tendency of first increasing and then decreasing with an increase in the POSS content. The maximum T_g reached 137.2°C when 0.84 mol % POSS was blended into the hybrid system, which was 28.2°C higher than that of the mother PMMA. The X‐ray diffraction patterns, transmission electron microscopy micrographs, and Fourier transform infrared spectra were employed to investigate the structure–property relationship of these hybrid nanocomposites and the T_g enhancement mechanism. The results showed that at a relatively low POSS content, POSS as an inert diluent decreased the interaction between the dipolar carbonyl groups of the homopolymer molecular chains. However, a new stronger dipole–dipole interaction between the POSS and the carbonyl of PMMA species formed at the same time, and a hindrance effect of nanosize POSS on the motion of the PMMA molecular chain may have played the main role in the T_g increase of the hybrid nanocomposites. At relatively high POSS concentrations, the strong dipole–dipole interactions that formed between the POSS and carbonyl groups of the PMMA gradually decreased because of the strong aggregation of POSS. This may be the main reason for the resultant T_g decrease in these hybrid nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Molecular mobility of CU(II)-containing liquid crystalline ionomers: dielectric relaxation and thermally stimulated depolarization currents

Molecular mobility of functionalized liquid crystalline (LC) copolymer (P1) containing mesogenic cyanobiphenyl groups and acrylic acid fragments (28%) as well as LC ionomers P2 (Cu 2.5() and P3 (Cu 7() with copper ions were studied by dielectric spectroscopy (DS) and by thermally stimulated depolarization current (TSDC) methods. For P1-P3, the frequency dependences of dielectric losses and temperature dependences of depolarization current were obtained and four relaxation processes γ₁, β, α, and δ were found. For each of them a molecular mechanism was proposed. Moreover, for P1, P2, and P3, at high temperatures the TSDC global curves indicate the peak of depolarization current, which has no analogue in the dielectric spectrum. For P1 this peak is a ρ-process of low intensity. For P2 and P3 ionomers the intensity and temperature position of the high temperature peak increase as compared to those of P1. The mechanisms of the high temperatures peak for the P2 and P3 systems containing copper ions were attributed to the free space charge polarization and to the dipole polarization process of polymer chains included in ionic associates (multiplets). There is good correlation between the peak temperature positions obtained from the global TSDC spectrum at equivalent frequency and those obtained from DS.     

Binary polymer blend of ArPTU/PI with advanced comprehensive dielectric properties and ultra-high thermally stability

Flexible high-temperature polymeric dielectrics with advanced dielectric properties are urgently demanded in various applications. In this work, series of polymer blend films were prepared from aromatic polythiourea (ArPTU) and polyimide (PI). The experimental results revealed that the blend films were properly engineered to achieve higher breakdown strength, greater dielectric constant, and larger energy density than pure PI film. For instance, the optimum property was obtained from the blend film with 10 wt% ArPTU, exhibiting prominent dielectric properties (K = 4.52, E_b = 443 MV/m), enhanced energy density (4.00 J/cm³) as well as excellent heat resistance (T_g = 419°C). In addition, stable dielectric properties at broad temperature range from −50 to 250°C were also acquired. It is deduced that the good compatibility from ArPTU and PI with similar polarity are responsible for the improved properties. The superior comprehensive properties which combine the advantages of ArPTU and PI suggest the potential applications of ArPTU/PI blend film in high-temperature dielectric areas.     

Miscibility and thermal behavior of poly(vinyl chloride)/feather keratin blends

Various poly(vinyl chloride) (PVC)/feather keratin (FK) blends were prepared via a solution blending method in the presence of N,N‐dimethylformamide as a solvent. The miscibility of the blends was studied with different analytical methods, such as dilute solution viscometry, differential scanning calorimetry, refractometry, and atomic force microscopy. According to the results obtained from these techniques, it was concluded that the PVC/FK blend was miscible in all the studied compositions. Specific interactions between carbonyl groups of the FK structure and hydrogen from the chlorine‐containing carbon of the PVC were found to be responsible for the observed miscibility on the basis of Fourier transform infrared spectroscopy. Furthermore, increasing the FK content in the blends resulted in their miscibility enhancement. The thermal stability of the samples, as an important characteristic of biobased polymer blends, was finally examined in terms of their FK weight percentage and application temperature. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of poly(vinyl chloride)/chlorinated polyethylene blend composition on thermal stability

Blends of poly(vinyl chloride) (PVC) with different ratios of chlorinated polyethylene (CPE) were degradated by the thermogravimetric method under dynamic conditions (50–600°C) in an inert atmosphere. The effect of the miscibility and composition of the PVC/CPE blends on the thermal stability were investigated. DSC curves of the blends show neither a shift of the PVC glass transition temperature nor a shift of the CPE melting temperature, which means that these blends are heterogeneous. The characteristics of the TG curves were determined, some of which (T_1%,T_5%, Δm₁) can be used as indicators of the thermal stability of the blend. The apparent activation energy of PVC dehydrochlorination in the blends was also calculated. Comparison of the experimental TG curves and TG curves predicted by the additivity rule indicates the existence of the components' interaction in the PVC/CPE blends. The addition of CPE improves the thermal stability of PVC for all the investigated blends in the temperature range where α_calc is greater than α_exp. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 166–172, 2000     

Solution and solid‐state blend compatibility of poly(vinyl alcohol) and poly(methyl methacrylate)

The blend miscibility of poly(vinyl alcohol) and poly(methyl methacrylate) in N,N′‐dimethylformamide solution was investigated by viscosity, density, ultrasonic velocity, refractive index, and UV and fluorescence spectra studies. Differential scanning calorimetry and scanning electron microscopy were used to confirm the blend miscibility in the solid state. Blends were compatible when the concentration of poly(vinyl alcohol) was greater than 60 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2415–2421, 2006     

A critical phenomenon of phase transition in hydroxyapatite investigated by thermally stimulated depolarization currents

We observed a critical phenomenon of ferroelectric transition in hydroxyapatite (HAp) through measuring the thermally stimulated depolarization current of polycrystalline monoclinic HAp. Two peaks attributable to hydroxide (OH^?) ion dipole reorientations were observed. The one was very sharp, the other displayed a broad peak ranging from 350 to 550 K. While the broad peak can be attributed to the diffusive reorientation motions of OH^? ion dipoles, the sharp peak, related to the ferroelectric phase transition, implies the presence of ferroelectricity in HAp. The sharp peak was found near 380 K, the phase‐transition temperature from the monoclinic to hexagonal is ascribed to a critical phenomenon caused by the ferroelectric behavior of OH^? ion dipole reorientations.     

Preparation of atactic poly(vinyl alcohol)/sodium alginate blend nanowebs by electrospinning

Through the blending of a rigid polymer, sodium alginate (SA), and a flexible polymer, atactic poly(vinyl alcohol) (PVA), with various ratios of SA and PVA and through the electrospinning of SA/PVA solutions, SA/PVA blend nanowebs were successfully prepared. The structure and morphology of the SA/PVA blend nanowebs were investigated through a series of instrumental analyses. Through the examination of the morphological variations of each blend web, it was found that with only PVA, the electrospun nanowebs had very uniform and fine fiber structures, but the SA/PVA blend nanowebs had a mixture of large beads and fibers, which were generated with increasing SA content. A thermal analysis indicated that the endothermic peaks of the SA/PVA blend nanowebs decreased with an increase in the SA content. The SA content was determined by the observation of the changes in the SA peak intensity via Fourier transform infrared spectroscopy. The tensile strength decreased with increasing SA content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Electromagnetic interference shielding properties of graphene quantum-dots reinforced poly(vinyl alcohol)/polypyrrole blend nanocomposites

Graphene quantum dots (GQDs) reinforced poly(vinyl alcohol) (PVA)/polypyrrole (WPPy) nanocomposite films with various GQDs loadings were synthesized using the versatile solvent casting method. The structural and morphological properties of PVA/WPPy/GQDs nanocomposite films were investigated by employing Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy. The thermogravimetric analysis revealed enhanced thermal stability of synthesized nanocomposites while enhanced dielectric properties were also observed. The maximum dielectric constant value for PVA/WPPy/GQDs nanocomposite films was observed to be ε = 6,311.85 (50 Hz, 150°C). The electromagnetic interference (EMI) shielding effectiveness (SE) of nanocomposite films was determined in the X-band (8–12 GHz) and Ku-band (12–18 GHz) frequency region. The EMI SE was found to be increased from 0.8 dB for the pure PVA film to 9.8 dB for the PVA/WPPy/GQDs nanocomposite film containing 10 wt% GQDs loading. The enhanced EMI shielding efficiency of nanocomposite films has resulted from the homogenous dispersion of GQDs in PVA/WPPy blend nanocomposites. Thus, the prepared nanocomposites are envisioned to utilize as a lightweight, flexible, and low-cost material for EMI shielding applications.