Thermally stimulated depolarization currents in poly(2,6-dimethyl-1,4-phenylene oxide) films

Electrical properties of poly(2,6- dimethyl-1,4-phenylene oxide) (PPO) have been studied by measuring thermally stimulated discharge currents. Depolarization behavior of poled PPO film exhibits temperature- and time-dependent single relaxation around 468 K which is attributed to dipole reorientation. The peak maxima, however, shifts from 468 K to 484 K with increasing poling temperature. This indicates that the peak has a distribution of relaxation times. The polarization in semicrystalline PPO is found to decay slowly, indicating that the overall dipoles are more stable in comparison to amorphous PPO; hence, crystalline PPO forms comparatively stable electrets. © 1996 John Wiley & Sons, Inc.     

Thermally stimulated discharge currents in poly(vinyl formal) films

Thermally stimulated discharge currents (t.s.d.c.) of pure poly(vinyl formal) films of thickness 42.5 μm grown by the solution growth technique have been studied as a function of polarizing field and polarizing temperature. The temperature corresponding to a peak in t.s.d.c. is found to be independent of polarizing field but dependent on the polarizing temperature. Activation energies and relaxation parameters are evaluated.     

Thermally stimulated discharge currents in poly(vinyl alcohol) thermoelectrets

The depolarization currents in poly(vinyl alcohol) thermoelectrets have been measured by thermally stimulated discharge (t.s.d.) current techniques. The polarization is found to be uniform. The activation energy and the relaxation time have been calculated under different polarizing conditions. The formation of heterocharge is explained by dipole alignment and migration of charge over microscopic distances with trapping.     

Sulfonated poly(ethylene‐ran‐styrene) ionomers

Ionomers were prepared by partially sulfonating the styrene units of a poly(ethylene‐ran‐styrene) (ES) copolymer. The metal salt derivatives of sulfonated ES had higher T_g, melt viscosity and rubbery modulus than did the parent ES because of the formation of labile, physical crosslinks from intermolecular dipole–dipole associations between metal sulfonate groups. Microphase separation of ion‐rich aggregates with a characteristic size of 3–9 nm also occurred as a result of the strong intermolecular associations. Copyright © 2005 Society of Chemical Industry     

Thermal degradation of poly(p‐phenylenebenzobisoxazole) and poly(p‐phenylenediamine terephthalamide) fibres

This study investigates the thermal stability of poly(p‐phenylenediamine‐terephtalamide) (PPT) and poly(p‐phenylenebenzobisoxazole) (PBO) fibres. Excellent behaviour of PBO is shown in comparison to that of PPT. The thermal stability (under pyrolytic or thermo‐oxidative conditions) of PBO is 150 °C higher than that of PPT. Moreover, the strong influence of oxygen, which plays the role of an initiator of degradation, on the degradation of fibres is shown. Using the invariant kinetic parameter (IKP) method, it is shown that the degradation rate of PBO is strongly reduced in comparison with that of PPT. It provides a simulation of the ‘fuel flow’ able to feed the flames, which can explain the high fire performance of PBO compared to PPT. © 2001 Society of Chemical Industry     

Thermally stimulated depolarization (TSD) current study of plasticized PVC

Summary Plasticized PVC samples of different plasticizer concentration were tested by the thermally stimulated discharge current (TSD) method. Processing conditions were also varied. It has been found that plasticized PVC consists of at least three structural units having different molecular mobility. Their amount and characteristics strongly depend on the processing conditions, i.e. the thermal- and shear history of the material. TSD method because of its excellent resolving power proved to be a useful tool detecting these structural units. Received: 9 June 1998/Revised version: 2 November 1998/Accepted: 2 November 1998     

Thermally stimulated depolarization effect in thiourea-formaldehyde condensate

A thiourea-formaldehyde condensate was synthesized in an acid medium and characterized by elemental analysis, infra-red spectroscopy, and thermal methods of analysis. The thermally stimulated depolarization effect was studied in samples polarized under different conditions. The results indicate two distinct transitions in the temperature ranges 94°–100°C and 122–126°C. The polarization-depolarization phenomena were correlated with the physicochemical changes occurring in the matrix. Depolarization kinetics data such as activation energy and relaxation times of the electrets are reported.     

Thermally stimulated depolarization current behavior of polyethylene/poly(vinyl acetate) blends: Effect of blending

Thermally stimulated depolarization currents (TSDCs) were investigated in polyethylene/poly(vinyl acetate) blends as a function of the polarizing temperature, applied field, and poly(vinyl acetate) weight percentage in the blend. The magnitude of the TSDC peak current decreased and the peak current position shifted toward the lower temperature side as the poly(vinyl acetate) weight percentage in the blends was increased. The tendency of the current toward anomalous behavior (flowing in the same direction as the charging current) also increased. It was concluded that blending with poly(vinyl acetate) modified the polyethylene morphology such that the amorphous part was increased. The carriers with mobility enhanced by hopping centers due to the C?O group in the amorphous part were localized largely in shallow traps. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3040–3045, 2006     

Thermally stimulated currents in methacrylonitrile-styrene copolymer films

Summary Measurements are reported on thermally stimulated discharge current in methacrylonitrile — styrene copolymer films. The values of activation energy and relaxation times were calculated.     

Effect of tacticity on the transition behaviour of poly(methyl methacrylate)/poly(vinyl chloride) blends. Thermally stimulated depolarization study

The transition behaviour of blends of poly(vinyl chloride) (PVC) and poly(methyl methacrylate) isotactic (i-PMMA) and syndiotactic (s-PMMA) was determined in the temperature range ?150°C to +130°C by the thermally stimulated depolarization currents method (TSDC). The evolution of the current spectra was analysed as a function of blend composition. From the variation of properties of the peaks (presence or not of two T_g peaks, shifting or not of their positions, existence or not of interfacial components, regular or complex variation of the peak amplitudes ...), it was concluded that i-PMMA and PVC form an incompatible system over the entire concentration range while in s-PMMA/PVC blends, some compatibility probably exists but only for concentrations in s-PMMA not higher than 10 wt%. By referring to literature data, this value is much smaller than the compatibility range found from d.s.c. and mechanical measurements but is close to that determined from optical and electronic spectroscopy methods. These results emphasize the important role played by the type of method used to find out compatibility of a given polymer pair and show that the TSDC technique may be particularly useful for studying the interfacial phenomena associated with phase separation owing to its exceptional ability for easily detecting Maxwell-Wagner-Sillars polarization generated by the trapping of charge carriers at phase boundaries.     

Fracture toughness of modified polypropylene/poly(styrene‐ran‐butadiene) blends

Fracture toughness of polypropylene (PP)/poly(styrene‐ran‐butadiene) rubber (SBR) blends as a function of concentration of maleic anhydride (MA) in the maleated polypropylene (MAPP) compatibilizer was investigated under uniaxial static and impact loading conditions. The addition of MAPP to the unmodified PP/rubber blend enhanced the tensile modulus and yield stress as well as the Charpy impact strength. The maximum values were recorded at 1.0 wt% grafted MA in the compatibilizer. V‐shaped blunt‐notched specimens exhibited typical ductile behavior and no breakage of the specimens occurred during the impact fracture tests. Sharp‐notched specimens of uncompatibilized and low‐content MA blends broke in a semibrittle manner, supported by a rapid crack propagation process. Increasing MA content in the blends led to semibrittle‐to‐ductile transition characterized by stable crack propagation. Fracture mechanics experiments, supplemented by scanning electron microscopy (SEM), were also employed to obtain a better understanding of the fracture and deformation behavior. Copyright © 2005 Society of Chemical Industry     

Synthesis and properties of poly(acrylonitrile‐co‐p‐trimethylsilylstyrene) and poly(acrylonitrile‐co‐p‐trimethylsilylstyrene‐co‐styrene)

Copolymerization of acrylonitrile (AN) with p‐trimethylsilylstyrene (TMSS) was carried out at 60°C in bulk and in solution in the presence of 2,2′‐azobisisobutyronitrile (AIBN). The reactivity ratios of AN (M₁) and TMSS (M₂) were determined to be r₁ = 0.068 and r₂ = 0.309. The effects of the AIBN concentration and that of the chain transfer agent CCl₄ on the molecular weights (MWs) of the copolymers were investigated. An increase in the concentrations of AIBN or CCl₄ in solution led to a decrease in MW. Poly(AN‐co‐TMSS‐co‐St) was synthesized in solution using AIBN as the initiator. The molar fraction of AN was 0.415, while the molar ratio of TMSS/St varied from 1 : 1 to 1 : 9. The transition temperatures and thermal and thermooxidative stabilities of poly(AN‐co‐TMSS) and poly(AN‐co‐TMSS‐co‐St) were investigated. The differential scanning calorimeter technique was used to determine the compatibility of the poly(AN‐co‐TMSS) and poly(AN‐co‐TMSS‐co‐St) with commercial poly(AN‐co‐St). All the blends show a single glass transition temperature, which indicates the compatibility of the blend components. The surface film morphology of the blends mentioned above was examined by X‐ray photoelectron spectroscopy. The data obtained indicate that the silicon‐containing copolymer is concentrated in the surface layer. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1920–1928, 2000     

Stimuli sensitive copolymer poly(N‐tert‐butylacrylamide‐ran‐acrylamide): Synthesis and characterization

Temperature sensitive random linear and crosslinked copolymers of N‐tert‐butylacrylamide (NTBA) and acrylamide (Am) were synthesized by the solution polymerization method, using regulated dosing of comonomer Am having a higher reactivity ratio (r_Am = 1.5) than NTBA (r_NTBA = 0.5). Copolymers with varying feed ratios of NTBA and Am (80 : 20 to 20 : 80 mol %) were synthesized and characterized. For the synthesis of copolymer hydrogels, N′, N‐methylene bisacrylamide (MBA) (1.13 mol %) was used along with monomers. The effect of composition on transition properties was evaluated for the linear copolymers and their hydrogels. A definite trend was observed. The incorporation of a higher percentage of the hydrophilic comonomer Am in the structure resulted in the shifting of the transition temperature towards a higher value. The transition temperatures of the copolymers synthesized with feed compositions of 80 : 20, 70 : 30, 60 : 40, 50 : 50, 40 : 60, 30 : 70, and 20 : 80 mol % were found to be 2, 10, 19, 27, 37, 45, and 58°C, respectively. Differential scanning calorimetry (DSC) studies confirmed the formation of random copolymers. The copolymers synthesized with a monomer feed ratio of 50 : 50 with regulated dosing showed a single glass transition temperature (T_g) at 168°C, while the copolymer synthesized with full dosing of Am at the beginning of the reaction showed two T_gs, at 134 and 189°C. The copolymer samples were analyzed by Fourier transform infrared spectroscopy (FTIR) for ascertaining the composition. The composition of the copolymers followed the trend of the feed ratio, but the incorporation of NTBA in the copolymers was found to be lower than the feed ratio because of lower than quantitative yields of the reactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 672–680, 2005     

Ultraviolet resistance modification of poly(p‐phenylene‐1,3,4‐oxadiazole) and poly(p‐phenylene terephthalamide) fibers with polyhedral oligomeric silsesquioxane

Octa‐ammonium chloride salt of polyhedral oligomeric silsesquioxane (POSS) was synthesized by a hydrolysis reaction and introduced into poly(p‐phenylene‐1,3,4‐oxadiazole) (p‐POD) and poly(p‐phenylene terephthalamide) (PPTA) fibers by a finishing method to enhance the UV resistance. The effects of the POSS concentration, treatment temperature, and time on the tensile strength of the fibers were investigated. The surface morphology, mechanical properties, crystallinity, degree of orientation of fibers, and intrinsic viscosity of the polymer solution were characterized in detail. The results indicate that the tensile strength retention and intrinsic viscosity retention of the fibers treated with POSS were much higher than those of the untreated fibers after the same accelerated irradiation time; this demonstrated that this treatment method was feasible. We also found that the efficacy of the protection provided by POSS was more beneficial to p‐POD than PPTA because of the different structure. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42643.     

Polymer blends of stereoregular poly(methyl methacrylate) and poly(styrene‐co‐p‐hydroxystyrene)

Isotactic, atactic, and syndiotactic poly(methyl methacrylates) (PMMAs) (designated as iPMMA, aPMMA, and sPMMA) were mixed with poly(styrene‐co‐p‐hydroxystyrene) (abbreviated as PHS) containing 15 mol % of hydroxystyrene separately in 2‐butanone to make three polymer blend systems. Differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy were used to study the miscibility of these blends. The three polymer blends were found to be miscible, because all the prepared films were transparent and there was a single glass transition temperature (T_g) for each composition of the polymers. T_g elevation (above the additivity rule) is observed in all the three PMMA/PHS blends mainly because of hydrogen bonding. If less effective hydrogen bonding based on the FTIR evidence is assumed to infer less exothermic mixing, sPMMA may not be miscible with PHS over a broader range of conditions as iPMMA and aPMMA. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 431–440, 1999     

New copolymer of poly(N‐vinylcarbazole) and poly(p‐phenylenevinylene) for optoelectronic devices

A novel diblock copolymer based on poly(N‐vinylcarbazole) PVK and poly(p‐phenylenevinylene) (PPV) precursor was synthesized by oxidative cross‐linking. The grafting of PPV with PVK moieties was elucidated by infrared absorption analysis. A structural study by X‐ray diffraction and a morphological study of the copolymer by scanning and transmission electron microscopy reveal a multiscale one‐dimensional self‐organization both at the molecular and at the sub‐micrometric level. The resulting copolymer exhibits original optical properties compared to those of PVK and PPV ones and presents an improved thermal behavior. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2839–2847, 2013     

Miscible blends containing bacterial poly(3‐hydroxyvalerate) and poly(p‐vinyl phenol)

The miscibility of poly(3‐hydroxyvalerate) (PHV)/poly(p‐vinyl phenol) (PVPh) blends has been studied by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. The blends are miscible as shown by the existence of a single glass transition temperature (T_g) and a depression of the equilibrium melting temperature of PHV in each blend. The interaction parameter was found to be −1.2 based on the analysis of melting point depression data using the Nishi–Wang equation. Hydrogen‐bonding interactions exist between the carbonyl groups of PHV and the hydroxyl groups of PVPh as evidenced by FTIR spectra. The crystallization of PHV is significantly hindered by the addition of PVPh. The addition of 50 wt % PVPh can totally prevent PHV from cold crystallization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 383–388, 1999     

Reactive compatibilization of poly(methyl acrylate‐ran‐acrylonitrile)/poly(ethylene) blends through amine–anhydride coupling

Methyl acrylate/acrylonitrile copolymers (MA/AN) were reactively compatibilized as the dispersed phase into poly(ethylene) (PE) for potential hydrocarbon barrier materials. The MA/AN was made reactive by including p‐aminostyrene (PAS), yielding terpolymers (MA/AN/PAS) with pendant primary amine functionality (number average molecular weight = 65–133 kg mol^?1, dispersity (?)=1.83–2.53, molar composition of PAS in copolymer F_PAS = 0.03–0.14, molar composition of AN = F_AN = 0.27–0.52). The non‐functional MA/AN and amino functional MA/AN/PAS were each melt blended into PE that was grafted with maleic anhydride (PE‐g‐MAnn) at 200 °C at 70:30 wt % PE‐g‐MAnn:co/terpolymer. After extrusion, the dispersed phase particle size (volume to surface area diameter, ) was coarse (12.6 μm) for the non‐reactive blend whereas it was much lower for the reactive blend ( = 1.2 μm). Coarsening after annealing at 150 °C was slow, but the domain sizes increased only slightly for both cases. The reactive blend was deemed sufficiently stable and thus was suitable as a candidate barrier material for further testing against olefins. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44177.     

Reactive compatibilization of poly(styrene‐ran‐acrylonitrile)/poly(ethylene) blends through the acid–epoxy reaction

Two families of acid functional styrene/acrylonitrile copolymers (SAN) for application as dispersed phase barrier materials in poly(ethylene) (PE) were studied. One type is SAN made by nitroxide mediated polymerization (NMP), which was subsequently chain extended with a styrene/tert‐butyl acrylate (S/tBA) mixture to provide a block copolymer (number average molecular weight M_n = 36.6 kg mol^?1 and dispersity ? = 1.34, after which the tert‐butyl protecting groups were converted to acid groups (SAN‐b‐S/AA). The other acid functional SAN is made by conventional radical terpolymerization (SAN‐AA). SAN‐AA and SAN‐b‐S/AA were each melt blended with PE grafted with epoxy functional glycidyl methacrylate (PE‐GMA) at 160 °C in a twin screw extruder (70:30 wt % PE‐GMA:SAN co/terpolymer). The non‐reactive PE‐g‐GMA/SAN blend had a volume to surface area diameter = 3.0 μm while the reactive blends (via epoxy/acid coupling) (PE‐GMA/SAN‐b‐SAA and PE‐GMA/SAN‐AA) had = 1.7 μm and 1.1 μm, respectively. After thermal annealing, the non‐reactive blend coarsened dramatically while the reactive blends showed little signs of coarsening, suggesting that the acid/epoxy coupling was effective for morphological stability. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44178.