Annealing effect on chain segment motion and charge detrapping in polyamide 610

The chain segment motion and charge detrapping in polyamide 610 films have been investigated by means of thermally stimulated depolarization current (TSDC) and wide‐angle X‐ray diffraction. There are three current peaks (namely α, ρ₁, and ρ₂ peaks) in the TSDC spectra above room temperature. α peak is attributed to a dipole relaxation by the motion of chain segments ρ₁ peak is caused by space charge trapped in amorphous phase and the interphase between crystalline and amorphous phases, and ρ₂ peak is brought about by space charge trapped in crystalline phase. By analyzing the characteristic parameters of these peaks, it is found that annealing induces the decrease of chain segment mobility and promotes the creation of structural traps in polyamide 610. The decrease of chain segment mobility in amorphous phase makes intensity of α peak weak and activation energy increscent. The higher the annealing temperature, the higher the degree of crystallinity, the more the charge carriers trapped in crystalline phase. So, the increase of degree of crystallinity makes intensity of ρ₂ peak strong and increases the stability of trapped charge in the crystalline phase. The increase of annealing temperature makes intensity of ρ₁ peak strong and decreases the stability of trapped charge in the amorphous phase and interphase. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of Cure Conditions on the Adhesion of Rubber Compound to Brass-plated Steel Cord. Part II. Cure Time

The effect of the cure time of a rubber compound on the adhesion with brass-plated steel cord was investigated. The formation, growth and degradation of the adhesion interphase formed between the rubber compound and brass-plated steel cord was also observed as well as the formation of a weak boundary layer in the rubber near the adhesion interphase. With increase in the cure time from a fourth to four times of t ₉₀, the pull-out force after vulcanization increased significantly up to one-half of t ₉₀ followed by a slight increase to t ₉₀, and then decreased slowly with further increase in cure time. This decrease in pull-out force upon prolonged vulcanization may be explained by the severe degradation of rubber compound attached to the adhesion interphase. Also, upon prolonged vulcanization, the adhesion interphase with a rich ZnS layer may act as a barrier to copper diffusion which is required to form the adhesion interphase of copper sulfide. After thermal aging of the adhesion samples, the pull-out force decreased in comparison with that of the unaged. The decrease of pull-out force after thermal aging stemmed mainly from the decline of tensile properties after thermal aging. The adhesion after humidity aging was different from that after thermal aging. Upon increasing the cure time to one-half of t ₉₀, the pull-out force increased. But a further increase in the cure time caused a decline in pull-out force. This phenomenon can be explained by the degradation of the adhesion interphase. At longer cure time, a severe growth of copper sulfide and a large amount of dezincification were observed in the adhesion interphase. At shorter cure time, a significant growth of copper sulfide in the adhesion interphase does not occur, whereas the formation a of a ZnS layer appeared after humidity aging. With increasing cure time, the formation of a weak boundary layer in the rubber near the adhesion interphase increased, resulting in the cohesive failure of the rubber layer. The proper formation of the adhesion interphase and the good physical properties of the rubber compound at optimum cure time can lead to the high retention of adhesion.     

Influence of Cure Conditions on the Adhesion of Rubber Compound to Brass-plated Steel Cord. Part II. Cure Time

The effect of the cure time of a rubber compound on the adhesion with brass-plated steel cord was investigated. The formation, growth and degradation of the adhesion interphase formed between the rubber compound and brass-plated steel cord was also observed as well as the formation of a weak boundary layer in the rubber near the adhesion interphase. With increase in the cure time from a fourth to four times of t₉₀, the pull-out force after vulcanization increased significantly up to one-half of t₉₀ followed by a slight increase to t₉₀, and then decreased slowly with further increase in cure time. This decrease in pull-out force upon prolonged vulcanization may be explained by the severe degradation of rubber compound attached to the adhesion interphase. Also, upon prolonged vulcanization, the adhesion interphase with a rich ZnS layer may act as a barrier to copper diffusion which is required to form the adhesion interphase of copper sulfide. After thermal aging of the adhesion samples, the pull-out force decreased in comparison with that of the unaged. The decrease of pull-out force after thermal aging stemmed mainly from the decline of tensile properties after thermal aging. The adhesion after humidity aging was different from that after thermal aging. Upon increasing the cure time to one-half of t₉₀, the pull-out force increased. But a further increase in the cure time caused a decline in pull-out force. This phenomenon can be explained by the degradation of the adhesion interphase. At longer cure time, a severe growth of copper sulfide and a large amount of dezincification were observed in the adhesion interphase. At shorter cure time, a significant growth of copper sulfide in the adhesion interphase does not occur, whereas the formation a of a ZnS layer appeared after humidity aging. With increasing cure time, the formation of a weak boundary layer in the rubber near the adhesion interphase increased, resulting in the cohesive failure of the rubber layer. The proper formation of the adhesion interphase and the good physical properties of the rubber compound at optimum cure time can lead to the high retention of adhesion.     

Accelerated aging of elastomeric composites with vulcanized ground scraps

The aim of this work is to study the effect of thermal aging on the mechanical, dynamic‐mechanical, and chemical properties of SBR (styrene‐butadiene rubber) composites filled with SBR industrial rubber scraps. Eight composites with varying proportions (10–80 phr) of the SBR ground scraps (SBR‐r) were prepared and subjected to accelerated aging in an air‐oven. The composites were evaluated, and the results were compared with a control sample (base formulation with 0 phr of SBR‐r), before and after thermal aging. The accelerated aging led to a decrease in the mechanical properties as a result of an increase in the stiffness of the material, related to an increase in the crosslink density. However, these properties were not affected by the addition of rubber scraps up to 50 phr, either before or after aging. The increase in the glass transition temperature of the composites after aging, measured using dynamic mechanical analysis, confirmed the occurrence of a postcrosslinking process. Fourier transform infrared spectroscopy and crosslink density revealed that the aging mechanism was dependent on the SBR‐r content. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of Cure Conditions on the Adhesion of Rubber Compound to Brass-plated Steel Cord. Part I. Cure Temperature

The effect of the cure temperature of rubber compound on the adhesion with brass-plated steel cord was investigated in conjunction with the formation, growth and degradation of the adhesion interphase formed between the rubber compound and brass-plated steel cord. With increasing cure temperature from 130°C to 190°C, the pull-out force after cure decreased linearly. This decrease in adhesion force at higher temperature may be explained by the limitation of the mass transfer of vulcanizing agents into the adhesion interphase and/or rubber compound near the adhesion interphase, resulting in a deficiency of sulfur due to the fast cure of the rubber compound which significantly retards the diffusion of vulcanizing chemicals. Also, at a high temperature, an adhesion interphase with a ZnS-rich layer, which may act as a barrier to copper diffusion for the formation of the adhesion interphase of copper sulfide, was formed. After thermal aging of the adhesion samples, the pull-out force decreased in comparison with that of the unaged. The decrease of pull-out force after thermal aging stemmed mainly from the decline of the tensile properties after thermal aging. The adhesion property after humidity aging was completely different from that after thermal aging. With increase in the cure temperature to 160°C, the pull-out force increased. But further increase in the cure temperature caused a decline in pull-out force. This phenomenon can be explained by the degradation of the adhesion interphase. At lower cure temperatures, a severe growth of copper sulfide and a large extent of dezincification were observed in the adhesion interphase. At higher cure temperatures, a significant growth of copper sulfide in the adhesion interphase appeared. The proper formation of the adhesion interphase and good physical properties of the rubber compound at a moderate cure temperature can result in high retention of adhesion properties.     

Influence of Cure Conditions on the Adhesion of Rubber Compound to Brass-plated Steel Cord. Part I. Cure Temperature

The effect of the cure temperature of rubber compound on the adhesion with brass-plated steel cord was investigated in conjunction with the formation, growth and degradation of the adhesion interphase formed between the rubber compound and brass-plated steel cord. With increasing cure temperature from 130°C to 190°C, the pull-out force after cure decreased linearly. This decrease in adhesion force at higher temperature may be explained by the limitation of the mass transfer of vulcanizing agents into the adhesion interphase and/or rubber compound near the adhesion interphase, resulting in a deficiency of sulfur due to the fast cure of the rubber compound which significantly retards the diffusion of vulcanizing chemicals. Also, at a high temperature, an adhesion interphase with a ZnS-rich layer, which may act as a barrier to copper diffusion for the formation of the adhesion interphase of copper sulfide, was formed. After thermal aging of the adhesion samples, the pull-out force decreased in comparison with that of the unaged. The decrease of pull-out force after thermal aging stemmed mainly from the decline of the tensile properties after thermal aging. The adhesion property after humidity aging was completely different from that after thermal aging. With increase in the cure temperature to 160°C, the pull-out force increased. But further increase in the cure temperature caused a decline in pull-out force. This phenomenon can be explained by the degradation of the adhesion interphase. At lower cure temperatures, a severe growth of copper sulfide and a large extent of dezincification were observed in the adhesion interphase. At higher cure temperatures, a significant growth of copper sulfide in the adhesion interphase appeared. The proper formation of the adhesion interphase and good physical properties of the rubber compound at a moderate cure temperature can result in high retention of adhesion properties.     

Thermal aging on mechanical properties and crosslinked network of natural rubber/zinc Dimethacrylate composites

This article dealt with the relationship between mechanical properties and crosslinked networks of natural rubber (NR) reinforced by zinc dimethacrylate (ZDMA) after thermal aging. After thermal aging at the present experimental conditions, the covalent crosslink density showed a decrease all the time, whereas the ionic crosslink density was stable at 80°C but decreased at a higher temperature. The decrease in the total crosslink density after aging indicates the degradation of the crosslinked network. However, an experimental phenomenon observed was that the tensile strength and tear strength increased in a certain degree after aging at 80°C or at a 100°C for a short time. In addition, the thermal stability of the NR/ZDMA composite was evaluated by thermal gravimetric analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

X‐ray diffraction,Raman, and differential thermal analyses of the thermal aging of a Kevlar®‐PBI blend fabric

A previous study of the effects of thermal aging on the tensile properties of a fabric made of a 60–40 wt % blend of Kevlar and PBI fibers has shown that exposure to elevated temperatures between 190 and 320°C results in a rapid decrease in tensile breaking force retention. In this article, X‐ray diffraction and Raman spectroscopy analyses were carried out to evaluate the consequences of thermal aging on the material's crystallinity. Differential thermal analyses were also undertaken to examine the evolution of the glass transition temperature of PBI following thermal exposure. X‐ray diffraction profiles show a gradual increase in the crystallinity with temperature and aging time, whereas a complete disappearance of spectral lines for aged samples in Raman analysis suggests instead a decrease in crystallinity as a consequence of exposure to elevated temperatures. The seemingly contradictory outcome obtained when using the two techniques led to the proposal of a new, alternative hypothesis to explain the observed results. This hypothesis involves two simultaneous events that occur during thermal aging: the increase of crystallite size in the direction parallel to coplanar sheets, and the disruption of the crystalline lattice in the direction perpendicular to those sheets. The glass transition temperature of PBI was found to shift towards the lower temperatures after thermal aging, a phenomenon that can be associated with random polymer chain scission caused by thermal aging. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Weibull statistics in electrical aging of polyesterimide under AC voltage

This article is aimed at the investigation of electrical aging of polyesterimide under AC voltage using Weibull statistical analysis. It's shown that the time to breakdown characteristic (V–t) of polyesterimide includes two zones (segments of straight line). The first zone characterizes a statistical dispersion of the intrinsic defects of material. The second zone expresses the real aging of polymer. The variation of the slope of lifetime curve is attributed to the change in the degradation mechanism. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Formation and inhibition of free radicals in electrically stressed and aged insulating polymers

Previous work has shown that prebreakdown, electrical aging, and breakdown phenomena are directly associated with charge carriers injected from electrical contacts and their subsequent dissociative trapping and recombination. In addition, the energy released from each trapping or recombination event is dissipated in the breaking of the bonds of macromolecules, thus forming free radicals and new traps in the electrically stressed insulating polymers, as predicted by Kao's model. It is this gradual degradation process that leads to electrical aging and destructive breakdown. New experimental results are presented to confirm previous findings and a new approach to inhibit the degradation process by the incorporation of suitable dopants into the polymer. The concentration of free radicals in the polymer increases with an increasing electric field at a fixed stress time of 250 h and with increasing stress time at a fixed electric field of 833 kV cm^?1. The concentration of free radicals is directly related to the concentration of new traps created by stress. However, when suitable dopants are incorporated, the initiation voltage for the occurrence of electrical treeing and the breakdown strength are both increased. The dopants tend to create shallow traps and have little effect on the deep trap concentration. This implies that the dopants act as free‐radical scavengers that tend to satisfy the unpaired electrons of the broken bonds, which create new acceptor‐like electron traps and new shallow traps. By doing so, the shallow traps screen the deep traps, thereby reducing the energy released during trapping and recombination and the probability of breaking the macromolecular bonds and causing structural degradation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3416–3425, 2003     

Effect of thermal aging on the electrical properties of crosslinked polyethylene

This article reports on the effect of thermal aging on the electrical properties of crosslinked polyethylene (XLPE) used in high voltage cables. It was shown that thermal aging modifies the electrical properties of the polymer. The degradation is accelerated when the temperature is increased. This degradation is due to a thermooxidation, followed by a loss of antioxidant, and a change in color of the material. At 80 and 100°C, the antioxidant is practically efficacious during the aging, whereas at 120 and 140°C, it is consumed after 1500 and 1000 h, respectively, which results in an increase in the dielectric losses and a diminution in the volume resistivity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Oxidation and crosslinking processes during thermal aging of low‐density polyethylene films

This work analyzes the influence of thermal degradation on the microstructure and the mechanical properties of low‐density polyethylene subjected to aging at 70°C in the dark for times up to 21 months. It is found that the polymer shows a gradual increase of its elastic modulus and a dramatic reduction of its ductility, due to secondary crystallization. Infrared spectroscopy (FTIR) reveals the autoaccelerated oxidation of the polymer after 5 months aging. It is observed that the unsaturated vinylidene groups initially present in the material are gradually overridden by vinyl groups and, eventually, by t‐vinylene groups. Nuclear magnetic resonance (¹³C NMR) shows that the initial butyl chain branches are progressively completed by shorter ramifications, namely ethyl branches. These results are discussed in term of macromolecular mechanisms: (i) oxidation, (ii) chain scission, and (iii) crosslinking. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Surface oxidation of low‐density polyethylene films to improve their susceptibility toward environmental degradation

Polyethylene wastes, particularly as films, have accumulated over the last several decades resulting in a major visual litter problem. The aim of this study was to investigate the ability of chemical reagents to oxidize the low‐density polyethylene (LDPE) film surface to increase their susceptibility toward photodegradation and thermal degradation. Three chemical agents, namely, potassium permanganate, potassium persulfate, and benzoyl peroxide, were used to oxidize the film surface to generate chromophoric groups, such as carbonyl groups, which are the main reason for the enhanced environmental degradation of photolytic polymers, such as ethylene–carbon monoxide and ethylene–vinyl ketone copolymers. For the chemical treatment, LDPE films of 70 ± 5 μm thickness were prepared by a film‐blowing technique and subsequently reacted with the aforementioned oxidizing agents. To aid the oxidation process, the reaction with potassium persulfate and potassium permanganate was performed under microwave irradiation heating. In the case of benzoyl peroxide aided oxidation, the films were subjected to repeated coating–heating treatments up to a maximum of 10 cycles. The treated films were subjected to accelerated aging, that is, xenon‐arc weathering and air‐oven aging (at 70°C), for extended time periods. The chemical and physical changes induced as a result of aging were followed by the monitoring of changes in the mechanical, structural, and thermal properties. The results indicate that the surface‐oxidized LDPE films exhibited enhanced susceptibility toward degradation; however, the extent was reduced as compared to photolytic or other degradable compositions. The ability of the chemicals to initiate degradation followed the order potassium persulfate < potassium permanganate < benzoyl peroxide. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Epoxy‐boehmite nanocomposites as new insulating materials

The results of a comparative analysis performed on specimens of nanostructured epoxy resins obtained by different boehmite filler concentrations are reported in this paper. The specimens were prepared by dispersion of boehmite nanoparticles into a cycloaliphatic epoxy resin cross linked under UV. Photopolymerization process was followed by RT‐FTIR and the properties of uv‐cured films investigated. Dielectric properties, in particular space charge accumulation, are measured as a function of nanofiller content. Results indicate that space charge build up and charge mobility are affected largely by filler content. Concentrations of nanofiller of 5–7 wt % show significant decrease of the space charge with respect to the base‐epoxy resin and an increased mobility of negative carriers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Charge transport and its characterization using photo‐CELIV in bulk heterojunction solar cells

This mini‐review gives a simple overview of the workings of organic photovoltaic (OPV) devices, the way in which charge transfer occurs through the active layers, and then introduces how photo‐induced charge carrier extraction by linearly increasing voltage (photo‐CELIV) and time of flight (TOF) techniques can be employed to give comprehensive indications of charge carrier mobility, density and recombination in OPVs. It is shown how photo‐CELIV and TOF characterizations, using extraction current transients, can give an understanding of degradation mechanisms through observation of the trapping of charge carriers and bimolecular recombination. Examples of deployment and the interpretation of the results are given. It is hoped that this brief introduction will serve as a stepping stone into more in‐depth papers and books and encourage wider use of photo‐CELIV and TOF technologies which can be employed with whole devices. © 2016 Society of Chemical Industry     

Study on lanthanum‐pentaerythritol alkoxide as a thermal stabilizer for rigid polyvinyl chloride

Lanthanum‐pentaerythritol (La‐PE) alkoxide, a polyol‐based metal alkoxide, had been synthesized and used as a thermal stabilizer for polyvinylchloride (PVC) . Thermogravimetric (TG), differential thermal analysis (DTG), mass spectrum (MS), and Fourier transform infrared (FTIR) spectroscopy were used to confirm the synthesis reaction. The thermal stability of rigid PVC stabilized with La‐PE was tested by means of the Congo Red test, conductivity test, thermal aging test, thermal gravimetric analysis (TGA), and UV‐visible (UV‐vis) spectroscopy. The results showed that addition of La‐PE could significantly prolong static stability time of PVC and increase the apparent activation energy for degradation reaction. The oven aging test showed that La‐PE could improve the initial color of PVC. Moreover, addition of La‐PE could significantly reduce the concentrations of the conjugated double bonds of PVC and reduce weight loss . The possible thermal stability mechanism had also been discussed. Besides having good ability to neutralize hydrochloric acid (HCl), La‐PE could substitute or inactivate the labile chlorine atoms in the PVC chains. J. VINYL ADDIT. TECHNOL., 23:55–61, 2017. © 2015 Society of Plastics Engineers     

Stress photo‐oxidative aging behaviour of polyamide 6

The long‐term stress accelerating aging behaviour of polyamide 6 (PA6) was studied by exposure to UV irradiation. The aging behaviour and mechanism were investigated in terms of creep behaviour, mechanical properties, chemical structure, crystallization and orientation behaviour. It was found that the creep deformation of PA6 under stress/UV irradiation was lower than that of the sample aging only under stress, resulting from crosslinking and low mobility of molecules under UV irradiation. The tensile strength of PA6 under stress and stress/UV irradiation substantially increased at the primary aging stage due to stress‐induced molecular orientation. The oxidation of PA6 may also be inhibited by orientation, leading to a relatively low content of carboxylic groups. Under UV irradiation, stress accelerates the degradation of PA6, resulting in strengthening UV absorption due to formation of isolated carbonyl groups. The melt temperature and crystallinity both showed an increase with time, which were much higher for the sample aged under stress/UV irradiation than for that aged only under UV irradiation. Wide‐angle X‐ray diffraction analysis also showed that the orientation factor and crystallinity of PA6 increased with aging time before 16 days, indicating a clear orientation and crystallization of molecules induced by stress. The UV‐induced crosslinking reduced the mobility of PA6 chains, resulting in a lower crystallinity and orientation factor of the sample aged under stress/UV irradiation compared with that under stress aging only. Copyright © 2011 Society of Chemical Industry     

Nonisothermal degradation kinetics for epoxy resin systems containing polymethylphenylsilsesquioxane

The thermal degradation behaviors of polymethylphenylsilsesquioxane/epoxy resin (PMPSQ/EP) systems were investigated by thermogravimetric analysis (TGA) under nonisothermal conditions in nitrogen atmosphere. During nonisothermal degradation, Kissinger's and Flynn‐Wall‐Ozawa's methods were both used to analyze the thermal degradation process. The results showed that a remarkable increase of activation energy was observed in the presence of PMPSQ, which indicated that the addition of PMPSQ retarded the thermal degradation of EP. Flynn‐Wall‐Ozawa's method further revealed that PMPSQ significantly increased the activation energy of EP thermal degradation especially in the early and final stage of thermal degradation process, which illustrated that the PMPSQ stabilized the char layer and improved the flame retardancy of EP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Stress–thermooxidative aging behavior of polyamide 6

The long‐term stress–thermooxidative aging behavior of polyamide 6 (PA6) was studied in terms of the creep behavior, mechanical properties, chemical structure, crystallization, and orientation behavior. During aging, a thermooxidation reaction occurred, which included molecular chain degradation and crosslinking, in PA6. Meanwhile, when the samples were subjected to stress, crystallization, orientation, and chain scission were induced. In the initial stages of aging, the stress‐induced crystallization and orientation dominated; this resulted in an increase in the creep deformation, mechanical strength, crystallinity, and orientation factor. Molecular degradation and chain scission dominated in the subsequent aging process and resulted in a decrease of the mechanical strength, reduced viscosity, crystallinity, and orientation factor and an increase in the formation of oxide and peroxide products. The stress may have promoted the chain scission of PA6 during thermal aging and resulted in a decrease in the reduced viscosity and an increase in the carboxylic acid concentration. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dielectric constant and loss investigations of pristine,iodine‐doped and annealed polyetherimide film

Temperature‐ and frequency‐dependent dielectric behaviour has been investigated for pristine, iodine‐doped and annealed polyetherimide (PEI) in the temperature range 303–523 K at various frequencies (120 Hz, 1 kHz, 10 kHz and 100 kHz). In pristine PEI, the rapid decrease in the dielectric constant (ε′) in the temperature range 303–373 K is governed by the Kirkwood model whereas the gradual decrease in ε′ in the temperature range 373–473 K is governed by β‐relaxation (dipolar) and αβ‐relaxation (hybrid) processes. The occurrence of these relaxations is confirmed by the appearance of tan δ loss peaks at ca 403 and 443 K, respectively, in ε″–T curves. The temperature‐independence of ε′ in the temperature range 473–523 K is mainly governed by the α‐relaxation process associated with large segmental groups. The tan δ loss peak appearing at 503 K confirms this relaxation process. In iodine‐doped samples, an overall increase in ε′ is attributed to the formation of charge‐transfer complexes in the polymer structure. The dominance of a new relaxation process due to interaction of iodine with ether linkages neutralizes the 1/T rule in the low‐temperature region. A significant decrease in ε′ in annealed samples below 393 K is due to the suppression of the dipolar relaxation process. The enhancement in ε′ above 393 K is due to the dominance of the α‐relaxation process. The shift in the high‐temperature tan δ loss peak towards higher temperature with increasing frequency shows the distributive nature of relaxation time for this relaxation process. Copyright © 2011 Society of Chemical Industry