Slow relaxations in semicrystalline poly(butylene succinate) below and above Tg

The slow molecular mobility in the amorphous part of the semi‐crystalline polymer poly(butylene succinate) (PBS) has been studied by the thermally stimulated depolarization current (TSDC) technique. Experiments were carried out in the temperature range, which includes the glassy state, the glass transformation region, and the rubber state. A broad and low intensity secondary relaxation was observed in the temperature region from ?140°C up to the glass transition region; the activation energy of the motional modes of this secondary relaxation was in the range between 35 and 55 kJ mol^?1. The glass transition temperature of PBS, provided by the TSDC technique, was T_g = ?40 °C, and the fragility index was found to be m = 43. The aging behavior of the main and of the secondary relaxations was analyzed. A strong relaxation above T_g was observed, whose molecular origin was discussed. The thermal behavior of the PBS was also characterized by differential scanning calorimetry. POLYM. ENG. SCI., 55:1873–1880, 2015. © 2014 Society of Plastics Engineers     

Effects of blending on the molecular dynamics of highly interacting binary polymer blends of poly(methyl methacrylate) and poly[styrene‐co‐(maleic anhydride)]

The molecular dynamics and miscibility of highly interacting binary polymer blends of poly(methyl methacrylate) (PMMA) and poly[styrene‐co‐(maleic anhydride)] random copolymer with 8 wt% maleic anhydride content (SMA) were investigated as a function of composition over a wide range of frequency (10^?2–10⁶ Hz) at different constant temperatures (30–160 °C). Only one common glass relaxation process (α‐process) was detected for all measured blends, and its dynamics and broadness were found to be composition dependent. The existence of only one common α‐relaxation process located at a temperature range between those of the pure polymer components indicated the miscibility of the two polymer components over the entire range of composition. The miscibility was also confirmed by measuring the glass transition temperatures of the blends, T_g, using differential scanning calorimetry. The composition dependence of T_g of the blends showed a positive deviation from the linear mixing rule and well described by the Gordon–Taylor–Kwei equation. The relaxation spectrum of the blends was resolved into α‐ and β‐relaxation processes using the Havriliake–Negami (HN) equation and ionic conductivity. The dielectric relaxation parameters obtained from HN analysis, such as broadness of relaxation processes, maximum frequency, f_max, and dielectric strength, Δ? (for the α‐ and β‐relaxation processes), were found to be blend composition dependent. The kinetics of the α‐relaxation process of the blends were well described by the Meander model, while an Arrhenius‐type equation was used to evaluate the molecular dynamics of the β‐relaxation process. Blending of PMMA and SMA was found to have a considerable effect on the kinetics and broadness of the β‐relaxation process of PMMA, indicating that the strong interaction and miscibility between the two polymer components could effectively change the local environment of each component in the blend. © 2013 Society of Chemical Industry     

Detection of polymer transition temperatures by infrared absorption spectrometry

Infrared bands in the 900–1100 cm^?1 region are sensitive to thermal energy. These bands can result from intermolecular coupling, producing the crystal lattice, or from intramolecular coupling of the various atomic groups in a regular helix or coiled chain. In either case an increase in temperature will disrupt the coupling mode, resulting in a form of structural relaxation and a reduction in the integrated absorbance. It is proposed that the temperature at which the peak areas begin to decrease be assigned as the T_g. This is measured by continuously scanning a selected peak in the infrared spectrum of a polymer film while it is heated at a rate of about 1°C/min. Using this technique polyamides (nos. 6,66, and 610) exhibited transitions in the 30–50°C range, and by studying the increase in the free NH region (3440 cm^?1) of nylon 66 two other transitions were detected at 80 and 137°C; the latter represents a change in the nylon 66 crystal state. An amorphous film of poly(ethylene terephthalate) displayed a transition at 58–68°C (T_g) and at 85°C, which is the crystallization temperature. Films of poly(vinyl acetate) and polystyrene exhibited transitions at 25–37°C and at 70°C, respectively.     

Study of dielectric relaxation of an epoxide oligomer by a direct current transient method

Dielectric α-relaxation of a bisphenol-A type epoxide oligomer has been investigated in the vicinity of the glass transition temperature (T_g) by the direct current (DC) transient method. The logarithm of the DC transient current for the oligomer was well approximated by the third order function of the logarithm of time. The complex dielectric constant was calculated through the Fourier transformation of that approximation function according to Simpson's integration rule in a frequency range of 10^?5 ? 1 Hz. At the temperature around the T_g (45°C), the dielectric α-relaxation process of the oligomer was found to be governed by the Havriliak-Negami equation. The relationship between the DC conductivity (σ) and the dielectric relaxation time (τ), σ·τ^m = const, is valid near and above the T_g of the oligomer. The DC transient current method combined with the DC conduction and the dielectric bridge measurements is considered to be a practical tool for analyzing the dielectric α-relaxation process of the epoxide oligomer over a wide frequency and temperature range.     

Straining phenomena of POY revealed by thermal retraction and other techniques

Partially oriented polyesters yarns (POY) were strained at different strain rates (0.03–12.00 min^?1) and temperatures above and below T_g (3–92°C). Thermal retraction, density, DSC, and WAXS techniques show that strain-induced crystallization takes place by straining at temperatures above as well as below T_g. Above T_g, depending upon the strain rate, two regimes are observed: Below the strain rate of 1.5 min^?1, the flow regime; the degree of crystallinity is reduced as the strain rate increases. Above the strain rate of 1.5 min^?1, the strain-induced crystallization regime; the degree of crystallinity increases as the strain rate increases. Thermal retraction, stress–relaxation, and sonic modulus techniques indicate that, upon cold straining, instead of the original T_g at 65–69°C, two glass transitions occur: an upper T_g (u) and a lower T_g (l). For POY strained at 3°C and at a strain rate of 10 min^?1, the values are 78°C and 37°C, respectively. The higher the strain rate and the lower the straining temperature, the large the difference between T_g (u) and T_g (l).     

The glass transition temperature of poly(phenylene sulfide) with various crystallinities

The glass transition temperature (T_g) of poly(phenylene sulfide) (PPS) with various crystalline fractions has been studied using dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). The DSC measurements show that T_g can be observed from the heating curves for the PPS sample with very low crystallinity, and no T_g is observed when the crystallinity is over 8%. DMA indicates that crystallinity has an important effect on molecular chain segment motion of PPS. When the crystallinity, X_c, of PPS is over 38%, there is only one chain segment motion, which mainly results from the crystalline chain vibration; while three different chain segment motions occur for PPS samples with lower crystallinity (X_c < 26%), which are amorphous chain segment motion, crystalline chain segment motion and constrained amorphous chain segment motion. T_g of PPS is mainly caused by the amorphous chain segment motion which is independent of the crystallinity, while the relaxation temperature corresponding to crystalline chain motion shifts to lower temperature as the crystallinity increases. The reduction of the relaxation temperature can be attributed to the disorder‐order transition of amorphous chains for PPS with lower crystallinity. © 2012 Society of Chemical Industry     

Effect of Hydrothermic Ageing on Dielectric and Mechanical Properties of Rigid Poly(vinyl chloride)

An accelerated hydrothermic ageing (according to N.F.T. 54043 method) was performed on samples of rigid poly(vinyl chloride). The test consisted of sample immersion in boiling water at 100°C for different exposure periods up to 480 h. The samples were removed from the boiling water every two hours for mechanical and dielectric characterization and color test. The dielectric measurements carried out on aged samples, up to 40 h, showed that the permittivity remained almost constant and its value was found to be 2.3 in the range –100 to +62.8°C. However, as the temperature approaches the glass transition (T_g = 88.3°C), the permittivity was observed to increase rapidly. It was also found that the permittivity of aged samples was lower than that of the non‐aged samples. The dielectric loss factor (tan δ) measurements with respect to temperature have confirmed the presence of two relaxations: β at low temperature (around –35°C) and α near the T_g. The combined action of water and temperature reduced the intensity of the corresponding relaxation peaks. The sample color index was evaluated up to 480 h using the SYNMERO scale in order to estimate the degradation extent. Unexpectedly, elongation at break under uniaxial traction remained unaffected by the hydrothermic ageing, meaning that two competing processes were involved simultaneously (sample degradation via chain scission and sample plastification via water absorption).     

Dynamic infrared measurements of poly(vinyl chloride) in the vicinity of the glass transition

The temperature dependences of some selected infrared bands of poly(vinylchloride) in the vicinity of the glass transition were examined. The intensities of 1333 and 1427 cm^?1 bands changed discontinuouly at T_g; on the other hand, 2920 cm^?1 did not show any significant changes at this temperature. From these results, the nature of the temperature dependence of infrared intensity of the polymer was discussed. The procedure introduced in this work offers a rapid method for the determination of the T_g as compared with the conventional infrared methods.     

Dielectric investigation of the molecular dynamics in blends: polymers with similar molecular architecture (TMPC/PC blend)

Broad band dielectric spectroscopy was used in the investigation of the molecular dynamics and compatibility of tetramethyl polycarbonate/polycarbonate (TMPC/PC) blends. Frequency scan measurements in the range 10^?2?10^?5 Hz were carried out in the temperature range 50–220°C for several blends with different compositions, namely, 0, 12.5, 25, 50, 75, 87.5 and 100 wt% of TMPC. The results obtained show that these two polymers are ideally compatible over the entire composition range. The blends reveal only one common glass process. The dielectric relaxation strength and the common glass transition temperature, T_g, were found to vary linearly with composition. Moreover, it was found, surprisingly, that blending has no effect on the distribution of relaxation times of the common glass process of the blends. Furthermore, neither the kinetics (relaxation frequency at a certain temperature) nor the distribution of relaxation times of the local process were influenced by blending. It is concluded that the polymeric chains of the different components are not miscible on a segmental level although the blend exhibits only one glass transition temperature.     

Real-time monitoring of segmental dynamics during crystallization of poly(l(-)-lactide) by simultaneous DRS/SALS technique

A novel experimental set up consisting of dielectric spectroscopy and small angle light scattering (or potentially any other optical technique used in combination) is introduced. The sample is enclosed in a Dielectric-Optical-Shear (DOS) cell capable of precisely controlling temperature and thickness. This method allows for simultaneous in situ, real-time monitoring of the changes in the molecular dynamics and corresponding development of supramolecular structure of a given polymer system during various time-sensitive processes. The DOS cell is utilized to investigate relaxation phenomena related to the glass transition, T_g, of poly(l(−)-lactide) during isothermal crystallization under quiescent, partially constrained conditions. A decrease in T_g was observed in situ via a shift in dipolar relaxation to higher frequency (confirmed calorimetrically, ex situ). The shift was most rapid in the spherulitic impingement stage of crystallization, at approximately 30% overall crystallinity.     

Physical aging in poly(methyl methacrylate)poly(styrene-co-acrylonitrile) blends. Part II: Enthalpy relaxation

An investigation of the effect of physical aging on excess enthalpy of compatible polymer blends was carried out. Poly(methyl methacrylate) (PMMA) and poly(styrene-co-acrylonitrile) (SAN) were chosen for this study. Blends of different ratios of PMMA and SAN were physically aged at different times and temperatures below their glass transition (T_g) and then subjected to enthalpy relaxation measurement in a differential scanning calorimeter (DSC). An improved procedure was developed and, employed to analyze the data. The error associated with the calculation of the normalized deviation in enthalpy, known as the “Φ” function, was below 4%. The relaxation was observed to proceed faster at higher aging temperature. It was also found that at higher aging temperatures of T_g – 20 and T_g– 35°C, enthalpy relaxation in SAN-rich blends proceeds faster than in PMMA rich blends, while at the low aging temperature of T_g– 50°C the rate of relaxation becomes independent of the composition.     

Laser light scattering studies of bulk polymers in the glass transition regime

The application of laser light scattering techniques to characterize the structural and dynamical properties of bulk polymers near the glass transition temperature is reviewed. Preliminary results of a study of poly(n-butyl methacrylate) are presented. As in an earlier study of atactic polystyrene, the results suggest the coexistence of two relaxation mechanisms near T_g: a fast, single exponential decay; a slow process characterized by a wide distribution of relaxation times. The slow relaxation mechanism is evidently the main-chain glass transition process; it appears possible that the fast decay is a manifestation of side-chain motion. However, in contrast to the polystyrene system where the fast mechanism is always of small amplitude in the temperature range amenable to study (T_g < T < T_g + 40°), the fast mechanism in the poly(n-butyl methacrylate) system exhibits a sudden transition to high amplitude (～50 percent of the total observable relaxation amplitude) at T ～ T_g + 30°. At this point therefore, we suggest that a strong resonant coupling of the fast process with the slow relaxation is occurring.     

Analysis of the dielectric spectra of composite sealing coatings in a wide frequency range

Polymer coatings on the basis of the biphenol-Novolac potting epoxy compound with a 65% content of spherical particles of fused quartz as a filler were studied by the method of dielectric spectroscopy in a wide frequency range. Dielectric measurements were performed in frequency and temperature ranges of (10⁻² to 5 × 10⁹) Hz and 20 to 200°C, respectively, on film samples of composite coatings formed on different substrates. It was shown that the application of dielectric spectroscopy allows one to study the effect of the degree of the adhesion interaction with the substrate on the processes of structuring in the epoxy polymer matrix and to investigate the degradation processes in the coatings under the effect of high temperature and relative humidity. It was also shown that the values of the glass transition temperature (T _g ) of the composite determined by applying the method of low-frequency dielectric spectroscopy agree well with the T _g values obtained by applying the method of dynamic mechanical analysis (DMA).     

Dielectric behavior of some polar high polymers at ultra-high frequencies (microwaves)

The dielectric behavior of different polar high polymers at ultra-high frequencies has been investigated by means of a dielectrometer, suitably modified to permit measurements at different temperatures. Experimental measurements were made at about 9 × 10⁹ cps over the temperature range of ?150 to 200°C. for polyoxymethylene, polythiomethylene, poly(3,3′-chloromethyl)oxetane (Penton), polycarbonate of 4,4′-dioxydiphenyl-2,2′-propane (Makrolon), poly(vinyl alcohol), poly(vinyl acetate), poly(vinyl chloride), vinyl chloride–vinyl acetate copolymer, and two ABS plastics, type B (blend) and type G (graft). On comparing the dielectric behavior of the examined materials at ultra-high frequencies with the corresponding ones determined at low or at radiofrequencies, it is observed that, in the microwave region, all relaxation peaks, either connected with cooperative motions in main chain (primary processes) or with local motions in the backbone or in side chains (secondary processes), usually observed at lower frequencies, tend to disappear; the corresponding relaxation effects, however, manifest themselves through a progressive increase of losses with increasing temperature, which is particularly marked above the glass transition temperature T_g. The latter transition, in spite of the very high frequency, is easily distinguished, in most cases, by the sudden change of slope in the tan δ versus temperature curve which accompanies its onset. This is explained on the basis of the very wide distribution times of molecular relaxation processes in polymers and the increase in strength of the secondary relaxation effects, which is verified at T_g, as a consequence of the increased kinetic energy of macromolecules and of the larger free volume for orientation of side chains. Each case is discussed separately and the experimental results interpreted on the basis of the molecular structure and chain mobility of the examined polymers.     

Evaluation of local polarity of polymer solids by a rigid fluorescent probe of carbazole-terephthalate cyclophane

A novel rigid fluorescent probe, carbazole-terephthalate cyclophane (Cz-TP) was applied to evaluate local dielectric constants (ε) of various polymer solids in a wide range of temperatures. For poly(vinylidene fluoride), the ε increased above the glass transition temperature (T_g), due to relaxations of the polar segment -(CH₂CF₂)- of the main chain. For poly(alkyl methacrylate)s, the ε increased above the T_g or the melting temperature of the side chain, where motions of the polar ester groups are activated. For cyanoethylated polymers, the ε increased owing to motions of the polar cyano groups at the end of the side chain and the ε corresponded to the dielectric constant evaluated by dielectric relaxation measurement at a high frequency, because the Cz-TP exciplex has a lifetime of tens of nanoseconds. For a cyanoethylated polymer with a high content of cyano groups, the ε was larger at low temperatures than the dielectric constant obtained by the macroscopic dielectric relaxation measurement. These results show that the Cz-TP molecule is a useful probe for evaluation of the local polarity in polymer solids over a wide temperature range and can detect even a small change in ε at transition temperatures such as glass transition, side-chain melting, and side-chain relaxation.     

Comparison of the enthalpic relaxation of poly(lactide–co‐glycolide) 50:50 nanospheres and raw polymer

The phenomenon of enthalpic relaxation was evaluated for poly(lactide‐co‐glycolide) (PLGA, 50:50), in terms of storage of nanospheres for use as a controlled drug delivery system. Samples were stored for different times and temperatures below the glass transition temperature (T_g). Relaxation occurred at a significant rate up to 15 degrees below the T_g of 39.2°C. The effect of polymer morphology was considered by comparing the relaxation kinetics of the raw polymer with that of nanospheres formed using a novel technique. The nanospheres were shown to have a larger change in heat capacity at the glass transition and a longer average relaxation time than that of the raw polymer, and the relationship between these two parameters was discussed. For both the raw polymer and the nanospheres, relaxation was found to occur at a significant rate at room temperature. The storage of this system at subambient temperatures was therefore deemed important for maintaining the physicochemical properties of the system. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1868–1872, 2002     

Preparation and performance analysis of barium titanate incorporated in corn starch‐based polymer electrolytes for electric double layer capacitor application

Polymer electrolyte membranes composing of corn starch as host polymer, lithium perchlorate (LiClO₄) as salt, and barium titanate (BaTiO₃) as composite filler are prepared using solution casting technique. Ionic conductivity is enhanced on addition of BaTiO₃ by reducing the crystallinity and increasing the amorphous phase content of the polymer electrolyte. The highest ionic conductivity of 1.28 × 10^?2 S cm^?1 is obtained for 10 wt % BaTiO₃ filler in corn starch‐LiClO₄ polymer electrolytes at 75°C. Glass transition temperature (T_g) of polymer electrolytes decreases as the amount of BaTiO₃ filler is increased, as observed in differential scanning calorimetry analysis. Scanning electron microscopy and thermogravimetric analysis are employed to characterize surface morphological and thermal properties of BaTiO₃‐based composite polymer electrolytes. The electrochemical properties of the electric double‐layer capacitor fabricating using the highest ionic conductivity polymer electrolytes is investigated using cyclic voltammetry and charge‐discharge analysis. The discharge capacitance obtained is 16.22 F g^?1. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43275.     

Relaxation behavior of conductive carbon black reinforced EPDM microcellular vulcanizates

Dynamic mechanical analysis and dielectric relaxation spectra of conductive carbon black reinforced microcellular EPDM vulcanizates were used to study the relaxation behavior as a function of temperature (−90 to +100°C) and frequency (0.01–10⁵ Hz). The effect of filler and blowing agent loadings on dynamic mechanical and dielectric relaxation characteristics has been investigated. The effect of filler and blowing agent loadings on glass transition temperature was marginal for all the composites (T_g value was in the range of −39 to −35°C), which has been explained on the basis of relaxation dynamics of polymer chains in the vicinity of fillers. Strain-dependent dynamical parameters were evaluated at dynamic strain amplitudes of 0.07–5%. The nonlinearity in storage modulus has been explained based on the concept of filler–polymer interaction and interaggregate attraction (filler networking) of carbon black. The variation in real and complex part of impedance with frequency has been studied as a function of filler and blowing agent loading. Additionally, the effect of crosslinking on the dielectric relaxation has also been reported. POLYM. ENG. SCI., 47:984–995, 2007. © 2007 Society of Plastics Engineers     

Dielectric properties of copolymers based on cyano monomers and methyl α‐acetoxyacrylate

With the aim of developing dielectric polymers containing CN groups with strong dipole moment, alternating and statistical copolymers of the cyano monomers vinylidene cyanide (VCN), acrylonitrile and methacrylonitrile with methyl α‐acetoxyacrylate (MAA) were synthesized and characterized. The copolymer's composition and microstructure were analysed by NMR spectroscopy, SEC and elemental analysis. The reactivity ratios calculated from the Q–e Alfrey–Price parameters for these copolymers indicated the alternating and statistical structures confirmed by NMR analysis. The copolymers have glass transition temperatures T_g in the range 83–146 °C and are stable up to 230 °C. The thermal stability of the copolymers depends on the nature of the cyano monomers. Their molecular dynamics were investigated by dielectric relaxation spectroscopy. We revealed a weak relaxation β at sub‐T_g temperature for poly(VCN‐co‐MAA) usually originating from molecular motions that are restricted to the scale of a few bond lengths. Strong α‐relaxation processes occurred above T_g for these copolymers. This primary relaxation was associated with cooperative movements of the polar groups (CN) at the time of mobility of the principal chains. The activation energy of the α‐relaxation process was also calculated. The values of the dielectric increment Δε for these copolymers were determined by Cole–Cole plots and indicated that the copolymers exhibit interesting dielectric properties compared with similar cyano materials. The polarity–permittivity relationship was also established. © 2012 Society of Chemical Industry     

Time–temperature dependent brittle fracture of viscoelastic solids

The Griffith formulation is used to study fracture behavior of poly(methyl methacrylate) (PMMA) as a function of strain rate and temperature over the range 4.4 × 10^?5 ≤ ε ≤ 4.4 × 10^?2 in./in./sec and 25°C ≤ T ≤ T_g, T_g being the glass transition temperature. It is found that the transition from brittle to ductile failure occurs abruptly at a temperature T_f which is dependent on strain rate and is approximately the same as the glass transition temperature of the material. The Griffith brittle fracture criterion is found to apply below T_f for all strain rates. The brittle fracture behavior is shown to obey the time–temperature equivalence principle in the same way as the material's other viscoelastic properties, having the same shift function.