The effect of increased crystallization on the electrical properties of nylon-12

The dielectric properties of 30% crystalline dry Nylon-12 have been measured over the frequency range 10–10⁵ Hz and temperature range 300–450 K, and the effect of its annealing at 423 K investigated both by dielectric measurement and differential scanning calorimetry. Annealing causes its crystallization to α phase, which increase the dc conductivity and decreases the contribution to orientation polarization, but does not alter the shape of the relaxation spectrum. The orientation polarization in Nylon-12 involves two processes, each of which occurs above the glass-transition temperature of Nylon-12, but only the spectra of the lowest temperature process could be clearly resolved. © 1993 John Wiley & Sons, Inc.     

Relaxations in thermosets. XIII. Effects of post-cure and aging on the sub-Tg relaxations of nonstoichiometric epoxide-based thermosets

The dielectric permittivity and loss of diglycidyl ether of bisphenol-A (DGEBA) cured with greater than and less than the stoichiometric amounts of diaminodiphenyl methane (DDM) have been measured over a temperature range 77–350 K prior to curing and gelation, after curing at about 340 K and further aging for a predetermined period. The height of the γ-relaxation peak monotonically decreases during the post-cure period and becomes masked by the contributions from the β-relaxation peak, whose height, in turn, first increases on postcuring to a same maximum value for both nonstoichiometric thermosets and then decreases. This decrease is attributed to physical aging effects. The β-relaxation peak shifts towards higher temperature on postcuring. Comparison between the changes in the dielectric properties of the saturated and starved thermosets show that while the γ-relaxation process may be attributed to the motion of the epoxide dipolar groups of the unreacted DGEBA, the β-relaxation process is not attributable entirely to the motion of ? OH groups and of the unreacted amines in the thermoset. Explanations involving the chain and network packing in the structure of a thermoset are necessary for the observed behavior of the β-relaxation process in amine saturated and starved thermosets.     

Dielectric relaxation of LC-thermotropic poly(ester imide)s

Two different series of poly(ester imide)s, which are distinguished from each other in the orientation of the ester linkages and show well-differentiated thermotropic behavior, are investigated by means of model calculations and dielectric relaxation spectroscopy. Model calculations show that the orientation of the ester linkages has a strong influence on the rotational energy barriers. The dielectric relaxation spectra of both series shows three relaxation regions in the temperature range between 100 and 400 K that have been identified as the α-, β- and γ-relaxation processes. A difference of about two orders of magnitude between the characteristic rates of the γ-relaxation is the main feature observed in the dielectric response. However, the β-relaxation shows very similar behavior for both series. The differences in the relaxation behavior in the solid state are interpreted on the basis of the rotational barriers deduced from the model calculation results. © 1997 John Wiley & Sons, Inc.     

FTIR separation of nylon-6 chain conformations: Clarification of the mesomorphous and γ-crystalline phases

Specific infrared absorptions for each form of Nylon-6 have been indentified. Quenched films were prepared by melt casting and converted in turn to the α-crystalline and γ-crystalline structures. The films were examined using Fourier transform infrared spectroscopy (FTIR) with the attenuated total reflection configuration and by X-ray diffractometry. The FTIR spectrum of the pure mesomorphous component of the quenched film was calculated by subtracting away the contribution of α-crystalline peaks present due to incomplete quenching. A curve-fitting procedure was applied to the pure mesomorphous and gamma crystalline spectra. Several peaks in the mesomorphous spectrum are observed to develop a shoulder upon conversion to the γ-crystalline form. This is due to the extra gauche character imparted to the C? N bond between the methylene unit and the amide group. These and other band assignments were confirmed by analysis of model compounds.     

Low-Temperature TSDC Studies of Molecular Dynamics in Pristine and O7+ Ion–Modified Liquid Crystalline Polyurethane

The molecular dynamics of pristine and 100 MeV O⁷⁺ ion–modified liquid crystalline polyurethane (LCPU) was carried out using the thermally stimulated depolarization currents (TSDC) method. The TSDC spectra of pristine LCPU samples consist of current peaks appearing around 110,160, 210, and 260 K and are called the γ, β, α, and δ peaks respectively. The γ-peak is attributed to the crankshaft motion of the spacer group (but-2-ene group). The β-peak is due to the localized rotational fluctuations of C?O groups. The α-peak is associated with the dipolar orientation of imines group present in the urethane linkage, and the δ-peak has its origin in the space charge trapping mechanism. In the TSDC spectra of O⁷⁺ ion–irradiated LCPU samples the γ-peak almost disappears, which shows that the ion induced modification in the methylene linkage. A relaxation process owing to new sub-polar groups formed due to dehydrogenation of CH₂ groups and occurring in the vicinity of β-relaxation is discussed. The radiation-induced chain scissioning at NH groups in LCPU is also confirmed from the fluence effect on the α-peak. The irradiation results in the production of a large number of defect sites and an increase in the same results in the enhancement of δ-relaxation.     

Moisture effect on the low- and high-temperature dielectric relaxations in nylon-6

The effect of water sorption on the dielectric relaxation processes of nylon-6 samples with water concentrations ranging from the dry to the water-saturated polymer has been studied by thermally stimulated depolarization currents experiments in a broad temperature range, from 77 to 365 K. The strengths of the low-temperature modes, γ- and β-peaks, are affected in opposite ways by the water concentration, h, as the first one shows a decrease in intensity and the second one grows as h increases. The precise determination of the relaxation parameters is made by the decomposition in elementary Debye processes and best fitting to the experimental profile of the complex peak. For h < 3%, the reorienting energies are almost independent of the water content, and the most significant intensity variations occur. The firmly bound water is held responsible for these effects. As for the higher temperature zone besides the α-peak, which is the dielectric manifestation of the glass transition, intermediate temperatures modes are observed at high h values and are originated by the loosely bound water, while the highest temperature peak is attributed to a Maxwell–Wagner interfacial polarization. The characteristic parameters of the α-mode are determined and related to the plasticization effect of water. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2879–2888, 1997     

Dynamic mechanical analysis of RIM nylon-6

The β relaxation process was shown to occur at different temperatures and exhibit a different activation energy for dry and wet samples prepared by reaction injection molding (RIM) of Nylon-6. By employing a low operating frequency and controlled low moisture levels, it became possible to distinguish the two β relaxation processes, β₁ and β₂, in one sample by dynamic mechanical spectroscopy. It was shown that while β₁ was associated with moisture in the sample, β₂ was related to a structural mechanism independent of moisture. The effect of moisture content on the chain-chain association (α relaxation process) and chain-water association (β₁, relaxation process) in nylon-6 was assessed. The annealing mechanism of RIM Nylon-6 at 85°C was probed by both dynamic mechanical spectroscopy and x-ray diffraction.     

Calorimetric and relaxation properties of xylitol-water mixtures

We present the first broadband dielectric spectroscopy (BDS) and differential scanning calorimetry study of supercooled xylitol-water mixtures in the whole concentration range and in wide frequency (10(-2)-10(6) Hz) and temperature (120-365 K) ranges. The calorimetric glass transition, T(g), decreases from 247 K for pure xylitol to about 181 K at a water concentration of approximately 37 wt. %. At water concentrations in the range 29-35 wt. % a plentiful calorimetric behaviour is observed. In addition to the glass transition, almost simultaneous crystallization and melting events occurring around 230-240 K. At higher water concentrations ice is formed during cooling and the glass transition temperature increases to a steady value of about 200 K for all higher water concentrations. This T(g) corresponds to an unfrozen xylitol-water solution containing 20 wt. % water. In addition to the true glass transition we also observed a glass transition-like feature at 220 K for all the ice containing samples. However, this feature is more likely due to ice dissolution [A. Inaba and O. Andersson, Thermochim. Acta, 461, 44 (2007)]. In the case of the BDS measurements the presence of water clearly has an effect on both the cooperative α-relaxation and the secondary β-relaxation. The α-relaxation shows a non-Arrhenius temperature dependence and becomes faster with increasing concentration of water. The fragility of the solutions, determined by the temperature dependence of the α-relaxation close to the dynamic glass transition, decreases with increasing water content up to about 26 wt. % water, where ice starts to form. This decrease in fragility with increasing water content is most likely caused by the increasing density of hydrogen bonds, forming a network-like structure in the deeply supercooled regime. The intensity of the secondary β-relaxation of xylitol decreases noticeably already at a water content of 2 wt. %, and at a water content above 5 wt. % it has been replaced by a considerably stronger water (w) relaxation at about the same frequency. However, the similarities in time scale and activation energy between the w-relaxation and the β-relaxation of xylitol at water contents below 13 wt. % suggest that the w-relaxation is governed, in some way, by the β-relaxation of xylitol, since clusters of water molecules are rare at these water concentrations. At higher water concentrations the intensity and relaxation rate of the w-relaxation increase rapidly with increasing water content (up to the concentration where ice starts to form), most likely due to a rapid increase of small water clusters where an increasing number of water molecules interacting with other water molecules.     

The influence of short branches on the α, β and γ-relaxation processes of ultra-high strength polyethylene fibers

Dynamic mechanical measurements were conducted for several kinds of ultra–high-strength polyethylene fibers with different methyl branch contents. As is the case with conventional polyethylene materials, UHSPE fibers also exhibit α, β, and γ-relaxation dispersions. Each relaxation process is the function of both the tensile moduli and the branch contents of UHSPE fibers. It was also found that the γ-process of UHSPE fibers is dominated mainly by the localized molecular motion in the crystalline part, such as a dislocation mode of crystallite defects, which is very sensitive to the branching content. From the time and temperature superposition of the frequency dispersion experiments, it was found that activation energies for both the α2-process and α3-process increase proportionally to the methyl branch content, while the α1-process is not so affected by the branch content. This result shows that the incorporated branch sites in the crystalline part effectively hinder the chain-to-chain slippage; meanwhile, they have not hindered the slippage at the grain boundary so far, which also enables us to explain the creep improvement of UHSPE fibers through branch incorporation with the same mechanism. © 1994 John Wiley & Sons, Inc.     

Relaxations in thermosets. XIX. Dielectric effects during curing of diglycidyl ether of bisphenol-A with a catalyst and the properties of the thermoset

Changes in the dielectric permittivity ε′ and loss epsiv;″ during the curing of DGEBA catalyzed by 10 mole % dimethylbenzylamine have been studied from sol to gel to glass formation regions at different temperatures from 323 to 390 K. The ε′ monotonically decreases with time of cure, and ε″ initially decreases by several orders of magnitude and then increases to reach a peak value before finally decreasing to a low value characteristic of the glassy state. The features shift to shorter times and the peak vanishes as the curing temperature is increased. The decrease of ε″ at the initial stage of cure has been analyzed in terms of dc conductivity σ₀, which follows a power law, σ₀ ∝? (t_g–t)^x, as well as a new singularity equation, σ₀ ∝? exp[–B/(t₀–t)] where t_g, x, B, and t₀ are empirical constants that vary with the curing temperature; t_g is close to the time for gelation; and t₀ ≥ time for vitrification. The dielectric properties of the thermoset formed after different periods of cure have been studied from 77 to 325 K. Similar studies of the thermosets formed at different temperatures have been made. Increase in the curing period decreases the heights of both the γ-and α-relaxation peaks and increases their separation, while a β-relaxation peak emerges. Isothermal curing at high temperatures decreases the height of the γ peak to a vanishingly small value and increases that of the β peak from a vanishingly small value. In both the uncured and fully cured states, there is only one sub-T_g relaxation process named γ for the uncured and β for the cured state. These results are discussed in terms of our general physical concepts of local mode motions in an amorphous matrix. © 1993 John Wiley & Sons, Inc.     

Relaxations in thermosets. VI. Effects of crosslinking on sub-Tg relaxations during the curing and aging of epoxide-based thermosets

The dielectric permittivity and loss of diglycidyl ether of bisphenol-A-based thermosets cured with diaminodiphenyl methane and diaminodiphenyl sulfone have been measured over a temperature range 77–400 K after curing or aging for a predetermined duration. Of the two sub-T_g relaxations, the height of the γ relaxation peak monotonically decreases during both the cure and postcure periods, and the height of the β relaxation peak first increases to a maximum value and then decreases. This decrease is attributed to physical aging effects. The height of the α-relaxation peak decreases. The γ- and β-relaxation peaks become increasingly separated in temperature. A concept of accumulated equivalent curing time which is based upon known chemical kinetics has been introduced for use in both theoretical and practical aspects of the study of thermosets. It is shown that substantial curing of the sample occurs during its slow heating to the curing temperature. The use of this concept in the curing of thermosets is illustrated. A procedure for the analysis of the distribution of relaxation times from a set of results limited in both frequency and temperature range is described. The distribution parameter is 0.20 and 0.16 for the γ and β process, respectively, and remains constant with postcuring and physical aging. The distribution parameter for the α process decreases from 0.60 to 0.36 on curing.     

Study of dielectric relaxations of anhydrous trehalose and maltose glasses

We investigated the frequency dependent dielectric relaxation behaviors of anhydrous trehalose and maltose glasses in the temperature range which covers a supercooled and glassy states. In addition to the α-, Johari-Goldstein (JG) β-, and γ-relaxations in a typical glass forming system, we observed an extra relaxation process between JG β- and γ-relaxations in the dielectric loss spectra. We found that the unknown extra relaxation is a unique property of disaccharide which might originate from the intramolecular motion of flexible glycosidic bond. We also found that the temperature dependence of the JG β-relaxation time changes at 0.95T(g) and it might be universal.     

Fundamentals of ionic conductivity relaxation gained from study of procaine hydrochloride and procainamide hydrochloride at ambient and elevated pressure

The pharmaceuticals, procaine hydrochloride and procainamide hydrochloride, are glass-forming as well as ionically conducting materials. We have made dielectric measurements at ambient and elevated pressures to characterize the dynamics of the ion conductivity relaxation in these pharmaceuticals, and calorimetric measurements for the structural relaxation. Perhaps due to their special chemical and physical structures, novel features are found in the ionic conductivity relaxation of these pharmaceuticals. Data of conductivity relaxation in most ionic conductors when represented by the electric loss modulus usually show a single resolved peak in the electric modulus loss M(")(f) spectra. However, in procaine hydrochloride and procainamide hydrochloride we find in addition another resolved loss peak at higher frequencies over a temperature range spanning across T(g). The situation is analogous to many non-ionic glass-formers showing the presence of the structural α-relaxation together with the Johari-Goldstein (JG) β-relaxation. Naturally the analogy leads us to name the slower and faster processes resolved in procaine hydrochloride and procainamide hydrochloride as the primary α-conductivity relaxation and the secondary β-conductivity relaxation, respectively. The analogy of the β-conductivity relaxation in procaine HCl and procainamide HCl with JG β-relaxation in non-ionic glass-formers goes further by the finding that the β-conductivity is strongly related to the α-conductivity relaxation at temperatures above and below T(g). At elevated pressure but compensated by raising temperature to maintain α-conductivity relaxation time constant, the data show invariance of the ratio between the β- and the α-conductivity relaxation times to changes of thermodynamic condition. This property indicates that the β-conductivity relaxation has fundamental importance and is indispensable as the precursor of the α-conductivity relaxation, analogous to the relation found between the Johari-Goldstein β-relaxation and the structural α-relaxation in non-ionic glass-forming systems. The novel features of the ionic conductivity relaxation are brought out by presenting the measurements in terms of the electric modulus or permittivity. If presented in terms of conductivity, the novel features are lost. This warns against insisting that a log-log plot of conductivity vs. frequency is optimal to reveal and interpret the dynamics of ionic conductors.     

Influence of the crystalline phase on the molecular mobility of PVDF

Dielectric relaxation and pyrocurrent of PVDF were studied by thermostimulated current spectroscopy. The transition spectrum of the material was investigated by differential scanning calorimetry. Two well-resolved relaxation peaks have been observed in the temperature range [?100–100°C]. The molecular mechanisms of these phenomena have been discussed, based on a comparative study of α-PVDF. and β-PVDF. The β relaxation mode is located at ?41°C in α-PVDF and is slightly shifted toward higher temperatures in the stretched material. This mode has been ascribed to the dielectric manifestation of the glass transition (T_g) of PVDF. It is comprised of two components corresponding to the free and constrained amorphous phases, respectively, in the order of increasing temperatures. The α_c transition/relaxation has been associated with molecular motions in the crystalline/amorphous interphase. At higher temperatures, a compensation phenomenon corresponding to cooperative movements liberated at the Curie transition has been observed in β-PVDF. © 1993 John Wiley & Sons, Inc.     

Dielectric properties of novel poly(aryl prehnitimide)s

Six different variants of a new type of polyimide, poly(aryl prehnitimide)s, containing various moisture contents have been studied using dielectric relaxation spectroscopy. Dielectric loss measurements show the presence of a double peak near 200 K (depending on frequency) due to water relaxation. The two peaks have been designated γ₁ and γ₂. The γ₂ peak appears as a shoulder on the γ₁ peak at lower temperatures and is very sensitive to moisture content. The γ₁ peak is less sensitive to moisture content and is associated with isolated water molecules coupled to the polymer chains. Both of the γ-relaxation peaks were studied in detail to obtain the associated activation energies. © 1996 John Wiley & Sons, Inc.     

尼龙-1010结晶结构

用WAXD方法测定了Nylon-1010为三斜晶系结晶结构;α=4.9(?),b=5.4(?),c=27.8(?),α=49°,β=77°,γ=63.5°,每个聚合物单胞含有一个重复单元,空间群为P(?)。模压试样用Ruland方法分析结晶度为60％。以上。电子密度相关函数法分析了SAXS现象,求得了Nylon-1010结晶片层厚度、过渡层厚度、长周期、比内表面及电子密度差。     

THE DEGREE OF CRYSTALLINITY OF NYLON-1010 BY WAXD

Based on the X-ray scattering intensity theory and using the atomic scattering factorapproximate expression,the correction factors for three main crystalline peaks and an amorphouspeak of Nylon-1010 were calculated and the formula of degree of crystallinity of Nylon-1010 wasderived by graphic multipeak resolution method. The results calculated are compatible with the density measurement and calorimetry.     

Water effect in the thermal and molecular dynamics behavior of poly(<Emphasis Type="Italic">L</Emphasis>-lactic acid)

A detailed dielectric characterization of the relaxation modes found in a poly(L-lactic acid), PLLA, film containing 0.4 mass% of water is provided. The sub-glass relaxation process is a superposition of two processes, one highly influenced by water with activation energy of 50 kJ mol^–1, and another one, with longer relaxation times and lower intensity having activation energy of 38 kJ mol^–1. Dried PLLA exhibits an abnormally broad secondary β-relaxation that probably corresponds to the superposition of multiple processes. Upon water sorption the strength of the more mobile process significantly increases being shifted to lower temperatures which allows the detection of the underlying process. The glass transition relaxation process is deviated to higher frequencies almost one decade due to the water plasticizing effect. The reported results show that small quantities of water may have a profound impact in the relaxational features in PLLA, which should be taken in account when considering the properties and performance of this system.     

Influence of Phase Morphology on Molecular Mobility of Poly(propylene)-(ethylene-vinyl acetate) Copolymer Blends

The dynamic mechanical and dielectric behaviours of Polypropylene (PP) and (Ethylene-Vinyl Acetate) Copolymer (EVA) blends are reported as a function of the morphology. For EVA contents lower than 20%, blends show the two-phase morphology characteristic of immiscible blends, with spherical EVA droplets finely dispersed in the PP matrix. After stretching in the molten state, the morphology of EVA fibers is observed. Mechanical Relaxation Spectroscopy display three relaxation processes: the EVA and PP α-relaxations associated to the glass transitions and a β-transition corresponding to a PP crystalline phase relaxation. The PP α-relaxation shifts to higher temperatures when EVA presents a fiber morphology, corresponding to a decrease of PP chain mobility since it is hindered by the reinforcement effect of EVA fibers. Quite different results are obtained by DRS analysis. In blends containing EVA fibers, only one main relaxation associated to the EVA α-transition is observed whereas one additional relaxation can be noticed in the blends containing EVA droplets. This new relaxation might be assigned to interfacial polarization effects, phenomena that are sometimes observed in heterogeneous polymer blends when a low content of one polar component is embedded in a non conductive matrix. In this case, the occurrence of a characteristic interfacial polarization relaxation appears to be correlated to the accessible experimental frequency.     

Study on rheological properties and relaxational behavior of poly(dianilinephosphazene)/low-density polyethylene blends

Rheological properties and relaxational behavior of blends of low-density polyethylene (LDPE) and poly(dianilinephosphazene) (PDAP) have been investigated to check miscibility and molecular relaxations in the crystalline and amorphous phases. In the studied shear rate range, all PDAP/LDPE blends exhibited a shear thinning behavior. The experimental data were fitted using the logarithmic rule and serial model to investigate the miscibility of blends. It was found that LDPE and PDAP can achieve a certain degree of miscibility in the molten state. The dynamic mechanical α-, β- and γ-relaxation behavior obtained from dynamic mechanical thermal analysis imply that the two components in the amorphous phase were miscible. The wide-angle X-ray diffraction result showed that these two components interact with each other.