Dielectric relaxation and aging effect in interpenetrating network polymers of poly(urethane)-poly(methyl methacrylate)

The permittivity and loss of poly(methyl methacrylate) (PMMA) network crosslinked with trimethylol-1,1,1 propane and its interpenetrating network polymers with 10, 34, and 50% (by weight) poly(urethane) have been measured from 100 to 400 K over a frequency range of 12 to 1 × 10⁵ Hz. Two relaxation processes, γ and β, are observed in the PMMA network, and a third process, α_pu, in the 10% poly(urethane) IPN. At higher concentrations of poly(urethane), the γ process is removed from the temperature-frequency range of our study. Crosslinking in pure PMMA slows the segmental motions involved in the β process and raises its activation energy. Physical aging of the 10 wt% poly(urethane)-PMMA causes its γ process to become indiscernible and the α_pu process to become better resolved. A discussion of these results in terms of local regions of segmental motion is provided.     

Capable Lie algebras with the derived subalgebra of dimension 2 over an arbitrary field

In this paper, we classify all capable nilpotent Lie algebras with the derived subalgebra of dimension 2 over an arbitrary field. Moreover, the explicit structure of such Lie algebras of class 3 is given.     

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.     

A dielectric study of chain motions in poly(vinyl methyl ether)

The dielectric permittivity and loss of poly(vinyl methyl ether) (mol. wt. 30,000) have been measured from 12 Hz to 100 kHz at temperatures from 77 K to 320 K. Two relaxation processes, γ and β, are observed at T < T_g (245 K), and one above T_g. The Arrhenius plots of the γ and β processes have activation energies of 20 and 41 kJ mole^?1 respectively. The relaxation rate of the α process is described by the Vogel-Fulcher-Tamman equation or the William-Landel-Ferry equation. The relaxation rates of γ and β processes evaluated from the isochrones differ from those evaluated from the isothermal spectrum. The features of chain motions observed are similar to those in other polymer and rigid molecular glasses.     

The dielectric properties of dry and water-saturated nylon-12

The dielectric relaxation of 30% crystalline Nylon-12 of molecular weight 20,000 has been studied at frequencies from 12 Hz to 0.1 MHz and temperatures from 77 to 375 K, and the effect of water on the relaxation spectra has been investigated. Absorbed water increases both the rate and the intensity of both its α-and β-relaxation processes and increases the rate but decreases the intensity of its γ-relaxation process. These results are interpreted in terms of the hydrogen bonding effects of water on localized motions of dipoles in Nylon-12. The relatively large half-width of the α-relaxation, which becomes better resolved at high temperatures, is attributed mainly to the random distribution of crystalline regions in the polymer. It is suggested that water lowers the steric hindrance for the localized mode of dipolar reorientation and causes a redistribution of local sites such that the β-relaxation process grows at the expense of the γ-process.     

Debye process and dielectric state of an alcohol in a nonpolar solvent

To investigate the origin of the first order molecular kinetics of the most prominent, Debye-type polarization, a detailed dielectric relaxation study of 66.5, 40, and 20 mole% solutions of 5-methyl-2-hexanol in 2-methylpentane (2:1, 0.67:1, and 0.25:1 molar ratios) was performed. The Debye-type polarization remains prominent in the solutions, despite the extensive loss of intermolecular hydrogen bonds. At high temperatures, its contribution to permittivity extrapolates close to the statistically scaled values for the 2:1 solution. For others, the measured values of its contribution crossover the scaled values in a temperature plane. The faster relaxation process of about 4% magnitude has an asymmetric distribution of times in the solutions and, relative to those of the pure alcohol, their values decrease on heating more at high temperatures and less at low. This is attributed to an increase in the alcohol cluster size by consumption of monomers as well as the growth of smaller clusters as the solution is cooled. It is argued that structural fluctuation in solutions, as in the pure alcohol, is determined by the rates of both the Debye-type and the faster polarizations in the ultraviscous state.     

Simultaneous dielectric spectroscopy and calorimetry of the dynamics during a macromolecules growth

Summary A method and an instrument has been developed for measuring almost simultaneously and continuously in time three different quantities: i) the heat evolved during the course of exothermic reactions, ii) the heat capacity and iii) the dielectric spectra of a liquid or solid sample. By using this instrument, we have studied the decrease in the d.c. conductivity and the increase in the relaxation time as molecules in an isothermally kept liquid chemically react to produce, irreversibly, a macromolecular structure until the liquid vitrifies and becomes rigid. The number of covalent bonds formed in the structure,n, has been calculated and the dielectric relaxation time, τ, is related ton. This τ increases progressively more rapidly withn, and decreases, of course, on increasing the temperature. A compensation between these two effects determines the dynamic behaviour observed during rate heating. The effect of temperature is found to predominate. Such observations have been made possible by means of the new instrument.     

Calorimetric relaxation and glass transition in poly(propylene glycols) and its monomer

The glass transition temperature T_g of propylene glycol (PG) and poly(propylene glycols) (PPGs) of molecular weight up to 4000 has been measured by differential scanning calorimetry, and the activation energy and change in heat capacity ΔC_p have been determined in the glass transition range. The activation energy increases with an increase in the molecular weight of the polymer, and ΔC_p measured at a fixed heating rate decreases. The increase in T_g with molecular weight is remarkably more rapid for poly(propylene glycols) than for other polymers, and a limiting value of T_g is reached for a chain containing 20 monomer units. These results are discussed in terms of the Fox-Flory and the entropy theories. The calorimetric relaxation times are comparable with the extrapolated dielectric relaxation times. The initial increase of ΔC_p from PG to PPG 200 is attributed to the decrease of H-bonding sites from 12 in 3 monomers to 4 on polymerization to PPG 200 and further decrease with increase in molecular weight to an increasingly large amplitude of the β-process at T < T_g.     

Water's size-dependent freezing to cubic ice

Water has been occasionally found to freeze to cubic ice. To investigate this occurrence thermodynamically, we use the known enthalpy and interfacial energy of hexagonal and cubic ices and calculate a critical radius r(c) of appromximately 15 nm for a water droplet and a critical thickness delta(c) of approximately 10 nm for water's flat film. Accordingly, water droplets smaller than 15 nm radius and films thinner than 10 nm would freeze to cubic ice in the 160-220 K range and bigger droplets and thicker films would freeze to hexagonal ice. This provides a thermodynamic basis for the occasionally found presence of cubic ice in the atmosphere, and explains why water's nanometer-sized clusters and water confined to nanometer-sized pores freeze to cubic ice. Conditions for cubic ice-hexagonal ice phase inversion have been discussed. Impurities in water and different extents of proton ordering in the crystallites of cubic and hexagonal ices would have a significant effect on r(c) and delta(c).