Selective polymeric effects on solvent NMR relaxations

Measurements of the spin-lattice relaxation times (T₁) of solvent protons have been performed on systems containing mixed solvents with and without polymer. It has been found that the motion of solvent is selectively affected by polymers present in the system. Polyisobutylene (10%) in mixed solvents of carbon tetrachloride (or cyclohexane) and dichloromethane at various proportions produces little effect on T₁ values of dichloromethane, but it affects significantly the T₁ values of cyclohexane; whereas poly(methyl methacrylate) (10%) in carbon tetrachloride and dichloromethane (or acetone) selectively associates with dichloromethane (or acetone), resulting in an approximate 50% reduction of the T₁ values for dichloromethane (or acetone). In systems of poly(methyl methacrylate) and three mixed solvents of carbon tetrachloride, dichloromethane, and cyclohexane, the polymer (10%) has a negligible effect on the T₁ values of cyclohexane, but brings about a 50% reduction of the T₁ values of dichloromethane. These phenomena are discussed in terms of local selective interactions between the solvent molecules and the polymeric chain segments.     

Dielectric and shear mechanical alpha and beta relaxations in seven glass-forming liquids

We present shear mechanical and dielectric measurements taken on seven liquids: triphenylethylene, tetramethyltetra-phenyltrisiloxane (Dow Corning 704 diffusion pump fluid), polyphenyl ether (Santovac 5 vacuum pump fluid), perhydrosqualene, polybutadiene, decahydroisoquinoline (DHIQ), and tripropylene glycol. The shear mechanical and dielectric measurements are for each liquid performed under identical thermal conditions close to the glass transition temperature. The liquids span four orders of magnitude in dielectric relaxation strength and include liquids with and without Johari-Goldstein beta relaxation. The shear mechanical data are obtained by the piezoelectric shear modulus gauge method giving a large frequency span (10(-3)-10(4.5) Hz). This allows us to resolve the shear mechanical Johari-Goldstein beta peak in the equilibrium DHIQ liquid. We moreover report a signature (a pronounced rise in the shear mechanical loss at frequencies above the alpha relaxation) of a Johari-Goldstein beta relaxation in the shear mechanical spectra for all the liquids which show a beta relaxation in the dielectric spectrum. It is found that both the alpha and beta loss peaks are shifted to higher frequencies in the shear mechanical spectrum compared to the dielectric spectrum. It is in both the shear and dielectric responses found that liquids obeying time-temperature superposition also have a high-frequency power law with exponent close to -12. It is moreover seen that the less temperature dependent the spectral shape is, the closer it is to the universal -12 power-law behavior. The deviation from this universal power-law behavior and the temperature dependencies of the spectral shape are rationalized as coming from interactions between the alpha and beta relaxations.     

Moisture effects on the glass transition and the low temperature relaxations in semiaromatic polyamides

The influence of moisture absorption on the primary (glass) transition (T_a or T_g) and the low temperature relaxations of semiaromatic amorphous polyamides synthesized by isomeric aliphatic diamine and metha or para oriented phthalicdiacids has been investigated by means of differential scanning calorimeter (DSC) and dynamic mechanical thermal analyser (DMTA). The glass transition of semiaromatic polyamides was lowered due to the water absorption, and the β and the γ relaxations were as well. From the observed T_g and the difference in the heat capacity, the calculated T_g depression per 1 wt % water content was 12.3 K and the result was in good agreement with the experimental data. The depression of the glass transition may be expressed by the same manner as the plasticization of nylon 6 by water. The depressed β relaxation observed in the specimen containing a few percent of moisture was splitted into two transitions due to the reduction of water content, of which one was the elevation of the T_β and another was the simultaneous appearance of the T_γ, and then the single T_γ solely was observed for the completely dried specimen. The T_γ seemed to be merged into or not to be observed by the large and broad T_β transition when the sample was governed by a few percent of water, then it was emerged from the T_β due to water desorption. Thus, the T_β is believed to arise from the intermolecular hydrogen bonding between water molecules or between water and amide groups in wet polyamides. In addition, the γ relaxation originated from the peptide groups is attributable to the inter- and intramolecular hydrogen bonding between amide groups. © 1997 John Wiley & Sons, Inc. J Polyn Sci B: Polym Phys 35: 807–815, 1997     

Effect of physical aging on the Johari-Goldstein and alpha relaxations of D-sorbitol: a study by thermally stimulated depolarization currents

The relaxations in amorphous D-sorbitol have been studied by thermally stimulated depolarization currents during annealing at 255 K, which is 17 K below its calorimetric glass transition temperature Tg=272 K. As the glass structurally relaxes on aging, the features of the alpha relaxation and of the Johari-Goldstein (JG) relaxation change with time. For the alpha relaxation (i) the dielectric strength decreases; (ii) the activation energy decreases; and (iii) the relaxation time increases. For the JG relaxation the dielectric strength also decreases but with a different time dependence, and there is no evidence for any modification of the kinetic features of the mobility. The amplitude of response to aging is higher for the higher temperature motional components of the Johari-Goldstein relaxation compared with the lower temperature ones.     

Reconstructions and relaxations on metal surfaces

On metal surfaces the top layer of atoms usually relaxes inwards, and several metal surfaces reconstruct, particularly W and Mo (001) and Ir, Pt and Au (001) and (110). This paper reviews the electronic origins of these atomic displacements, and the physical effects which they lead to. The surface relaxations are explained in terms of the change in balance between electronic forces at the surface. The W (001) surface reconstructs from (1 × 1) to (?2 × ?2)R45° in a continuous phase transition on cooling below room temperature, and the structure of these phases and the nature of the phase transition are discussed. The driving force for the reconstruction is discussed in terms of calculations and photoemission studies of the surface electronic structure. Phenomenological Landau theory is used to describe the effect of surface steps on the transition, and the origin of the long wavelength modulation in the Mo (001) reconstruction. Finally the reconstructions of Ir, Pt and Au (001) and (110) are briefly described; these involve a more substantial movement of atoms than in the W and Mo reconstructions.     

Pressure effects on the fluorescence from naphthalene vapour

The fluorescence lifetimes and yields of naphthalene vapour have been measured at low pressure as a function of exciting wavelength and of the pressure of added foreign gases. The lifetimes and yields increase with pressure for short wavelength excitation (< 305 nm) and decrease with increasing pressure for excitation > 305 nm. The pressure dependence of the naphthalene S 1 state at low excitation energies is interpreted in terms of collisionally induced vibrational redistribution.     

Effect of free volume and temperature on the structural relaxation in polymethylphenylsiloxane: a positron lifetime and pressure-volume-temperature study

The microstructure of the free volume and its temperature dependence in polymethylphenylsiloxane (PMPS) have been examined using positron annihilation lifetime spectroscopy (PALS) and pressure-volume-temperature experiments. The hole-free volume fraction h and the specific hole-free and occupied volumes, Vf=hV and Vocc=(1-h)V, were estimated employing the Simha-Somcynsky (SS) lattice-hole theory. From the PALS spectra analyzed with the new routine LT9.0 the hole size distribution, its mean, , and mean dispersion, sigmah, were calculated. A comparison of with V and Vf delivered a constant specific hole number Nh'. Using a fluctuation approach the temperature dependency of the volume of the smallest representative freely fluctuating subsystem, , is estimated to vary from approximately 8.5 nm3 at Tg to approximately 3 nm3 at T/Tg>or=1.15. Unlike other polymers, the segmental relaxation from dielectric spectroscopy of PMPS follows the Cohen-Turnbull free volume theory almost perfectly in the temperature and pressure ranges between 243 and 279 K and 0 and approximately 100 MPa. This behavior correlates with the small mass of the SS lattice mer which indicates the high flexibility of the PMPS chain. Above 293 K and approximately 150 MPa, the free volume prediction gives relaxation times that are too small, which indicates that effects of thermal energy must be included in the analysis. To quantify the degree to which volume and thermal energy govern the structural dynamics the ratio of the activation enthalpies, Ei=R[(d ln taudT1)]i (tau-relaxation time of alpha relaxation), at constant volume V and constant pressure P, EV/EP, is frequently determined. The authors present arguments for necessity to substitute EV with EVf, the activation enthalpy at constant (hole) free volume, and show that EVf/EP changes as expected: increasing with increasing free volume, i.e., with increasing temperature and decreasing pressure. EVf/EP (=0.04-0.1) exhibits remarkably smaller values than EV/EP (=0.44-0.53), which leads to the inference that the free volume plays a distinctly larger role in dynamics than traditionally concluded from EV/EP. This conclusion is in agreement with the results of our more direct Cohen-Turnbull free volume analysis.     

Transitions and relaxations in aromatic polymers

Transition and relaxation phenomena in 26 structurally related polyquinoxalines and other aromatic polymers were studied over a temperature range from 70 to 770°K by means of calorimetric, dilatometric, dynamic mechanical, and dielectric techniques. Differential thermal analysis and x-ray data showed these polymers to be essentially amorphous. The lack of crystallinity is attributed to geometric isomerism, resulting in conformational as well as configurational disorder. Calorimetric measurements gave discontinuities in heat capacities ranging from 12 to 54 cal/°C per mole of repeat-unit structures and provided unambiguous assignments of glass transition temperatures of these polymers. Depending upon structure, T_g varied from 489 to 668°K. Thermal expansion curves of annealed bulk polymer samples between 70 and 770°K exhibited only one discontinuity over the entire temperature range, namely at T_g, thus indicating the absence of any motion leading to transitions in the solid state of these polymers. Viscoelastic properties were obtained by means of torsional braid analysis and a longitudinal vibrational apparatus. In a typical case, the dynamic mechanical relaxation spectrum contained three loss maxima. A peak of low amplitude occurring at 483°K was attributed to impurity effects, resulting from endgroups and species of low molecular weight. The second and only major relaxation process occurred at 579°K, in the glass transition interval. A third, weak loss peak of unknown origin was found in the liquid state at 683°K. On the other hand, the dielectric loss curves of various polymers exhibited only one broad and strong absorption maximum at temperatures 30 to 100°K higher (depending upon a particular polymer) than equivalent major mechanical loss peaks. These differences are interpreted from a mechanistic point of view. Major mechanical relaxations occurring in the glass transition interval of these polymers are proposed to result from translational motions.     

Pressure and temperature effects on the excess deuteron and proton conductance

The limiting molar conductances ° of deuterium chloride DCl in D₂O were determined as a function of pressure and temperature in order to examine the proton-jump mechanism in detail. The excess deuteron conductances °_E(D ⁺), as estimated by the equation [°_E(D ⁺) = °(DCl/D ₂ O) – °(KCl/D ₂ O)], increases with an increase in the pressure and temperature as well as the excess proton conductance [°_E(H ⁺) = °(HCl/H ₂ O) – °(KCl/H ₂ O)]. The isotope effect on the excess conductances, however, depends on the pressure and temperature contrary to the model proposed by Conway et al.: °_E(H ⁺)/°_E(D ⁺) decreases with increasing pressure and temperature. The magnitude of the decrease with pressure becomes more prominent at lower temperature. These results are discussed in terms of the pre-rotation of adjacent water molecules, the bending of hydrogen bonds with pressure, and the difference in strength of hydrogen bonds between D₂O and H₂O.     

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     

Mechanical relaxations in polyamides

Dynamic mechanical measurements were carried out as a function of temperature (?100 to + 180°C) and frequency (3.5 to 110 cps) for a series of aliphatic terpolyamides, nylon 6 and nylon 12. Effect of crosslinking with toluene diisocyanate, of absorbed water, and of frequency are used to estimate the statistical segment length associated with the α′ relaxation. The effects of variations in the aliphatic chain length in the repeating unit on the temperature of the α′ relaxation are examined by means of copolymer rules with a view to explaining the reported insensitivity of the glass transition temperature of these polymers to changes in (CH₂)/(amide) group ratio. From the estimated length of the segmental motion associated with the α′ relaxation it is inferred that in a series of polyamides of the type nylon X or nylon X,Y (where X or Y = 3, 4, 5, 6, etc.) there should be a relatively small change in the temperature of the α′ transition for those polyamides having X or Y less than about 45. Experiments which are intended to establish the position of the crystalline α–γ transition are discussed.     

Pressure effects on resolution in ion mobility spectrometry

This paper explains the effect of pressure on separation factor, resolving power (defined based on a single peak), and resolution (defined based on two adjacent peaks) in ion mobility spectrometry. IMS spectra were recorded at various pressures ranging from 39 hPa (29 Torr) up to atmospheric pressure and various ion gates ranging from 50 to 225 μs. The results show that the IMS peaks shift perfectly linear with pressure so that separation factors remain unaffected by pressure. However, pressure has strong influence on resolving power and resolution. Reducing pressure at constant pulse width decreases the resolving power and resolution. On the other hand, the decrease in resolution can be compensated by shortening the ion pulse width since reducing pressure results in a higher ion current.     

Pressure effects in hot-atom chemistry

It is shown that the yield of ³H.H, formed by the reaction of recoil tritium with a hydrocarbon, is enhanced by low hydrocarbon pressures (< 10 cm/Hg).     

Analysis of the relaxations on polymers from the real part of a general complex susceptibility. Application to dielectric relaxations

From a thermodynamic relation that involves the generalized relaxation function, an approximated method that allows estimation of the thermal dependence of the imaginary part of the general complex susceptibility from the real part is discussed. Several conditions such as broad distribution of relaxation times, the applicability of the time–temperature superposition principle, and the temperature dependence of the relaxation strength are considered and analyzed, together with the expected thermal behavior of the relaxed and unrelaxed susceptibilities. The method is tested by means of dielectric measurements on the poly(vinyl acetate) polymer in the temperature range corresponding to the segmental dynamics and the secondary relaxation. An acceptable agreement respect with the maximum temperature of the ε″(T) and the width and shape of the loss peak is obtained between the experimental and estimated imaginary part. This comparison gives validity to the method when the imaginary part is experimentally not well resolved due to the signal–resolution ratio or to the presence of other contributions that mask the thermal behavior of the imaginary part. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1337–1349, 1999     

Pressure effects on relative retention in capillary gas-liquid chromatography

Equations have been obtained for the dependence of relative retention and retention indexes on average column pressure. The equations suggested conform well with experimental data. It was shown that limiting value of relative retention (at the pressure approaches zero) is an invariant retention value. The nature of the stationary liquid phase used and its film thickness have a substantial influence on the dependence of relative retention and capacity factor on the pressure.     

Pressure effects on the electron spin relaxation of several radicals in solution

The pressure effect on the decay rate of chemically induced dynamic electron spin polarization (CIDEP) was investigated on several free-radical intermediates in photolysis, and the spin-lattice relaxation times for these radicals were estimated from the decay rates of CIDEP signals at various pressures. The spin-lattice relaxation rates were retarded by increasing external pressure. From the pressure dependence of the spin-lattice relaxation rates the activation volume was estimated. The activation volumes of these radicals divide into two groups; ≈30 cm³ mol⁻¹ for negative ions and ≈10 cm³ mol⁻¹ for neutral radicals.     

Pressure effects on the transitions between disordered phases in supercooled liquid silicon

We investigate the pressure effects on the transitions between the disordered phases in supercooled liquid silicon through Monte Carlo simulations and efficient methods to compute free energies. Our calculations, using an environment dependent interatomic potential for Si, indicate that at zero pressure the liquid-liquid phase transition, between the high density liquid and the low density liquid, occurs at a temperature 325K below melting. We found that the liquid-liquid transition temperature decreases with increasing pressure, following the liquid-solid coexistence curve. As pressure increases, the liquid-liquid coexistence curve approaches the region where the glass transition between the low density liquid and the low density amorphous takes place. Above 5 GPa, our calculations show that the liquid-liquid transition is suppressed by the glassy dynamics of the system. We also found that above 5 GPa, the glass transition temperature is lower than that at lower pressures, suggesting that under these conditions the glass transition occurs between the high density liquid and the high density amorphous.     

Pressure effects on the phase transition of urea adducts withn-paraffins and polyethylene

The decomposition of urea adducts with hydrocarbons is treated as a first-order phase transition and the pressure dependence is studied up to 0.7 GPa for several kinds of adducts. The thermodynamic quantities at the decomposition of the adduct can be analysed as a sum of those quantities of the component materials. The transition from the orthorhombic to the hexagonal form of the adduct with polyethylene is also investigated by X-ray diffraction and the pressure dependence of the lattice parameters is measured for the adducts. The results are compared with the phase transition in the pure paraffin.     

Pressure effects on the inhomogeneities of environmentally sensitive polymer gels

The effects of pressure at gel preparation on the inhomogeneities were investigated by small-angle neutron scattering. Poly(N-isopropylacrylamide) (PNIPA) gels, known as thermosensitive polymer gels undergoing volume transition, were prepared at various pressures ranging from 0.1 to 300 MPa. The scattering intensity increased with increasing P_prep, up to 200 MPa, then decreased by further increase in P_prep. The degree of inhomogeneities evaluated by the ratio of the static and dynamic correlators exhibited a similar behavior to that of the ensemble average light scattered intensity, <I>_E. The physical meaning of the gel inhomogeneities is discussed from the viewpoint of swelling thermodynamics. It will be shown that the increase in the swelling degree is due not to an increase in the miscibility of PNIPA with water but to the increase in inhomogeneities.     

Structural relaxations and energy effects of intramolecular motions inN,N-dimethylnitramine: A theoretical study

The equilibrium geometry of theN,N-dimethylnitramine molecule and changes in the energy and structural parameters due to the internal rotation of the nitro group and the inversion of the N atom in the amino fragment were calculated by the restricted Hartree-Fock (RHF) method and at the second-order Møller-Plesset (MP2) level of perturbation theory with inclusion of electron correlation using the 6–31 G^* and 6–31 G^** basis sets. The one-dimensional potential functions of these motions calculated at the RHF/6–31 G^* level were approximated by a truncated Fourier and power series, respectively. The frequencies of torsional and inversion transitions were determined by solving direct vibrational problems for a non-rigid model,i.e., taking into account the molecular geometry relaxation. The equilibrium conformation of the molecular skeleton ofN,N-dimethylnitramine is nonplanar. Transition states of the internal rotation of the nitro group and inversion of the amine N atom are characterized by pronounced concerted changes in its bond angles and the length of the N?N bond. In the MP2/6–31 G^* approximation, the height of the barrier to internal rotation calculated taking into account the difference in the zero-point vibrational energies is equal to 9.7 kcal mol^?1. Inversion in the amino fragment is accompanied by a relatively small energy change at the barrier height of ?1.0 kcal mol^?1 calculated in the same approximation.