Nuclear magnetic relaxation in polyolefin resins

Nuclear magnetic resonance (NMR) spin–lattice relaxation times (T₁) in various polyethylene and polypropylene resins were measured at 20 MHz and at temperatures of 130–490 K. At each temperature and for all resins, only a single value of T₁ was found, which was consistent with the occurrence of rapid spin diffusion throughout the protons attached to the polymer chains. The data were analyzed for the estimation of activation energies corresponding to molecular motion causing spin–lattice relaxation. Two well‐defined minima were found for log_e(T₁) plotted as a function of temperature for all of the polypropylene resins. Single very broad minima were found for all of the polyethylene samples. In contrast, the free induction decay signals from all of the resins following single radio‐frequency pulses were observed to contain a rapidly decaying component followed by a much more slowly decaying signal. These components were used to estimate the amount of rigid component present in the solid resins at room temperature. Samples of one high‐density polyethylene and one low‐density polyethylene were irradiated with γ radiation up to a 500‐kGy dose to examine the effects of crosslinking on the NMR relaxation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 572–584, 2002; DOI 10.1002/polb.10116     

Nuclear magnetic relaxation in polyelectrolyte solutions

Some applications of nuclear magnetic relaxation in the investigation of aqueous polyelectrolyte solutions are discussed. The main topics are solvent dynamics, counterion - polymer interaction, main chain mobility and diffusion.     

Nuclear magnetic relaxation in water revisited

In this study, we revisited nuclear magnetic relaxation of (1)H in water at very low Larmor frequencies that has been studied intensively in earlier years. We make use of the recently developed superconducting quantum interference device based ultra-low field NMR technique, which enables much easier access to the longitudinal spin-lattice relaxation time T(1) and the transversal spin-spin relaxation time T(2) below several kHz than traditional field cycling methods. Our data reproduce and complement the earlier results, in that they corroborate the finding of an exchange process with a correlation time of about 0.34 ms at room temperature which can be attributed to the migration of hydronium and hydroxyl ions in neutral water via hydrogen bridges. The corresponding relaxation process is driven by the interaction of the protons with (17)O and contributes to the T(1) and the T(2) relaxation rate by about 0.12 s(-1). In addition, we found evidence of a very slow exchange process at about 100 Hz that has hitherto not been reported.     

Nuclear magnetic resonance relaxation titration

Summary Quantitative determination of the concentration of paramagnetic ions in aqueous solutions is performed by NMR relaxation titration. By measurement of the nuclear spin-lattice relaxation time T ₁ or the nuclear spin-spin relaxation time T₂ redox titrations and complexometric determinations of the concentration of paramagnetic ions are possible. Also the precipitation of ions from the solution can be followed by this method. The use of a magnetic indicator in this analytical method is shown. The sensitivity of the method goes down to concentrations as low as 10^–3 M. The accuracy of NMR relaxation titration is better than 1%. A number of applications of the method are given.

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Kernmagnetische Relaxationstitration

Zusammenfassung Quantitative Bestimmungen von paramagnetischen Ionen in wäßrigen Lösungen können mit Hilfe der kernmagnetischen Relaxationstitration durchgeführt werden. Durch Messung der Kernspin-Gitter-Relaxationszeit T ₁ oder der Kernspin-Kernspin-Relaxationszeit T ₂ als Funktion der Ionenkonzentration sind Redoxtitrationen oder komplexometrische Titrationen möglich. Der quantitative Ablauf von Fällungen kann ebenfalls verfolgt werden. Die Verwendung von magnetischen Indicatoren bei der Relaxationstitration wird beschrieben. Bestimmungen von Ionenkonzentrationen bis herab zu 10^–3 M Lösungen sind z.Z. möglich. Die Methode erlaubt eine Genauigkeit der Konzentrationsbestimmung von 1% und besser. Die Anwendung der Methode wird an einer Reihe von Beispielen gezeigt.

     

Nuclear magnetic resonance proton dipolar order relaxation in thermotropic liquid crystals: a quantum theoretical approach

By means of the Jeener-Broekaert nuclear magnetic resonance pulse sequence, the proton spin system of a liquid crystal can be prepared in quasiequilibrium states of high dipolar order, which relax to thermal equilibrium with the molecular environment with a characteristic time (T1D). Previous studies of the Larmor frequency and temperature dependence of T1D in thermotropic liquid crystals, that included field cycling and conventional high-field experiments, showed that the slow hydrodynamic modes dominate the behavior of T1D, even at high Larmor frequencies. This noticeable predominance of the cooperative fluctuations (known as order fluctuations of the director, OFD) could not be explained by standard models based on the spin-lattice relaxation theory in the limit of high temperature (weak order). This fact points out the necessity of investigating the role of the quantum terms neglected in the usual high temperature theory of dipolar order relaxation. In this work, we present a generalization of the proton dipolar order relaxation theory for highly correlated systems, which considers all the spins belonging to correlated domains as an open quantum system interacting with quantum bath. As starting point, we deduce a formulation of the Markovian master equation of relaxation for the statistical spin operator, valid for all temperatures, which is suitable for introducing a dipolar spin temperature in the quantum regime, without further assumptions about the form of the spin-lattice Hamiltonian. In order to reflect the slow dynamics occurring in correlated systems, we lift the usual short-correlation-time assumption by including the average over the motion of the dipolar Hamiltonian together with the Zeeman Hamiltonian into the time evolution operator. In this way, we calculate the time dependence of the spin operators in the interaction picture in a closed form, valid for high magnetic fields, bringing into play the spin-spin interactions within the microscopic time scale. Then, by adopting the spin-temperature density operator to represent the collective state of the spin system, and removing the traditional hypothesis of high temperature, we deduce an expression for the first order quantum contribution to T1D (-1), in terms of spectral densities, with coefficients in form of spin traces. The properties that distinguish our result from the high-temperature T1D (-1) are as follows. (a) It is exclusively associated to cooperative fluctuations. (b) Because of its quantum character, it relies on both considering the lattice degrees of freedom quantum mechanically and including the spin-spin interactions in the microscopic time scale. With regard to the average dipolar Hamiltonian, only the nonsecular part plays a relevant role. (c) Associated with the structure of the spin operator involved in the quantum contribution, a term arises which is proportional to the number of spins in the correlated molecular domains, showing that the quantum contribution may be of macroscopic size in highly correlated systems. When applied to nematic liquid crystals, the new term exhibits the typical nu(-1/2) Larmor frequency dependence through the spectral density of the OFD, in consistence with the experimental results.     

Nuclear magnetic resonance relaxation studies of polyacrylamide solution

 The cohesive interaction among polymer chains in a polyacrylamide (PAAm)–D₂O solution has been studied by NMR relaxation. The NMR relaxation times of PAAm in the good solvent D₂O were measured at different temperatures. The results show that the solution system has a high local viscosity and that its relaxation characteristic is soft-solid-like. The temperature dependence of the relaxation behavior of the solution is obviously different from that of ordinary polymer solutions. The difference lies in the relaxation behavior of the methylene protons in the main chain of PAAm, as shown by analyzing the relaxation process with single exponential and biexponential decays. As the temperature increases, the solvation is weakened, leading polymer chains to form curling coils, thus hindering the movement of the methylene protons among the main chains. It can be expected from the existence of 80% fast-relaxing protons that there are a zhigh number of entanglements among the polymer chains in PAAm solution. The information about entanglements among the polymer chains can be deduced from the biexponential dependence of the spin–spin relaxation on the concentration of the polymer solutions. Received: 14 April 1999/Accepted in revised form: 12 October 1999     

Nuclear magnetic relaxation and structure of aqueous solutions

By the interpretation of the intermolecular nuclear magnetic relaxation rate of¹⁹F the orientation of the water molecules in the hydration sphere of F^– can be determined. Similarly, the orientation of the water molecules around the methyl group of propionic acid in aqueous solution has been studied. Experiments are described which give information about the nature of association of solute in aqueous solution of a number of carboxylic acids and of ethanol. The local dynamic details of the I^– ion have been investigated. Some new results are briefly descussed regarding the nuclear magnetic relaxation by quadrupole interaction in electrolyte solutions.This paper was presented at the symposium, The Physical Chemistry of Aqueous Systems, held at the University of Pittsburgh, Pittsburgh, Pennsylvania, June 12–14, 1972, in honor of the 70th birthday of Professor H. S. Frank.     

Nuclear magnetic relaxation and molecular motion in solid lysozyme

Nuclear magnetic relaxation data for both proton and carbon-13 nuclei in solid lysozyme are analysed together to obtain information on local internal motions in protein. For this analysis the “model-free” approach is used. Three types of internal motion appear to determine the observed nuclear relaxation in protein. They may be attributed to local rotations of methyl groups around symmetry axes, the motion of main and side chain atoms like in rigid lattice, and large-amplitude motions of side groups (mainly, methylene groups). Conclusions on hydrated water influence on local dynamics of protein are made.     

Nuclear magnetic relaxation in aqueous solutions of vinylpyrrolidone and polyvinylpyrrolidone

Deuteron magnetic spin-lattice relaxation times have been measured in D₂O solutions of vinylpyrrolidone and polyvinylpyrrolidone as a function of concentration and temperature. For the monomer the results are interpreted in terms of a hydrophobic hydrations effect in which 42 D₂O molecules per solute molecule have a correlation time of 3.2 psec at 298°K. Application of the transition state theory to the temperature dependence gave H^*=21 kJ mole^–1 for the relaxation process. In the case of the polymer it is argued that a hydrophilic hydration effect dominates the observed relaxation. These activation enthalpy at 298°K is 24 kJ-mole^–1. Assuming a hydration number of one D₂O per polymer unit, the correlation time for the bound water is 77 psec at 298°K. Polymer proton spin-lattice relaxation times were measured as a function of frequency, and the results are analyzed in terms of a log normal distribution of correlation times. The median value at 296°K is 1.2 nsec.     

Nuclear magnetic resonance relaxation of methane protons in aqueous solutions

Proton nuclear magnetic resonance longitudinal relaxation rates are reported at 100MHz for CH₄ and CHD₃ in deuterium oxide solutions. The results demonstrate that methane reorients with a correlation time on the order of 0.1 psec, considerably faster than molecule correlation times in aqueous solutions.     

Nuclear magnetic resonance diffusion with surface relaxation in porous media

Nuclear magnetic resonance (NMR) diffusion simulations with surface relaxation were performed numerically in unconsolidated and consolidated porous media by a random walk technique. Two uniform and nonuniform models of surface relaxation were proposed and compared. The apparent diffusion coefficient and extinction function were determined and studied in the fast, slow and intermediate diffusion regimes of relaxation. According to theoretical predictions, it was observed that the extinction function does not depend on surface relaxivity parameter rho 2 in the slow diffusion regime. The apparent diffusion coefficients are independent of rho 2 in the fast diffusion regime and tend to be superposed onto a single curve in the slow one. The evolution of the apparent diffusion coefficients is gathered by a reduced representation in the fast diffusion regime.     

Temperature dependence of the damping constant and the order parameter close to the lambda phase transitions in ammonium halides

This study gives our calculation for the damping constant, using the expressions derived for an Ising pseudospin-phonon coupled system in the ammonium halides (NH(4)Cl and NH(4)Br). For this calculation of the damping constant, we use the temperature dependence of the order parameter calculated from the molecular field theory. We predict here the damping constants for the v(5) (174 cm(-1)) and v(5) (177 cm(-1)) Raman modes of NH(4)Cl and NH(4)Br, respectively, below T(lambda) and compare them with our observed bandwidths measured as a function of temperature for those phonon modes at zero pressure. Our predictions agree well with the observed bandwidths below T(lambda) for those modes in both ammonium halide structures, in particular for NH(4)Br. Some discrepancy that occurs below T(lambda) for the v(5) (174 cm(-1)) mode of NH(4)Cl, is explained in terms of the model studied here.     

Thermoanalytical study on the reactions of selected rare earth oxides with ammonium halides

A comparative study has been made on the reactions of RE oxides (RE = Y, La, Gd and Lu) with ammonium bromide, and of yttrium oxide with ammonium halides NH₄X (X = F, Cl, Br and I) at different temperatures. Most of the reactions take place in three stages, with formation of two intermediate compounds, REX₃ · 3 NH₃ and REX₃ · 1.5 NH₃. The endothermic reactions begin between 200 and 300°C and the formation of the RE oxyhalide is completed between 340 and 470°C. These temperatures were observed to rise with the increasing atomic number of RE in the series LaOBrLuOBr, and of halide in the series YOFYOI.     

Nuclear magnetic relaxation in crosslinked elastomers subjected to uniaxial tensile drawing

For samples of crosslinked polyisoprene rubber subjected to stretching at different tensile strains λ, transverse magnetization decay is measured by NMR spectroscopy at a proton frequency of 25 MHz and second moment M ₂ of the residual dipole-dipole interaction is estimated. Theoretical dependence M ₂(λ) is constructed on the basis of the classical theory of rubber elasticity, which predicts that the distribution of distances between the junctions of chemical crosslinks is Gaussian and that deformation is affine. This theoretical dependence is substantially different from the experimental curve. Agreement between the theoretical and experimental data can be attained if the nonaffine character of deformation that is the consequence of the density distribution of chemical crosslinks within the volume of the sample is taken into account and when the Gaussian chain model is replaced with the Langevin model.     

Nuclear magnetic relaxation of ionic nuclei moving in an external electric field

We have experimentally investigated nuclear magnetic relaxation of some quadrupolar ionic nuclei (²³Na⁺, ⁸⁷Rb⁺ and ³⁵Cl⁻ ) in electrolyte solutions in non-equilibrium states. The measurements of relaxation rates 1/T₁ in the presence of a direct electric field, and thus also an electric current, revealed that differences can occur in comparison with relaxation in the absence of the field. In some systems no change in the relaxation rate was observed, but in certain other (non-aqueous) systems there was a change in the quadrupolar relaxation rate in the presence of the field.     

Novel ions of quaternary ammonium halides in FDMS

Field desorption mass spectrometry exhibited novel ions [ Y-n H+n R ]+and [ Y-nH+nX]+as well as cluster ions [nY+(n-1)X-mH+mR]+and [nY+( n-1)X-mH+mX]+(n,m=0-3; X and Y represent the cation and anion moieties of quaternary ammonium halides),whose formation mechanism was discussed.