Spin-lattice relaxation in 13CH3 compounds: application to 13C enriched aspirin

Spin-lattice relaxation processes in ¹³CH₃ groups in methyl compounds are studied both theoretically and experimentally. The four spin-½ nuclei in such methyl groups give rise to 16 spin-rotational states, which are split by rotational tunnelling. From the corresponding populations (15 independent) five long lived combinations are formed: the ¹³C magnetization M _C, proton magnetization M _H, tunnelling energy TE, rotational polarization RP and dipolar energy DE. Their spin-lattice relaxation via the transitions induced by the ¹³C-proton dipolar interaction is studied in detail. Direct relaxation rates and coupling terms between these combinations are derived. Predictions are compared with experimental data for ¹³C spin-lattice relaxation at 75.4 MHz in 99% enriched (only methyl carbons enriched) single crystal of aspirin. Above 40 K, the M _C recovery is exponential and describable in terms of the direct relaxation transitions without couplings. The same is true for the initial relaxation in the region of non-exponential relaxation between 30 K and 40 K. The orientation dependence of the initial relaxation rate agrees with the theoretical calculations. The non-exponentiality is related to resonant level-crossing transitions with ω_t, + ω_C = ω_H, where the angular frequencies represent rotational tunnelling and carbon and proton resonances, respectively. The resonant transitions produce couplings between M _C, M _H and TE that are described quite accurately by the present model.     

Recovery of electrical-resistivity and viscoelasticity relaxation in thermally aged bulk Pd<Subscript>40</Subscript>Cu<Subscript>30</Subscript>Ni<Subscript>10</Subscript>P<Subscript>20</Subscript> metallic glass

The structural relaxation of a bulk Pd₄₀Cu₃₀Ni₁₀P₂₀ metallic glass is studied by measuring the electrical resistivity and infralow-frequency (0.05 Hz) internal friction. It is demonstrated that the structural relaxation in thermally aged samples can be restored by quenching them from a supercooled liquid state. It is found that the degree of relaxation after quenching can exceed the initial one by several times.     

Irreversible structural relaxation in a bulk Pd-Cu-Ni-P metallic glass

The evolution of the shear modulus and the damping decrement during irreversible structural relaxation in a bulk Pd₄₀Cu₃₀Ni₁₀P₂₀ metallic glass in a temperature range below the glass transition temperature has been studied with an inverse torsion pendulum at a frequency of ～25 Hz. It is shown that the irreversible relaxation can be recovered via quenching from temperatures above the glass transition temperature. The spectrum shape, the characteristic activation energies, and the attempt frequencies of the irreversible structural relaxation are estimated.     

Mössbauer study of magnetic anisotropy and structural relaxation in amorphous Fe40Ni40P x B20−x alloys

The amorphous Fe₄₀Ni₄₀P _x B_20?x (x=0, 10, 12, 14, 17) alloys before and after annealing have been studied by means of Mössbauer spectroscopy, etc. Heat treatment of various samples were performed at 225, 250, 275, 300, 325 and 350°C, respectively, for 1 h in a quartz tube in an argon atmosphere. The results show that the magnetic anisotropy and structural relaxation in amorphous Fe₄₀Ni₄₀P _x B_20?x are related to the phosphorus element concentrations involved and the annealing temperatures. A possible mechanism of two-stage relaxation processes below the glass transition temperature is discussed.     

Isothermal kinetics and relaxation recovery of high-frequency shear modulus in the course of structural relaxation of Pd<Subscript>40</Subscript>Cu<Subscript>30</Subscript>Ni<Subscript>10</Subscript>P<Subscript>20</Subscript> bulk glass

Isothermal kinetics of relaxation of the high-frequency (1.4 MHz) shear modulus during structural relaxation of Pd₄₀Cu₃₀Ni₁₀P₂₀ bulk metallic glass below the glass transition temperature is studied by an in situ method of contactless electromagnetic acoustic transformation. The kinetic law of relaxation is established. It is shown that quenching of aged samples from the supercooled liquid state leads to a decrease in the absolute value of shear modulus to below the initial value; the degree of subsequent isothermal relaxation of the modulus may be several times higher than the initial value. Possible reasons for relaxation and recovery of the shear modulus are considered.     

Stress relaxation and viscosity of a bulk Pd<Subscript>40</Subscript>Cu<Subscript>30</Subscript>Ni<Subscript>10</Subscript>P<Subscript>20</Subscript> metallic glass under isochronous heating conditions

Isochronous relaxation of tensile stresses is measured in a bulk Pd₄₀Cu₃₀Ni₁₀P₂₀ metallic glass in the initial state and after certain thermal treatments. The results of measurements are used to find the energy spectrum of irreversible structural relaxation, from which the temperature dependence of shear viscosity is then calculated. This dependence is also found independently from measurements of creep in the same glass. The calculated viscosity is shown to agree well with the experimental data.     

Impedance of nonuniform distributed solid protonic electrolyte - polymer systems

The conductivity of mixtures of the solid electrolytes H₃[PMo₁₂O₄₀]·13H₂O and Cs₂H[PW₁₂O₄₀] · 13H₂O follows the predictions of the percolation theory, whereas the electrode impedance in the high frequency range fits well the model of double layer adsorption relaxation. It is concluded that both the adsorption relaxation and the reversibility of the electrodes are related to oxygen transfer, the oxygen ions being the minority charge carriers. Fast oxygen dispersion may occur at the polymer-solid electrolyte interface. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Computation of effective electron–phonon relaxation times in a high-Tc superconductor using the measured track radii

Energy relaxation processes after fast heavy ions passage through YBa₂Cu₃O_7−δ single crystal have been calculated. Effective times τ of electron–atom energy relaxation have been determined as fitting parameters for each pair of the measured track radius and the value of dE/dx. The latter quantity has been chosen over the interval of 20–40 keV/nm. The calculated results are compared with short pulse laser experiments and with Allen's theory, which predicts almost a linear dependence of τ on electron temperature.     

Anomalous magnetic relaxation in thin Pd<Subscript>0.99</Subscript>Fe<Subscript>0.01</Subscript> films

The magnetic relaxation in Pd_0.99Fe_0.01 films, which have the thicknesses that are practically important for cryoelectronics (25 and 40 nm), is detected and experimentally studied. The relaxation is shown to be substantial only in thin films. The magnetization relaxation is found to be well described by the sum of two exponential functions with characteristic times that differ by an order of magnitude from each other. The characteristic relaxation time and the ratio of the contributions of two relaxations depend on temperature. The activation energies of the relaxation processes are determined. The activation volume is shown to correspond to a 20-nm ferromagnetic cluster. The results obtained agree with the model of two-component magnetization in thin PdFe films [6].     

Kinetics of structural relaxation of bulk and ribbon Pd<Subscript>40</Subscript>Cu<Subscript>30</Subscript>Ni<Subscript>10</Subscript>P<Subscript>20</Subscript> glasses determined from electrical resistance measurements

The electrical resistances of ribbon and bulk Pd₄₀Cu₃₀Ni₁₀P₂₀ metallic glasses, whose quenching rates differ by four orders of magnitude, were precisely measured during cyclic heating. Three stages of electrical resistance relaxation are detected as the maximum heating temperature increases. The first and third stages decrease the electrical resistance, and the second stage increases it. The first stage is shown to be caused by the relaxation of deformation-induced internal stresses and not to be related to the excess free volume concentration, which differs by a factor of about 2 in the ribbon and bulk samples. The second stage reflects structural relaxation in the glass and is only partly related to its free volume. The third relaxation stage is assumed to be caused by fine precrystallization phenomena like phase separation. The effect of deformation by rolling or quenching from the temperature range of a supercooled melt on the resistance relaxation kinetics was also studied.     

Revisiting the Dielectric Relaxation of Ethylene-Vinylacetate Copolymers: Influence of Microstructure

The dielectric relaxation behavior of a series of ethylene-vinylacetate (EVA) copolymers was investigated by measuring the complex dielectric permittivity in a broad frequency and temperature range. Crystallinity of EVA copolymers was estimated by differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). The shape of the higher temperature relaxation, appearing above the glass transition temperature T _g depends on the VA content. It was found that this relaxation was asymmetric for VA concentrations higher than 40 wt% and changed to a symmetric shape at lower VA values. Concurrently, as the VA content decreased, a major broadening of the relaxation over a wide frequency range was observed. It is found that the dielectric relaxation was preserved on going through the melting range of the semicrystalline samples, although it exhibited changes of its characteristic parameters that are typical for segmental relaxation appearing at T _g. This finding allows one to associate this relaxation to the segmental motions at T _g in the amorphous phase and not to the existence of interfacial regions.     

Relaxation processes in glasses of the Ge-As-S system

The internal friction in Ge _x As_{40 ? x} S₆₀ glasses is investigated in the temperature range 100 K-T _g at infralow frequencies (10^?3?10^?1 Hz). It is shown that the concentration dependence of the internal friction of these materials changes as a result of the transformation of the dominant kinetic unit in dissipative processes of the relaxation and nonrelaxation types. It is established tha the change in the mechanism of internal friction in the Ge _x As_{40 ? x} S₆₀ glasses leads to a jump in the activation energy of the α relaxation and to a local minimum in the frequency factor τ₀.     

Creep strain recovery of Fe-Ni-B amorphous metallic ribbon

Creep strain recovery and structural relaxation of the amorphous metallic glass Fe₄₀Ni₄₁B₁₉ after longtime loading at different annealing temperatures below the glass transition temperature have been studied using anisothermal differential scanning calorimetry (DSC) and dilatometry (TMA). It has been demonstrated that structural relaxation effects depend on the stress-annealing temperature of the amorphous ribbon. The structural relaxation states of the amorphous ribbon annealed at different temperatures under and without applied stress have been compared. The activation energy spectra were calculated from the anisothermal dilatometric measurements using the modern method based on the Fourier transformation technique. The influence of the annealing temperature on the shape of creep strain recovery spectra has been analyzed.      

Critical conditions for spontaneous relaxation in self-organizing dissipative film systems

It is established that the necessary conditions for spontaneous relaxation of elastic strain energy in a copper-As₆₀Se₄₀ self-organizing dissipative heterostructure is that the elastic deformation energy and the temperature must reach their threshold values. It is shown that in the temperature range 270–340 K the spontaneous relaxation of elastic deformation energy is accompanied by structural-chemical ordering and anomalous diffusion of copper into the glassy chalcogenide semiconductor layer. The maximum concentration of copper dissolved in the films is 40 at. %. Conductivity inversion from p to n type is observed in doped layers obtained by this method. Zh. Tekh. Fiz. 69, 128–129 (August 1999)     

Recovery of the deformability of the aged metallic glass Pd40Cu30Ni10P20 under conditions of testing for shear stress relaxation

It has been established that quenching from the supercooled liquid state of the aged metallic glass Pd₄₀Cu₃₀Ni₁₀P₂₀ causes the recovery of its deformability, which manifests itself in measurements of the torque relaxation under conditions of isochronous heating.     

Mössbauer study of hyperfine field relaxations in soft magnetic amorphous alloys

Superimposed asymptotic exponential relaxation between 125 and 200°C of average hyperfine inductions and their orientations were detected by the⁵⁷Fe Mössbauer spectroscopy in the ferromagnetic Fe₄₀Ni₄₀B₂₀ and Fe₇₀Co₁₀B₂₀ amorphous alloys. From their Arrhenius type temperature dependence, average activation enthalpies ΔH were derived in agreement with the resistometric and coercivity data. The interpretation is proposed in terms of individual irreversible processes: stress relief, free volume shrinking and short-range ordering.     

Microwave conductivity of heavy fermions in UPd<Subscript>2</Subscript>Al<Subscript>3</Subscript>

Heavy-fermion compounds are characterized by electronic correlation effects at low energies which can directly be accessed with optical spectroscopy. Here we present detailed measurements of the frequency- and temperature-dependent conductivity of the heavy-fermion compound UPd₂Al₃ using broadband microwave spectroscopy in the frequency range 45 MHz to 40 GHz at temperatures down to 1.7 K. We observe the full Drude response with a relaxation time up to 50 ps, proving that the mass enhancement of the heavy charge carriers goes hand in hand with an enhancement of the relaxation time. We show that the relaxation rate as a function of temperature scales with the dc resistivity. We do not find any signs of a frequency-dependent relaxation rate within the addressed frequency range.     

Relaxation in the photoelectric and photovoltaic responses of thin-film Pb(Zr0.25, Ti0.75)O3 ferroelectric

We study the relaxation of photoresponses in self-polarized Pb(Zr_0.25, Ti_0.75)O₃ film structures with a semitransparent NiCr top electrode under focused laser illumination with a wavelength of 0.63 μm and a power of about 40 mW. Dependences of the relaxation times of the photoresponses on the field directed both along the self-polarization vector and opposite to it are experimentally obtained. The dependences are found to be qualitatively different. We assume that in the structure under study, a screening charge occurs due to the capturing of photoinduced carriers in deep traps localized in the contact region.     

Shear viscosity of the Pd<Subscript>40</Subscript>Cu<Subscript>40</Subscript>P<Subscript>20</Subscript> metallic glass under conditions of isochronous heating below the glass transition temperature

The shear viscosity is measured under conditions of isochronous (linear) heating below the glass transition temperature of the Pd₄₀Cu₄₀P₂₀ metallic glass, which is characterized by the polymorphic crystallization into the Pd₂Cu₂P tetragonal phase with a lower density than the initial glass. It is shown that the rate dependence of the shear viscosity can be interpreted as a result of the irreversible structural relaxation by analogy with the case of the previously studied metallic glasses despite the unusual ratio of the densities of the material in noncrystalline and crystalline states.     

添加Nb对CaCu3Ti4O12陶瓷介电性能的影响

采用固相反应法制备了CaCu₃Ti_4-xNb_xO₁₂(x=0，0.01，0.04，0.08，0.2)陶瓷，样品在x取值范围内形成了连续固溶体.在40Hz—110MHz频率范围对样品进行了介电频谱分析，实验结果表明，与纯CaCu₃Ti₄O₁₂不同，含Nb试样除了在频率大于10kHz范围内出现的德拜弛豫 关键词： 巨介电常数 德拜弛豫 阻挡层电容 等效电路