Lattice Relaxation Rate Research Articles

Quantum scaling of the spin lattice relaxation rate in the checkerboard J-Q model

Motivated by recent progress on the experimental realization of proximate deconfined quantum critical point in a frustrated quantum magnet, we study the low-energy spin dynamics of a related checkerboard J-Q model by using quantum Monte Carlo simulations. The ground state of this model undergoes a weakly first-order quantum phase transition with an emergent O(4) symmetry between an antiferromagnetic state and a plaquette valence bond solid. The calculated spin lattice relaxation rate of nuclear magnetic resonance, 1/T1 , exhibits distinct low-temperature behaviors depending on the ground states. With decreasing the temperature, 1/T1 rises up on the antiferromagnetic side, characterizing a crossover to the renormalized classical regime, whereas 1/T1 drops exponentially on the side of valence bond solid, reflecting the gap opening in the plaquette ordered phase. The extracted spin gap scales with the distance to the transition point as a power-law with an exponent φ ≈ 0.3, consistent with the scaling ansatz ϕ=νz with ν ≈ 0.3 and z = 1. Near the quantum phase transition, the temperature dependent 1/T1 shows a broad crossover regime where a universal scaling 1/T1∼Tη with η ≈ 0.6 is found. Our results suggest a quantum scaling regime associated with the emergent enhanced symmetry near this first-order quantum phase transition.

Characteristics of Langmuir monomolecular monolayers formed by the novel oil blends

Abstract The aim of this work was to assess the physical properties of Langmuir monolayers of three new oil blends “RBWg” (obtained by mixing rapeseed oil, black cumin oil, and wheat germ oil), “REp” (rapeseed oil and evening primrose oil), and “CRb” (camelina oil and rice bran oil), as well as to characterize the molecular dynamics of their protons using low-field nuclear magnetic resonance (LF NMR) method. The studied blends are rich in oleic acid (C18:1), linolenic acid (C18:2), and α-linolenic acid (18:3). The chromatographically determined ratio of n6 to n3 fatty acids was found to be in the range of 5.18–5.27. The appropriate n6/n3 fatty acid ratio was also confirmed by FT-IR analysis. The spin–lattice relaxation rate (R 1) and spin–spin relaxation time (R 2) measured by LF NMR method were similar for the RBWg and REp blends but different from the third oil blend (CRb), which indicates lower proton mobility in CRb. The observed changes in the properties of monolayers of oil blends suggest that the refined rice bran oil in the CRb blend also significantly changes the viscoelastic properties of this blend. The results obtained in this study provide a theoretical basis for the development of a well-balanced approach to using oils in food production technology.

In vitro oxygen imaging of acellular and cell-loaded beta cell replacement devices

Type 1 diabetes (T1D) is an autoimmune disease that leads to the loss of insulin-producing beta cells. Bioartificial pancreas (BAP) or beta cell replacement strategies have shown promise in curing T1D and providing long-term insulin independence. Hypoxia (low oxygen concentration) that may occur in the BAP devices due to cell oxygen consumption at the early stages after implantation damages the cells, in addition to imposing limitations to device dimensions when translating promising results from rodents to humans. Finding ways to provide cells with sufficient oxygenation remains the major challenge in realizing BAP devices’ full potential. Therefore, in vitro oxygen imaging assessment of BAP devices is crucial for predicting the devices’ in vivo efficiency. Electron paramagnetic resonance oxygen imaging (EPROI, also known as electron MRI or eMRI) is a unique imaging technique that delivers absolute partial pressure of oxygen (pO2) maps and has been used for cancer hypoxia research for decades. However, its applicability for assessing BAP devices has not been explored. EPROI utilizes low magnetic fields in the mT range, static gradients, and the linear relationship between the spin–lattice relaxation rate (R1) of oxygen-sensitive spin probes such as trityl OX071 and pO2 to generate oxygen maps in tissues. With the support of the Juvenile Diabetes Research Foundation (JDRF), an academic-industry partnership consortium, the “Oxygen Measurement Core” was established at O2M to perform oxygen imaging assessment of BAP devices originated from core members’ laboratories. This article aims to establish the protocols and demonstrate a few examples of in vitro oxygen imaging of BAP devices using EPROI. All pO2 measurements were performed using a recently introduced 720 MHz/25 mT preclinical oxygen imager instrument, JIVA-25™. We began by performing pO2 calibration of the biomaterials used in BAPs at 25 mT magnetic field since no such data exist. We compared the EPROI pO2 measurement with a single-point probe for a few selected materials. We also performed trityl OX071 toxicity studies with fibroblasts, as well as insulin-producing cells (beta TC6, MIN6, and human islet cells). Finally, we performed proof-of-concept in vitro pO2 imaging of five BAP devices that varied in size, shape, and biomaterials. We demonstrated that EPROI is compatible with commonly used biomaterials and that trityl OX071 is nontoxic to cells. A comparison of the EPROI with a fluorescent-based point oxygen probe in selected biomaterials showed higher accuracy of EPROI. The imaging of typically heterogenous BAP devices demonstrated the utility of obtaining oxygen maps over single-point measurements. In summary, we present EPROI as a quality control tool for developing efficient cell transplantation devices and artificial tissue grafts. Although the focus of this work is encapsulation systems for diabetes, the techniques developed in this project are easily transferable to other biomaterials, tissue grafts, and cell therapy devices used in the field of tissue engineering and regenerative medicine (TERM). In summary, EPROI is a unique noninvasive tool to experimentally study oxygen distribution in cell transplantation devices and artificial tissues, which can revolutionize the treatment of degenerative diseases like T1D.

Low-Temperature Magnetic Fluctuations Investigated by 125Te-NMR on the Uranium-Based Superconductor UTe2

To investigate the static and dynamic magnetic properties on the uranium-based superconductor UTe2, we measured the NMR Knight shift K and the nuclear spin–lattice relaxation rate 1/T1 in H || a by 125Te-NMR on a 125Te-enriched single-crystal sample. 1/T1T in H || a is much smaller than 1/T1T in H || b and c, and magnetic fluctuations along each axis are derived from the 1/T1T measured in H parallel to all three crystalline axes. The magnetic fluctuations are almost identical at two Te sites and isotropic at high temperatures, but become anisotropic below 40 K, where heavy-fermion state is formed. The character of magnetic fluctuations in UTe2 is discussed with the comparison to its static susceptibility and the results on other U-based superconductors. It is considered that the magnetic fluctuations probed with the NMR measurements are determined by the magnetic properties inside the two-leg ladder formed by U atoms, which are dominated by the qa = 0 ferromagnetic fluctuations.

Rate constants for saturation-recovery EPR and ELDOR of 14N-Spin labels

Saturation-recovery (SR)-EPR can determine electron spin–lattice relaxation rates in liquids over a wide range of effective viscosity, making it especially useful for biophysical and biomedical applications. Here, I develop exact solutions for the SR-EPR and SR-ELDOR rate constants of 14N-nitroxyl spin labels as a function of rotational correlation time and spectrometer operating frequency. Explicit mechanisms for electron spin–lattice relaxation are: rotational modulation of the N-hyperfine and electron-Zeeman anisotropies (specifically including cross terms), spin-rotation interaction, and residual frequency-independent vibrational contributions from Raman processes and local modes. Cross relaxation from mutual electron and nuclear spin flips, and direct nitrogen nuclear spin–lattice relaxation, also must be included. Both the latter are further contributions from rotational modulation of the electron-nuclear dipolar interaction (END). All the conventional liquid-state mechanisms are defined fully by the spin-Hamiltonian parameters; only the vibrational contributions contain fitting parameters. This analysis gives a firm basis for interpreting SR (and inversion recovery) results in terms of additional, less standard mechanisms.

Giant Density of States Enhancement Driven by a Zero-Mode Landau Level in Semimetallic Black Phosphorus under Pressure.

Dirac fermion systems form a unique Landau level at the Fermi level-the so-called zero mode-whose observation itself will provide strong evidence of the presence of Dirac dispersions. Here, we report the study of semimetallic black phosphorus under pressure by ^{31}P-nuclear magnetic resonance measurements in a wide range of magnetic field up to 24.0T. We have found a field-induced giant enhancement of 1/T_{1}T, where 1/T_{1} is the nuclear spin lattice relaxation rate: 1/T_{1}T at 24.0T reaches more than 20 times larger than that at 2.0T. The increase in 1/T_{1}T above 6.5T is approximately proportional to the squared field, implying a linear relationship between the density of states and the field. We also found that, while 1/T_{1}T at a constant field is independent of temperature in the low-temperature region, it steeply increases with temperature above 100K. All these phenomena are well explained by considering the effect of Landau quantization on three-dimensional Dirac fermions. The present study demonstrates that 1/T_{1} is an excellent quantity to probe the zero-mode Landau level and to identify the dimensionality of the Dirac fermion system.

Investigation of the Influence of Various Functional Groups on the Dynamics of Glucocorticoids.

The basic configuration of glucocorticoid consists of four-fused rings associated with one cyclohexadienone ring, two cyclohexane rings, and one cyclopentane ring. The ways the structure and dynamics of five glucocorticoids (prednisone, prednisolone, prednisolone acetate, methylprednisolone, and methylprednisolone acetate) are altered because of the substitution of various functional groups with these four-fused rings are studied thoroughly by applying sophisticated solid-state nuclear magnetic resonance (NMR) methodologies. The biological activities of these glucocorticoids are also changed because of the attachment of various functional groups with these four-fused rings. The substitution of the hydroxyl group (with the C11 atom of the cyclohexane ring) in place of the keto group enhances the potential of the glucocorticoid to cross the cellular membrane. As a result, the bioavailability of prednisolone (the hydroxyl group is attached with the C11 atom of the cyclohexane ring) is increased compared to prednisone (the keto group is attached with the C11 atom of cyclohexane rings). Another notable point is that the spin-lattice relaxation rate at crystallographically distinct carbon nuclei sites of prednisolone is increased compared to that of the prednisone, which implies that the motional degrees of freedom of glucocorticoid is increased because of the substitution of the hydroxyl group in place of the keto group of the cyclohexane ring. The attachment of the methyl group with the C6 atom of cyclohexane rings further reduces the spin-lattice relaxation time at crystallographically distinct carbon nuclei sites of glucocorticoid and its bioactivity is also increased. By comparing the spin-lattice relaxation time and the local correlation time at crystallographically different carbon nuclei sites of three steroids prednisone, prednisolone, and methylprednisolone, it is observed that both the spin-lattice relaxation time and the local correlation time gradually decrease at each crystallographically distinct carbon nuclei sites when we move from prednisone to prednisolone to methyl-prednisolone. On the other hand, if we compare the same for prednisolone, prednisolone acetate, and methylprednisolone acetate, then we also observe that both the spin-lattice relaxation time and the local-correlation time gradually decrease from prednisolone to prednisolone acetate to methylprednisolone acetate for all chemically different carbon nuclei. It is also noticeable that both the spin-lattice relaxation time and the local-correlation time gradually decrease from prednisone to prednisolone to prednisolone acetate to methylprednisolone to methylprednisolone acetate for most of the carbon nuclei sites. From in silico analysis, it is also revealed that the bioavailability and efficacy of the glucocorticoid increase from prednisone to prednisolone to prednisolone acetate to methylprednisolone to methylprednisolone acetate. Hence, it can be concluded that the biological activity and the motional degrees of freedom of the glucocorticoids are highly correlated. These types of studies provide a clear picture of the structure-activity relationship of the drug molecules, which will enlighten the path of developing highly potent glucocorticoids with minimum side effects. Another important aspect of these types of studies is to provide information about the electronics configuration and nuclear spin dynamics at crystallographically different carbon nuclei sites of five glucocorticoids, which will enrich the field of "NMR crystallography".

The effect of spin-lattice relaxation on DEER background decay

The common approach to background removal in double electron–electron resonance (DEER) measurements on frozen solutions with a three-dimensional homogeneous distribution of doubly labeled biomolecules is to fit the background to an exponential decay function. Excluded volume effects or distribution in a dimension lower than three, such as proteins in a membrane, can lead to a stretched exponential decay. In this work, we show that in cases of spin labels with short spin–lattice relaxation time, up to an order of magnitude longer than the DEER trace length, relevant for metal-based spin labels, spin flips that take place during the DEER evolution time affect the background decay shape. This was demonstrated using a series of temperature-dependent DEER measurements on frozen solutions of a nitroxide radical, a Gd(III) complex, Cu(II) ions, and a bis-Gd(III) model complex. As expected, the background decay was exponential for the nitroxide, whereas deviations were noted for Gd(III) and Cu(II). Based on the theoretical approach of Keller et al. (Phys. Chem. Chem. Phys. 21 (2019) 8228–8245), which addresses the effect of spin–lattice relaxation-induced spin flips during the evolution time, we show that the background decay can be fitted to an exponent including a linear and quadratic term in t, which is the position of the pump pulse. Analysis of the data in terms of the probability of spontaneous spin flips induced by spin–lattice relaxation showed that this approach worked well for the high temperature range studied for Gd(III) and Cu(II). At the low temperature range, the spin flips that occured during the DEER evolution time for Gd(III) exceeded the measured spin–lattice relaxation rate and include contributions from spin flips due to another mechanisms, most likely nuclear spin diffusion.

Water Molecular Dynamics in the Porous Structures of Ultrafiltration/Nanofiltration Asymmetric Cellulose Acetate–Silica Membranes

This study presents the characterization of water dynamics in cellulose acetate-silica asymmetric membranes with very different pore structures that are associated with a wide range of selective transport properties of ultrafiltration (UF) and nanofiltration (NF). By combining 1H NMR spectroscopy, diffusometry and relaxometry and considering that the spin-lattice relaxation rate of the studied systems is mainly determined by translational diffusion, individual rotations and rotations mediated by translational displacements, it was possible to assess the influence of the porous matrix's confinement on the degree of water ordering and dynamics and to correlate this with UF/NF permeation characteristics. In fact, the less permeable membranes, CA/SiO2-22, characterized by smaller pores induce significant orientational order to the water molecules close to/interacting with the membrane matrix's interface. Conversely, the model fitting analysis of the relaxometry results obtained for the more permeable sets of membranes, CA/SiO2-30 and CA/SiO2-34, did not evidence surface-induced orientational order, which might be explained by the reduced surface-to-volume ratio of the pores and consequent loss of sensitivity to the signal of surface-bound water. Comparing the findings with those of previous studies, it is clear that the fraction of more confined water molecules in the CA/SiO2-22-G20, CA/SiO2-30-G20 and CA/SiO2-34-G20 membranes of 0.83, 0.24 and 0.35, respectively, is in agreement with the obtained diffusion coefficients as well as with the pore sizes and hydraulic permeabilities of 3.5, 38 and 81 kg h-1 m-2 bar-1, respectively, reported in the literature. It was also possible to conclude that the post-treatment of the membranes with Triton X-100 surfactants produced no significant structural changes but increased the hydrophobic character of the surface, leading to higher diffusion coefficients, especially for systems associated with average smaller pore dimensions. Altogether, these findings evidence the potential of combining complementary NMR techniques to indirectly study hydrated asymmetric porous media, assess the influence of drying post-treatments on hybrid CA/SiO2 membrane' surface characteristics and discriminate between ultra- and nano-filtration membrane systems.

Microscopic properties of Mo4Ga20Sb intermetallic superconductor in normal and superconducting states as evidenced by NMR and NQR spectroscopy

A detailed study of novel intermetallic superconductor Mo4Ga20Sb (Tc = 6.6 K) by means of 69,71Ga nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) spectroscopy was performed to gain insight into the superconducting pairing mechanism and gap characteristics, as well as into the normal-state electronic properties on a microscopic scale. An unexpected step-like increase of the 69Ga1 NQR linewidth was observed at Tc with decreasing temperature, which may indicate coexistence of several superconducting phases on a microscopic scale with slightly different Tc values. Above 140 K, the NQR linewidth decreases rapidly with increasing temperature due to possible oscillatory and/or rotational modes of the gallium cluster network at the elevated temperatures. Nuclear spin lattice relaxation rate 1/T1 of 69Ga nuclei in the Ga1 position follows Korringa law characteristic for the compounds with good metallic conductivity. The calculated Korringa ratio S< 1 indicates the presence of antiferromagnetic correlations in Mo4Ga20Sb, in agreement with the magnetic susceptibility data. Below Tc, a pronounced intensive Hebel-Slichter peak was observed indicating s-wave superconductivity without point or line nodes in the k-space (full gap s-wave superconductivity). We have demonstrated that the best fit of the experimental data is achieved using two s-wave superconducting gaps of 13 K and 6 K with relative weights of 0.8 and 0.2, respectively. The obtained weighted average value of 11.6 K is consistent with the specific heat value of Δ = 12.05 K.

139La-NMR Study of Spin Dynamics Coupled with Hole Mobility in T*-type La0.86Eu0.86Sr0.28CuO4−δ

In T*-type cuprate oxides with five-oxygen coordination, the relationship between spin correlations and doped carriers has not been well understood. To clarify this relationship, and the magnetic and superconducting (SC) properties of T*-type cuprate oxides, we performed 139La-nuclear magnetic resonance (NMR) and electrical resistivity measurements on as-sintered (AS) and oxidation-annealed (OA) polycrystalline T*-type La0.86Eu0.86S0.28CuO4 (LESCO) to investigate its magnetic and SC properties. Upon cooling, the NMR spectrum of AS LESCO broadened below 3 K, where the nuclear spin–lattice relaxation rate 1/T1 with respect to the temperature exhibited a maximum, indicating the appearance of static magnetism. The temperature dependence of 1/T1 between 3 and 20 K was similar to that of resistivity, which displays semiconducting behavior. Furthermore, it was found that the energy scales of the transport gap and spin dynamics were comparable. These results suggest a close connection between the mobility of the doped carriers and low-energy spin dynamics, as reported for lightly doped T-type La2−xSrxCuO4. In the OA SC sample, we confirmed the absence of a magnetic order and the linear relation between 1/T1 and T above 10 K. These results suggest that the magnetic state coupled with holes markedly changes to the weakly correlated metallic state by oxidation annealing in the T*-type LESCO with x = 0.28.

High resolution solid state NMR in paramagnetic metal-organic frameworks

We study the metal-organic framework (MOF) ZIF-67 with 1H and 13C nuclear magnetic resonance (NMR). In addition to the usual orbital chemical shifts, we observe spinning sideband manifolds in the NMR spectrum due to hyperfine interactions of the paramagnetic cobalt with 1H and 13C. Both orbital and paramagnetic chemical shifts are in good agreement with values calculated from first principles, allowing high-confidence assignment of the observed peaks to specific sites within the MOF. Our measured resonance shifts, line shapes, and spin lattice relaxation rates are also consistent with calculated values. We show that molecules in the pores of the MOF can exhibit high-resolution NMR spectra with fast spin lattice relaxation rates due to dipole-dipole couplings to the Co2+ nodes in the ZIF-67 lattice, showcasing NMR spectroscopy as a powerful tool for identification and characterization of “guests” that may be hosted by the MOF in electrochemical and catalytic applications.

Modeling the Effect of Hyperoxia on the Spin-Lattice Relaxation Rate R1 of Tissues.

PurposeInducing hyperoxia in tissues is common practice in several areas of research, including oxygen‐enhanced MRI (OE‐MRI), which attempts to use the resulting signal changes to detect regions of tumor hypoxia or pulmonary disease. The linear relationship between PO2 and R1 has been reproduced in phantom solutions and body fluids such as vitreous fluid; however, in tissue and blood experiments, factors such as changes in deoxyhemoglobin levels can also affect the ΔR1.Theory and MethodsThis manuscript proposes a three‐compartment model for estimating the hyperoxia‐induced changes in R1 of tissues depending on B0, SO2, blood volume, hematocrit, oxygen extraction fraction, and changes in blood and tissue PO2. The model contains two blood compartments (arterial and venous) and a tissue compartment. This model has been designed to be easy for researchers to tailor to their tissue of interest by substituting their preferred model for tissue oxygen diffusion and consumption. A specific application of the model is demonstrated by calculating the resulting ΔR1 expected in healthy, hypoxic and necrotic tumor tissues. In addition, the effect of sex‐based hematocrit differences on ΔR1 is assessed.ResultsThe ΔR1 values predicted by the model are consistent with reported literature OE‐MRI results: with larger positive changes in the vascular periphery than hypoxic and necrotic regions. The observed sex‐based differences in ΔR1 agree with findings by Kindvall et al. suggesting that differences in hematocrit levels may sometimes be a confounding factor in ΔR1.ConclusionThis model can be used to estimate the expected tissue ΔR1 in oxygen‐enhanced MRI experiments.

Nematicity and Glassy Behavior Probed by Nuclear Magnetic Resonance in Iron-Based Superconductors

Nuclear magnetic resonance provides a wealth of information about the magnetic and nematic degrees of freedom in the iron-based superconductors. A striking observation is that the spin lattice relaxation rate is inhomogeneous with a standard deviation that correlates with the nematic susceptibility. Moreover, the spin lattice relaxation is strongly affected by uniaxial strain, and in doped samples it depends sensitively upon the history of the applied strain. These observations suggest that quenched strain fields associated with doping atoms induce a nematic glass in the iron pnictide materials.

NMR probe of suppressed bulk conductivity in the topological insulator Bi0.5Sb1.5Te3.

The relaxation behavior in the topological insulator (TI) Bi0.5Sb1.5Te3 has been investigated using 125Te nuclear magnetic resonance spectroscopy. We systematically investigate the spin–lattice relaxation rate (1/T1) in bulk electronic states with varying particle sizes. By analyzing the 1/T1 relaxation behavior, we find that with decreasing particle sizes the electronic states in the bulk exhibit more topological insulating behavior, indicative of an increasing energy gap supported by higher thermal activation energy. Besides, the decreasing density of states at the Fermi level was observed in the massive Dirac electrons with decreasing particle size by analyzing the spin–lattice relaxation according to a theoretical model in this spin–orbit coupled system.

Anisotropic nematic fluctuations above the ferroquadrupolar transition in TmVO4

TmVO$_4$ exhibits ferroquadrupolar order below 2.15 K with a well-isolated non-Kramers ground state doublet, and is a model system to understand Ising nematic order. We present $^{51}$V nuclear magnetic resonance data as a function of field orientation in a single crystal. Although the spectra are well understood in terms of direct dipolar hyperfine couplings, the spin lattice relaxation rate exhibits strong anisotropy that cannot be understood in terms of magnetic fluctuations. We find that the spin lattice relaxation rate scales with the shear elastic constant associated with the ferroquadrupole phase transition, suggesting that quadrupole (nematic) fluctuations dominate the spin lattice relaxation for in-plane fields.

Zero-field 29Si nuclear magnetic resonance signature of helimagnons in MnSi

The low temperature dependence of the nuclear magnetic resonance frequency and spin–lattice relaxation rate measured in the chiral magnet MnSi by Yasuoka and coworkers [J.Phys.Soc.Jpn.85, 073701 (2016)] is interpreted in terms of helimagnon excitations. The theoretically predicted gapless and anisotropic dispersion relation which is probed at extremely small energy is experimentally confirmed. Whenever comparison is possible, the results are found quantitatively consistent with those of the inelastic neutron scattering and muon spin rotation and relaxation techniques. Further studies are suggested.

Fast nuclear spin relaxation rates in tilted cone Weyl semimetals: redshift factors from Korringa relation

Spin lattice relaxation rate is investigated for 3D tilted cone Weyl semimetals (TCWSMs). The nuclear spin relaxation rate is presented as a function of temperature and tilt parameter. We find that the relaxation rate behaves as with α ≈ 9 where 0 ⩽ ζ < 1 is the tilt parameter. We demonstrate that such a strong enhancement for ζ ≲ 1 that gives rise to very fast relaxation rates, is contributed by a new hyperfine interactions arising from the tilt itself. This can be attributed to the combination of anisotropy of the Fermi surface and an additional part related to the structure of the spacetime: extracting an effective density of states (DOS) from the Korringa relation, we show that it is related to the DOS ρ of the tilted cone dispersion by the ‘redshift factor’ as . We interpret this relation as NMR manifestation of an emergent underlying spacetime structure in TCWSMs.

The3He nuclear magnetic relaxation in nematically ordered Al2O3 aerogels: effects of 4He and nitrogen pre-plating

The results of 3He gas pulsed NMR spin–lattice relaxation study in high-porosity (84.9%–97.9%) nematically ordered Al2O3 aerogels at 1.5 and 4.2 K are presented. The linear dependence of T 1 on gas pressure is observed in aerogels that are pre-plated by helium-4. Nitrogen pre-plating prior to helium-4 pre-plating weakly decreases the 3He gas spin–lattice relaxation rate. A few possible mechanisms plausibly involved in 3He nuclear magnetic relaxation in aerogels are considered. The suggested nuclear spin–lattice relaxation model due to some magnetically ‘dirty’ aerogel fibers allows to estimate the effective mean free path of 3He atoms in aerogel.

Glassy and Polymer Dynamics of Elastomers by 1H-Field-Cycling NMR Relaxometry: Effects of Fillers.

1H spin–lattice relaxation rate (R1) dispersions were acquired by field-cycling (FC) NMR relaxometry between 0.01 and 35 MHz over a wide temperature range on polyisoprene rubber (IR), either unfilled or filled with different amounts of carbon black, silica, or a combination of both, and sulfur cured. By exploiting the frequency–temperature superposition principle and constructing master curves for the total FC NMR susceptibility, χ″(ω) = ωR1(ω), the correlation times for glassy dynamics, τs, were determined. Moreover, the contribution of polymer dynamics, χpol″(ω), to χ″(ω) was singled out by subtracting the contribution of glassy dynamics, χglass″(ω), well represented by the Cole–Davidson spectral density. Glassy dynamics resulted moderately modified by the presence of fillers, τs values determined for the filled rubbers being slightly different from those of the unfilled one. Polymer dynamics was affected by the presence of fillers in the Rouse regime. A change in the frequency dependence of χpol″(ω) at low frequencies was observed for all filled rubbers, more pronounced for those reinforced with silica, which suggests that the presence of the filler particles can affect chain conformations, resulting in a different Rouse mode distribution, and/or interchain interactions modulated by translational motions.