High-field QCPMG NMR of large quadrupolar patterns using resistive magnets

Spectroscopy in a high magnetic field reduces second-order quadrupolar shift while increasing chemical shift. It changes the scale between quadrupolar and chemical shift of half-integer quadrupolar spins. The application of QCPMG multiple echo for acquiring large quadrupolar pattern under the high magnetic field of a 25 T resistive magnet is presented for acquiring large quadrupolar patterns. It shows that temporal field fluctuations and spatial homogeneity of the Keck magnet at the NHMFL contribute about ±20 ppm in line broadening. NMR patterns which have breadths of hundreds to thousands of kilohertz can be efficiently recorded using a combination of QCPMG and magnetic field stepping with negligible hindrance from the inhomogeneity and field fluctuations of powered magnets.     

High-resolution NMR with resistive and hybrid magnets: deconvolution using a field-fluctuation signal

A method for compensating effect of field fluctuation is examined to attain high-resolution NMR spectra with resistive and hybrid magnets. In this method, time dependence of electromotive force induced for a pickup coil attached near a sample is measured synchronously with acquisition of NMR. Observed voltage across the pickup coil is converted to field fluctuation data, which is used to deconvolute NMR signals. The feasibility of the method is studied by (79)Br MAS NMR of KBr under a 30T magnetic field of a hybrid magnet. Twenty single-scan NMR signals were accumulated after the manipulation, resulting in a high-resolution NMR spectrum.     

NMR dynamics in disordered magnets

The excitation dynamics of site diluted magnets can be described at low energies (long length scales) by magnons, and above a crossover frequency, ω_c, (short length scales) by fractons. The density of fracton states is given by , where is the fracton dimensionality. Dilution gives rise to a characteristic length ξ∝(p−p _c)^ν, wherep _c is the critical concentration for (magnetic) percolation. The crossover frequency ω_c is proportional to ξ^-1[1+(θ/2)], where θ is the rate at which the diffusion constant decays with distance for diffusion on an equivalent network. A fractal dimensionD describes the density of magnetic sites on the infinite network, and . For percolating networks, for all dimensions ≥2. Neutron scattering structure factor measurements by Uemura and Birgeneau compare well with calculations using fracton concepts. Magnons are extended at low energies, while the fracton states are geometrically localized, with a wave function envelope proportional to exp . Here, is the fracton length scale at frequency ω. The exponentd _ϕ lies between 1 andd _min, the chemical length index (of the order of 1.6 in three dimensions). The localization of the magnetic excitations causes a spread in the NMR relaxation rates. A given nuclear moment will experience only a limited set of fracton excitations, resulting in an overall non-exponential decay of the NMR relaxation signal. When strong cross-relaxation is present, the relaxation will be exponential, but the temperature dependence will be strongly altered from the concentrated result.     

Nuclear magnetic resonance measurement station in SECUF using hybrid superconducting magnets

Nuclear magnetic resonance(NMR) is one of the most powerful tools to explore new quantum states of condensed matter induced by high magnetic fields at a microscopic level. High magnetic field enhances the intensity of the NMR signal, and more importantly, can induce novel phenomena. In this article, examples are given on the field-induced charge density wave(CDW) in high-Tc superconductors and on the studies of quantum spin liquids. We provide a brief introduction to the high magnetic field NMR platform, the station 4 of the Synergetic Extreme Condition User Facility(SECUF), being built at Huairou, Beijing.     

NMR phase noise in bitter magnets

We have studied the temporal instability of a high field resistive Bitter magnet through nuclear magnetic resonance (NMR). This instability leads to transverse spin decoherence in repeated and accumulated NMR experiments as is normally performed during signal averaging. We demonstrate this effect via Hahn echo and Carr--Purcell--Meiboom--Gill (CPMG) transverse relaxation experiments in a 23-T resistive magnet. Quantitative analysis was found to be consistent with separate measurements of the magnetic field frequency fluctuation spectrum, as well as with independent NMR experiments performed in a magnetic field with a controlled instability. Finally, the CPMG sequence with short pulse delays is shown to be successful in recovering the intrinsic spin--spin relaxation even in the presence of magnetic field temporal instability.     

High-field QCPMG NMR of strontium nuclei in natural minerals

The only stable NMR-active isotope of strontium, (87)Sr, is a spin-9/2 quadrupolar nucleus that has a low gyromagnetic ratio, a low natural abundance, and a large nuclear electric quadrupole moment. In this work, we utilize the quadrupolar Carr-Purcell-Meiboom-Gill (QCPMG) pulse sequence and a 21.14 T NMR spectrometer at the Pacific Northwest National Laboratory to characterize the strontium sites in the natural minerals strontianite (SrCO(3)) and celestine (SrSO(4)). QCPMG at 21.14 T was found to provide sensitivity enhancements of roughly two orders of magnitude over Hahn-echo experiments at an 11.74 T magnetic field. We extracted the quadrupolar parameters for the strontium nuclei through iterative simulations of the experimental spectra with the SIMPSON program by Bak, Rasmussen, and Nielsen. The data show that the quadrupolar parameters of (87)Sr appear to be highly sensitive to the symmetry of the strontium coordination environment and can thus provide information about the strontium binding environment in complex systems.     

High-field cross polarization NMR from laser-polarized xenon to surface nuclei

A method for NMR investigations of surface nuclei using cross polarization from optically polarized xenon (OPCP) is described. We find this methodology results in enhancement factors of approximately 10³ upon application to surface protons. The dynamics of¹²⁹Xe transfer to protons is examined in some detail, including the time, temperature, and multiple contact dependences of signal intensities. Furthermore, we discuss the sensitivity of the transfer process to spatial diffusion. Finally, we report on application of the OPCP experiment to a low total surface area sample.     

High-field (75)As NMR study of arsenic oxysalts

Arsenic is an important environmental hazard, but there have been few NMR investigations of its molecular scale structure and dynamics, due principally to the large quadrupole moment of (75)As and consequent large quadrupole couplings. We examine here the potential of existing, single-field solid-state NMR technology to investigate solids containing arsenate and arsenite oxyanions. The results show that current techniques have significant potential for arsenates that do not contain both protonated H(x)AsO4-(3-x) groups and structural water molecules, but that the quadrupole couplings for the arsenites examined here are large enough that interpretation of the spectra is difficult, even at 21.1T. Compounds that contain both structural H(2)O molecules and protonated arsenate groups do not yield resolvable signal, likely a result of T(2) effects related to a combination of strong quadrupolar interactions and proton exchange. Spin-echo experiments at 11.7 and 14.1T were effective for Li(3)AsO(4) and CsH(2)AsO(4), as were whole-pattern spikelet experiments for arsenate oxide (As(2)O(5)) at 17.6 and 21.1T. The central transition resonance of Ca(3)(AsO(4))(2).8H(2)O is approximately 6 MHz broad and required a non-conventional, histogram-style spikelet method at high field to improve acquisition efficiency. This approach reduces the acquisition time due to the sensitivity enhancement of the spikelet sequence and a reduction in the number of frequency increments required to map the resonance. Despite the large quadrupole couplings, we have identified a correlation between the (75)As isotropic chemical shift and the electronegativity of the next-nearest neighbor cation in arsenate compounds.     

Exchange-coupled nanoscale SmCo/NdFeB hybrid magnets

Nanoscale hybrid magnets containing SmCo₅ and Nd₂Fe₁₄B hard magnetic phases have been produced via a novel “in-one-pot” processing route. The grain size of the processed bulk composite materials is controlled below 20 nm. The refinement of the nanoscale morphology leads to effective inter-phase exchange coupling that results in single-phase like magnetic properties. Energy product of 14 MGOe was obtained in the isotropic nanocomposite magnets at room temperature. At elevated temperatures, the hybrid magnets have greatly improved thermal stability compared to the Nd₂Fe₁₄B single-phase counterpart and have substantially increased magnetization and energy products compared to the single-phase SmCo₅ counterpart.     

NMR and other magnetic resonance techniques in unstable magnets

This paper reviews and compares the use of nuclear magnetic resonance (NMR) and related hyperfine techniques [muon spin rotation (μSR) and, to a lesser extent, other methods] in the study of 4f and 5f magnetism in “unstable magnets”, i.e., intermediate-valent and heavy-fermion materials. In both NMR and μSR the features of interest are the spectral shape, the frequency shiftK (Knight shift in metals) and the spin-lattice relaxation rate 1/T ₁. For temperatures below the characteristic or “Kondo” temperatureT ₀ these experiments given evidence for (1) modification of the transferred hyperfine field [nonlinearK(χ)]. (2) spin fluctuations with a characteristic fluctuation rate ∼k _B T ₀/h, (3) strong energy-gap anisotropy (zeros of the gap along lines on the Fermi surface) in heavy-fermion superconductors, (4) spin-singlet Cooper pairing from the change in muon Knight shift in superconducting UBe₁₃, and (5) very weak static magnetism (10⁻¹–10⁻³ μ_B/f atom) in CeAl₃, CeCu₂Si₂, U_1−x Th _x Be₁₃ (x=0.033), and UPt₃. There is some controversy concerning the interpretation of 1/T ₁ well aboveT ₀ in UBe₁₃; the situation is reviewed.     

High-field 127I NMR of solid sheelite structures: periodates revisited

We report new solid-state ¹²⁷I NMR results for sheelite periodates, MIO₄ (M = Na⁺ , K⁺ , Rb⁺ , and NH⁺ ₄), and for pseudo-scheelite CsIO₄ and HIO₄. The observed ¹²⁷I quadrupole coupling constants were between 1.0 and 43.0 MHz in agreement with previous NQR data. In contrast to an early ¹²⁷I NMR study (S. L. Segel and H. M. Vyas, 1980, J. Chem. Phys.72, 1406), we found that the ¹²⁷I chemical shift anisotropy is negligibly small in sheelite periodates. A small but definite ¹²⁷I chemical shift tensor was observed for pseudo-scheelite CsIO₄.     

Optimization calculations of polyhelix coils for hybrid magnets

In order to generate very high, steady magnetic fields for research in solid-state physics one can combine a high-power resistive magnet with an outer superconducting coil. If magnetic fields above 30 Tesla have to be produced it is advisable to use a water cooled polyhelix copper coil as an inner part of such a hybrid magnet. An algorithm is described which allows the optimization of the design paramaters of a polyhelix coil in an external magnetic field with respect to dimensions and material for various values of the heat flux. The calculations show that with an outside field of 13 Tesla generated by a Nb₃Sn−NbTi coil and with a 10 MW polyhelix magnet made of Cu (Al₂O₃) and Cu−Ag continuous magnetic fields around 40 Tesla may be generated in a 3 cm room temperature bore.     

High-field high-speed MAS resolution enhancement in 1H NMR spectroscopy of solids

Resolution in ¹H NMR spectra of solids can be significantly enhanced with fast magic-angle spinning and high magnetic fields. A variable field and spinning speed study up to 25 T and 40 kHz shows that the homogeneous line broadening is inversely proportional to the product of magnetic field strength and spinning speed. The combination of high field and fast speed yields a ¹H linewidth approaching the intrinsic limit determined by anisotropy of magnetic susceptibility. An analysis of the anisotropic magnetic susceptibility line broadening is presented.     

Reduction of magnetic field fluctuations in powered magnets for NMR using inductive measurements and sampled-data feedback control

Resistive and hybrid (resistive/superconducting) magnets provide substantially higher magnetic fields than those available in low-temperature superconducting magnets, but their relatively low spatial homogeneity and temporal field fluctuations are unacceptable for high resolution NMR. While several techniques for reducing temporal fluctuations have demonstrated varying degrees of success, this paper restricts attention to methods that utilize inductive measurements and feedback control to actively cancel the temporal fluctuations. In comparison to earlier studies using analog proportional control, this paper shows that shaping the controller frequency response results in significantly higher reductions in temporal fluctuations. Measurements of temporal fluctuation spectra and the frequency response of the instrumentation that cancels the temporal fluctuations guide the controller design. In particular, we describe a sampled-data phase-lead-lag controller that utilizes the internal model principle to selectively attenuate magnetic field fluctuations caused by the power supply ripple. We present a quantitative comparison of the attenuation in temporal fluctuations afforded by the new design and a proportional control design. Metrics for comparison include measurements of the temporal fluctuations using Faraday induction and observations of the effect that the fluctuations have on nuclear resonance measurements.     

High-field magnetic resonance imaging using solenoid radiofrequency coils

High-resolution magnetic resonance imaging using dedicated high-field radiofrequency micro-coils at 16.4 T (700 MHz) was investigated. Specific solenoid coils primarily using silver and copper as conductors with enamel and polyurethane coatings were built to establish which coil configuration produces the best image. Image quality was quantified using signal-to-noise ratio and signal variation over regions of interest. Benchmarking was conducted using 5-mm diameter coils, as this size is comparable to an established coil of the same size. Our 1.4-mm-diameter coils were compared directly to each other, from which we deduce performance as a function of conductor material and coating. A variety of materials and conductor coatings allowed us to choose an optimal design, which we used to image a kidney section at 10-micron resolution. We applied zero-fill extrapolation to achieve 5-micron resolution.