Visualization of Steady-State Ionic Concentration Profiles Formed in Electrolytes during Li-Ion Battery Operation and Determination of Mass-Transport Properties by in Situ Magnetic Resonance Imaging.

Accurate modeling of Li-ion batteries performance, particularly during the transient conditions experienced in automotive applications, requires knowledge of electrolyte transport properties (ionic conductivity κ, salt diffusivity D, and lithium ion transference number t(+)) over a wide range of salt concentrations and temperatures. While specific conductivity data can be easily obtained with modern computerized instrumentation, this is not the case for D and t(+). A combination of NMR and MRI techniques was used to solve the problem. The main advantage of such an approach over classical electrochemical methods is its ability to provide spatially resolved details regarding the chemical and dynamic features of charged species in solution, hence the ability to present a more accurate characterization of processes in an electrolyte under operational conditions. We demonstrate herein data on ion transport properties (D and t(+)) of concentrated LiPF6 solutions in a binary ethylene carbonate (EC)-dimethyl carbonate (DMC) 1:1 v/v solvent mixture, obtained by the proposed technique. The buildup of steady-state (time-invariant) ion concentration profiles during galvanostatic experiments with graphite-lithium metal cells containing the electrolyte was monitored by pure phase-encoding single point imaging MRI. We then derived the salt diffusivity and Li(+) transference number over the salt concentration range 0.78-1.27 M from a pseudo-3D combined PFG-NMR and MRI technique. The results obtained with our novel methodology agree with those obtained by electrochemical methods, but in contrast to them, the concentration dependences of salt diffusivity and Li(+) transference number were obtained simultaneously within the single in situ experiment.

Monitoring oil displacement processes with k-t accelerated spin echo SPI.

Magnetic resonance imaging (MRI) is a robust tool to monitor oil displacement processes in porous media. Conventional MRI measurement times can be lengthy, which hinders monitoring time-dependent displacements. Knowledge of the oil and water microscopic distribution is important because their pore scale behavior reflects the oil trapping mechanisms. The oil and water pore scale distribution is reflected in the magnetic resonance T2 signal lifetime distribution. In this work, a pure phase-encoding MRI technique, spin echo SPI (SE-SPI), was employed to monitor oil displacement during water flooding and polymer flooding. A k-t acceleration method, with low-rank matrix completion, was employed to improve the temporal resolution of the SE-SPI MRI measurements. Comparison to conventional SE-SPI T2 mapping measurements revealed that the k-t accelerated measurement was more sensitive and provided higher-quality results. It was demonstrated that the k-t acceleration decreased the average measurement time from 66.7 to 20.3 min in this work. A perfluorinated oil, containing no (1) H, and H2 O brine were employed to distinguish oil and water phases in model flooding experiments. High-quality 1D water saturation profiles were acquired from the k-t accelerated SE-SPI measurements. Spatially and temporally resolved T2 distributions were extracted from the profile data. The shift in the (1) H T2 distribution of water in the pore space to longer lifetimes during water flooding and polymer flooding is consistent with increased water content in the pore space. Copyright © 2015 John Wiley & Sons, Ltd.

A low-field ceramic magnet design for magnetic resonance.

We describe the design of a low-field portable magnet, based on two ceramic magnets, separated by a distance, with their magnetic poles aligned to create a large homogeneous region with a field strength of 425 gauss. Ceramic magnets are an uncommon choice compared to Neodymium Iron Boron magnets for low-field magnetic resonance but are preferable for our purposes to create a homogeneous region at lower field strength. The low cost of large ceramic magnets results in an inexpensive design with a large measurement volume. The magnets rest in a 3D-printed structure, which allows for the magnets to be moved by hand so the experimentalist has control over the field topology. To test the utility of the design, we explored an Overhauser dynamic nuclear polarization experiment with an aqueous solution of 4-Hydroxy-TEMPO. We also explored a simple flow measurement employing the ceramic magnets at a 6-degree pitch, creating a 14.6 gauss/cm constant gradient.

Selective enhancement of 1H signal from water and oil in porous media at low field with Overhauser DNP.

In porous media MR studies, discriminating between oil and water presents a challenge because MR lifetimes are often similar and spectra overlap. Low saturations might suggest an experimental strategy of increasing the static field for increased sensitivity, but susceptibility effects are exacerbated at higher field. Overhauser dynamic nuclear polarization, effective at low static field, was employed with water and oil-soluble nitroxide to selectively enhance water and oil signals. We employ a home-built 2 MHz ceramic magnet to achieve selective enhancement of water and oil, in bulk, and in a rock core. For imaging, we employ a 705 kHz ceramic magnet with a 4 gauss/cm constant gradient configuration to image the hyperpolarized signal. A rock core flooding experiment was undertaken to highlight the advantages of Overhauser enhancement. A simple phase cycling technique may be employed to cancel the thermally polarized 1H signal to isolate the enhanced signal of interest.

Fast spin echo MRI of reservoir core plugs with a variable field magnet.

Fast Spin Echo MRI is now widely employed in biomedicine for proton density and T2 contrast imaging. Fast Spin Echo methods provide rapid data acquisition by employing multiple echoes to determine multiple k-space lines with single excitations. Due to the multi-exponential behavior of T2 in typical porous media, and the strong dependence of T2 on the details of the experiment, acquiring a proton density image with Fast Spin Echo methods requires favorable sample and acquisition parameters. In recent years, we have shown the value of pure phase encode Free Induction Decay based methods such as SPRITE. However, in a reservoir rock, a typical T2* is hundreds of µs, whereas a typical T2 is hundreds of ms. Hence, there is merit in considering spin echo-based MRI measurements such as the Fast Spin Echo for rock core plug studies. A variable field superconducting magnet was employed in this study. This is a new class of magnet for MR/MRI. These magnets have the flexibility of operation in the field range of 0.01 Tesla to 3 Tesla. This is advantageous when working with rock core plugs, as it allows one to maximize sample magnetization, by increasing the static field while controlling magnetic susceptibility mismatch effects, and thereby T2 and T2*, through reducing the static field. The magnetic fields employed in the study were 0.79, 1.5, and 3 Tesla. Measurements were undertaken on five brine-saturated reservoir rock core plugs (Bentheimer, Berea, Buff Berea, Nugget, and Wallace). The results show that Fast Spin Echo measurements are more sensitive than SPRITE methods in amenable samples and usually feature higher resolution. Quantification of saturation with Fast Spin Echo methods requires correction for T2 attenuation. The results also show that 3 Tesla is too high a static field in general for rock core MRI studies with either method. While the current study is focused on five representative reservoir rock cores, the conclusions which result are general for MRI of fluids in porous media.

A comparison of magnetic resonance imaging methods for fluid content imaging in porous media.

Quantitative measurements are important for imaging fluid content in porous media. Conventional MRI methods suffer from contrast because of relaxation times in porous media, resulting in measurements of apparent fluid content, not the true fluid content. We compare four magnetic resonance imaging methods for fluid content imaging in several water-saturated reservoir core plugs: frequency-encoded spin echo, single point ramped imaging with T1 enhancement, hybrid spin echo single point imaging (SE-SPI), and T2 mapping SE-SPI. 1-D profiles obtained with each method were compared in terms of image quality, image sensitivity, and quantification of water content. The image quality of short T2 lifetime samples suffered from blurring in hybrid SE-SPI images. Image sensitivity was the highest in the profiles obtained with frequency-encoded spin echo. The quantification of frequency-encoded spin echo, T2 mapping SE-SPI, and hybrid SE-SPI suffered in core plugs with a significant population of short T2 components because of T2 attenuation. Overall, single point ramped imaging with T1 enhancement was found to be the most general method for fluid content imaging.

Rapid measurement of T1*-T2* relaxation correlation with a Look-Locker sequence.

Measurement of longitudinal-transverse (T1-T2*) relaxation may be time-consuming for samples with a long T1 lifetime. In this work, a fast measurement method of T1*-T2* relaxation correlation was presented based on a saturation recovery Look-Locker sequence. T1* is the effective T1 lifetime. The T1 lifetime can be calculated from the measured T1* lifetime and acquisition parameters. The new measurement method was verified by numerical simulation. Three representative samples, corn starch, Advil caplets, and shale in the fields of food, pharmaceutics, and energy, were employed as test samples. Comparisons of T1*-T2* and T1-T2* relaxation correlations show that the new two-dimensional magnetic resonance pulse sequence works well, with a high collection efficiency and good accuracy.

Design and validation of a single-sided magnet with a constant gradient parallel to its surface.

We present the design, validation, and testing of an optimized 5 MHz three-magnet array with a gradient parallel to the magnet surface. An approach to permanent magnet array design is explored with a genetic algorithm. The genetic algorithm was used to produce multiple designs based on an inventory of available block magnets. One three-magnet array was constructed for testing. Constant gradients of 205, 115, and 61 gauss/cm, parallel to the magnet surface are found at displacements of 1.5, 2.0, and 2.5 cm from the surface of the magnet, respectively. Regions of useful gradient are roughly 1 cm in length. We constructed and field plotted the three-magnet array and found good agreement between the experimental and simulated magnet fields. To test applicability, we performed T1 and T2 relaxation measurements on a cod liver oil sample, and a simple doped water flow measurement.

Coils for large standoff relaxometry with unilateral magnets.

Maximizing standoff distance by direct placement of probe coils on magnet bodies, while maximizing signal-to-noise is critical to the successful application of unilateral NMR. Two types of radio frequency (rf) coils for linear array, unilateral magnets are described: "simple fringe" and "split fringe coils." These coils are designed to fully exploit the standoff distance of the unilateral magnet by placement directly on the magnet surface. Such placement fails for normal surface coils used for magnetic resonance due to eddy current induced shielding by the conductive magnet surface. The coil design strategy includes a rectangular cross section solenoid coil, either continuous or split in the center, mounted with the center axis of the coil parallel to the magnet surface. These geometries, when placed on a conducting surface, enhance the rf field produced in the sample region, outside of the solenoid coil. The spatial homogeneity of both rf coils are characterized using the ANSYS™ finite element modelling software. ANSYS™ modeled coil geometries led to homogeneous, surface displaced rf fields. These coils were then constructed and characterized with magnetic resonance imaging. Finally, two experiments that use these coils to perform large standoff relaxation measurements are described.

Magnetic resonance T1-T2* and T1ρ-T2* relaxation correlation measurements in solid-like materials with non-exponential decays.

Magnetic resonance T1-T2* relaxation correlation is a newly emerging and powerful tool to study the structure and dynamics of materials. However, the T1-T2* of solid-like materials may consist of a linear combination of exponential decays and non-exponential decays, and the traditional methods for processing T1-T2 data would be not applicable. In this paper, a method of processing T1-T2* data with non-exponential decays was proposed. The critical idea is to decompose the data into two sub-datasets, exponential decays and non-exponential decays, employing a non-linear fitting method, and then to invert the sub-datasets and to combine the inversion results. We also introduce a related relaxation correlation measurement, T1ρ-T2*, for examination of solid-like materials. The same data processing strategy as for T1-T2* was implemented. The effectiveness of the proposed method for processing non-exponential data, Sinc Gaussian and Gaussian decay, was validated with simulation and experiment. The results showed that the proposed method recovers T1-T2* and T1ρ-T2* spectra with accurate relative signal intensities. The proposed method provides a platform for further development of MR methods applied to solid-like materials. These relaxation correlations are well suited to measuring composition of mixtures, with solid components in the mixture.

A portable, submersible, MR sensor - The Proteus magnet.

This paper details the design, fabrication, and testing of a new portable magnet, generically termed the Proteus magnet, that can undertake a wide range of MR measurements. The Proteus magnet is intended for 1H measurements of liquids and is fully functional when submersed in the sample of interest. The Proteus magnet is fabricated from a pair of low-cost, commercial, NdFeB disk magnets, axially polarized, with their North and South poles aligned. The two N52 NdFeB magnets - 31.75 mm diameter and 6.35 mm thickness were separated by 10 mm. The gap between the magnets is sufficient for a RF shield and transverse rectangular solenoid RF probe. The sensor was evaluated through a series of measurements including bulk CPMG, saturation recovery T1, self-diffusion, T1 - T2, and D - T2.

A parallel-plate RF probe and battery cartridge for 7Li ion battery studies.

A new parallel-plate resonator for 7Li ion cell studies is introduced along with a removable cartridge-like electrochemical cell for lithium ion battery studies. This geometry separates the RF probe from the electrochemical cell permitting charge/discharge of the cell outside the magnet and introduces the possibility of multiplexing samples under test. The new cell has a geometry that is similar to that of a real battery, unlike the majority of cells employed for MR/MRI studies to this point. The cell, with electrodes parallel to the B1 magnetic field of the probe, avoids RF attenuation during excitation/reception. The cell and RF probe dramatically increase the sample volume compared to traditional MR compatible battery designs. Ex situ and in situ 1D 7Li profiles of Li ions in the electrolyte solution of a cartridge-like cell were acquired, with a nominal resolution of 35 µm at 38 MHz. The cell and RF probe may be employed for spectroscopy, imaging and relaxation studies. We also report the results of a T1-T2 relaxation correlation experiment on both a pristine and fully charged cell. This study represents the first T1-T2 relaxation correlation experiment performed in a Li ion cell. The T1-T2 correlation maps suggest lithium intercalated into graphite is detected by this methodology in addition to other Li species.

Velocity mapping of fast flows using a linearly ramped gradient waveform.

We report a new pure phase encoding measurement for velocity mapping. Velocity-sensitization is achieved using a repeating, linearly ramped gradient waveform instead of rectangular bipolar pulsed field gradients. This approach reduces eddy current effects and results in the sample experiencing a gradient waveform that more closely matches the ideal input. Errors in k-space mapping and calculated velocity values are reduced when contrasted with the previous measurement method. Velocity maps were acquired of high-speed (c. 6 m/s) water flow through a pipe constriction. The application of linearly ramped gradient waveforms to non-velocity-encoded imaging measurements is discussed.

Ultra-short echo time imaging with multiple echo refocusing for porous media T2 mapping.

T2 relaxation time measurement is a powerful tool to distinguish signal components in porous media. As T2 weighting is generally achieved by spin-echo based methods, it is very challenging to capture very short T2 relaxation time components, approximately 1 ms, with high resolution spatial encoding. It is especially challenging when T2 relaxation times of the other signal components are not known a priori. We propose a method, combining ultrashort echo time (UTE) imaging with multiple spin echo refocusing, to generate a series of images with T2 weighting. The T2 decay curves for each image voxel were extracted, and multiple T2 relaxation components were quantitatively evaluated. The method has been applied to a fast relaxation system, namely, moisture content in wood samples to differentiate cell wall (bound) water and cell cavity (lumen) water.

A low cost, portable NMR probe for high pressure, MR relaxometry.

A low cost, portable, high volume, stainless steel pressure reactor is modified to easily perform magnetic resonance relaxometry at industrially relevant pressures. Unlike existing pressurization strategies common to nuclear magnetic resonance (NMR) spectroscopy, this approach is amenable to realistic samples that feature heterogeneity and have traditionally escaped NMR study at pressure. This pressure reactor/NMR probe combination is easily accommodated by most single-sided and other low magnetic field permanent magnet assemblies. The performance of the probe is demonstrated by accomplishing NMR relaxometry on polydimethylsiloxane at different pressures with two types of unilateral magnets.

Noninvasive, Nondestructive Measurement of Tomato Concentrate Spoilage in Large-Volume Aseptic Packages.

Low frequency nuclear magnetic resonance (NMR) is used to noninvasively and nondestructively detect spoiled tomato concentrate stored in >200 L metal-lined containers. It is shown that longitudinal and transverse NMR relaxation times change as the tomato concentrate spoils. A rapid, viscosity-dependent spoilage detection method that takes advantage of the inherent inhomogeneity in single-sided NMR instruments is proposed. Here, the effective transverse magnetization decay rate is used as a parameter to determine tomato concentrate spoilage. Three different low frequency, single-sided NMR instruments are described and compared to determine the optimum sensor for spoiled tomato concentrate detection in large-format, metal-lined, aseptic containers. The most effective NMR sensor for this application is temperature stable and has large magnetic field gradients and a homogeneous magnetic field region offset >0.5 cm from the magnet surface. PRACTICAL APPLICATION: This manuscript describes a noninvasive and nondestructive tomato concentrate spoilage detector for application to large-format, sealed, commercial storage bins.

Controlling susceptibility mismatch effects, signal lifetimes, and SNR through variation of B0 in MRI of rock core plugs.

1H relaxometry measurements of petroleum core plugs are commonly performed on low field magnets (<0.5 Tesla) to reduce the influence of magnetic susceptibility mismatch on measurements of the spin-spin relaxation time, T2. The Signal to Noise Ratio (SNR) of the MR signal, however, generally decreases with lower magnetic fields. Higher magnetic fields (>3 Tesla) are typically employed in small animal MRI studies to improve SNR and image resolution. For many rock core plug samples, susceptibility mismatch effects can be severe at these higher fields leading to decreased T2 and T2*. In this work we seek an answer to the general question of what is the best field for MRI of rock core plugs, anticipating that it will be both sample and measurement method dependent. Free Induction Decay (FID) relaxation time measurements were undertaken to investigate the conditions under which the SNR in Centric Scan SPRITE (Single Point Ramped Imaging with T1 Enhancement) MRI measurements is maximized. The image SNR benefits from greater signal at higher fields, but is negatively impacted by the correspondingly shorter signal lifetimes. Depending on the noise regime of the sample, the maximum SNR may be predicted for Centric Scan SPRITE MRI with T2* being B0 field dependent. In this work we describe a series of simple experimental considerations to determine the optimal B0 field for SPRITE MRI. Selection of the best field is aided by a new generation of superconducting magnets which allows the experimentalist to readily vary the field strength. Such magnets allow one to experimentally control sample magnetization for high sensitivity MRI measurements of core plug samples, while controlling the effect of susceptibility mismatch on the signal lifetimes.

A compact permanent magnet array with a remote homogeneous field.

We present the design and construction of a single sided magnet array generating a homogeneous field in a remote volume. The compact array measures 11.5 cm by 10 cm by 6 cm and weights approximately 5 kg. It produces a B(0) field with a 'sweet spot' at a point 1cm above its surface, where its first and second spatial derivatives are approximately zero. Unlike other sweet spot magnets of this general type, our array has B(0) oriented parallel to its surface. This allows an ordinary surface coil to be used for unilateral measurements, giving the potential for dramatic SNR improvement.

Quantitative discrimination of water and hydrocarbons in porous media by magnetization prepared centric-scan SPRITE.

MRI has considerable potential as a non-destructive probe of porous media, offering the possibility of rapid quantification of local oil and water content. This potential has not yet, however, been completely realized. In this paper, we explore a general magnetization preparation approach to the discrimination of water and oil in a model, representative, porous medium. These measurements have, as a common element, a centric scan pure phase encode readout based on the SPRITE methodology. Magnetization preparation permits facile T1, T2 and diffusion coefficient mapping as the basis for oil and water discrimination. Diffusion coefficient mapping proved to be the most robust approach to discrimination of oil and water. These methods are illustrated through static experiments and a dynamic immiscible fluid displacement experiment.

BLIPPED (BLIpped Pure Phase EncoDing) high resolution MRI with low amplitude gradients.

MRI image resolution is proportional to the maximum k-space value, i.e. the temporal integral of the magnetic field gradient. High resolution imaging usually requires high gradient amplitudes and/or long spatial encoding times. Special gradient hardware is often required for high amplitudes and fast switching. We propose a high resolution imaging sequence that employs low amplitude gradients. This method was inspired by the previously proposed PEPI (π Echo Planar Imaging) sequence, which replaced EPI gradient reversals with multiple RF refocusing pulses. It has been shown that when the refocusing RF pulse is of high quality, i.e. sufficiently close to 180°, the magnetization phase introduced by the spatial encoding magnetic field gradient can be preserved and transferred to the following echo signal without phase rewinding. This phase encoding scheme requires blipped gradients that are identical for each echo, with low and constant amplitude, providing opportunities for high resolution imaging. We now extend the sequence to 3D pure phase encoding with low amplitude gradients. The method is compared with the Hybrid-SESPI (Spin Echo Single Point Imaging) technique to demonstrate the advantages in terms of low gradient duty cycle, compensation of concomitant magnetic field effects and minimal echo spacing, which lead to superior image quality and high resolution. The 3D imaging method was then applied with a parallel plate resonator RF probe, achieving a nominal spatial resolution of 17 µm in one dimension in the 3D image, requiring a maximum gradient amplitude of only 5.8 Gauss/cm.