The Influence of the Magnetic Impurity Content on the Pore Size Distribution Determination via the DDIF Technique

The pore size distribution of porous media can be determined in a completely non-invasive manner using a new nuclear magnetic resonance (NMR) technique which monitors the magnetization decay due to diffusion in internal fields (DDIF). However, using of the DDIF technique is restricted to the low-phase encoding limit when only the relaxation mode and the first-order diffusion mode are excited. In the present work the fulfillment of such a limit is verified for a progressive increase of the magnetic impurity content of the porous media. If the higher order diffusion modes are excited they lead both to a stronger attenuation of the echo signal and to the appearance of ripples in the DDIF spectra which cannot be related to a pore size distribution. The samples used in this study are porous ceramics prepared using the replication technique and the magnetic impurity is iron (III) oxide which is introduced in an increasing concentration inside the porous matrix. All NMR experiments were done on water filling such porous ceramics using a low-field instrument operating at a proton resonance frequency of 20 MHz. The average pore dimension obtained with the DDIF technique in the weak encoding limit indicates a satisfactory agreement with that observed in optical microscopy images.     

Probing the Pore Size of Porous Ceramics with Controlled Amount of Magnetic Impurities via Diffusion Effects on the CPMG Technique

In our work, we will explore the possibility of implementing the well-known Carr–Purcell–Meiboom–Gill pulse sequence to determine the pore size of porous ceramics with magnetic impurities. The proposed approach exploits the diffusion dependence of the spin-echo signal in the presence of internal gradients occurring as a result of susceptibility contrast between the porous matrix and the confined liquid. For calibrating the technique, a comparison of the pore size data with those extracted from the so-called DDIF technique (DDIF, decay due to diffusion in the internal fields) is performed. This approach can be applied for nondestructive in situ characterization of soils, concrete, biological tissues or other structures with micrometer pore size.     

Internal Magnetic Field Gradients in Heterogeneous Porous Systems: Comparison Between Spin-Echo and Diffusion Decay Internal Field (DDIF) Method

Two techniques used for evaluating internal magnetic field gradient (G _i), spin-echo (SE) and diffusion decay internal field (DDIF), were investigated at 9.4 T and compared in porous systems characterized by different pores size ranging from 4 to 96 μm with magnetic susceptibility difference between solid and liquid phase, \(\Delta \chi\)  ≈ 1.6 ppm. Since diffusion of a fluid in a solid porous matrix plays a role in both SE and DDIF methods, we investigated these two different methods by highlighting their dependence on characteristic parameters and length scales used to describe diffusion behavior of fluids in porous systems. Therefore, G _i behavior as a function of the dephasing length (l _g), diffusion length (l _d) and pores size (l _s) was obtained. Moreover G _i was evaluated by using both free diffusion and measured apparent diffusion coefficient of water, to quantify diffusion effect in different porous samples. This study gives more insight into the physical dynamics process to explain contrast mechanisms recently exploited by DDIF and SE applications for cancellous bone quality measurements.     

Multidimensionally resolved pore size distributions

A novel method of determining median pore size and pore size distributions as a function of spatial position inside a porous sample is described. Pore sizes have been measured with 1-, 2- and 3-dimensional spatial resolution, using NMR cryoporometry in conjunction with magnetic resonance imaging techniques. The method is suitable for pore diameters in the range of 30 Å to over 2000 Å pore diameter, and is based on the technique of freezing a liquid in the pores and measuring the melting temperature by nuclear magnetic resonance. Since the melting point is depressed for crystals of small size, the melting point depression gives a measurement of pore size.     

Magnetic resonance imaging by synergistic diffusion-diffraction patterns

Inferring on the geometry of an object from its frequency spectrum is highly appealing since the object could then be imaged noninvasively or from a distance (as famously put by Kac, "can one hear the shape of a drum?"). In nuclear magnetic resonance of porous systems, the shape of the drum is represented by the pore density function that bears all the information on the collective pore microstructure. So far, conventional magnetic resonance imaging (MRI) could only detect the pore autocorrelation function, which inherently obscures fine details on the pore structure. Here, for the first time, we report on a unique imaging mechanism arising from synergistic diffusion-diffractions that directly yields the pore density function. This mechanism offers substantially higher spatial resolution compared to conventional MRI while retaining all fine details on the collective pore morphology. Thus, using these unique synergistic diffusion-diffractions, the "shape of the drum" can be inferred.     

Two-dimensional nuclear magnetic resonance petrophysics

Two-dimensional nuclear magnetic resonance (2D NMR) opens a wide area for exploration in petrophysics and has significant impact to petroleum logging technology. When there are multiple fluids with different diffusion coefficients saturated in a porous medium, this information can be extracted and clearly delineated from CPMG measurements of such a system either using regular pulsing sequences or modified two window sequences. The 2D NMR plot with independent variables of T2 relaxation time and diffusion coefficient allows clear separation of oil and water signals in the rocks. This 2D concept can be extended to general studies of fluid-saturated porous media involving other combinations of two or more independent variables, such as chemical shift and T1/T2 relaxation time (reflecting pore size), proton population and diffusion contrast, etc.     

The internal magnetic field distribution, and single exponential magnetic resonance free induction decay, in rocks

When fluid saturated porous media are subjected to an applied uniform magnetic field, an internal magnetic field, inside the pore space, is induced due to magnetic susceptibility differences between the pore-filling fluid and the solid matrix. The microscopic distribution of the internal magnetic field, and its gradients, was simulated based on the thin-section pore structure of a sedimentary rock. The simulation results were verified experimentally. We show that the 'decay due to diffusion in internal field' magnetic resonance technique may be applied to measure the pore size distribution in partially saturated porous media. For the first time, we have observed that the internal magnetic field and its gradients in porous rocks have a Lorentzian distribution, with an average gradient value of zero. The Lorentzian distribution of internal magnetic field arises from the large susceptibility contrast and an intrinsic disordered pore structure in these porous media. We confirm that the single exponential magnetic resonance free induction decay commonly observed in fluid saturated porous media arises from a Lorentzian internal field distribution. A linear relationship between the magnetic resonance linewidth, and the product of the susceptibility difference in the porous media and the applied magnetic field, is observed through simulation and experiment.     

Determining pore sizes using an internal magnetic field

A concept is proposed to measure the pore size length scale by the internal magnetic field (B_i) in porous materials. The spatial distribution of the magnetic field inhomogeneity, a result of the magnetic susceptibility contrast between the porous material and the fluid, reflects the underlying pore geometry. Diffusion in B_i causes the initial decay of magnetization. At long times, the effect of B_i saturates when the diffusion length reaches a characteristic pore size. This method is independent of surface spin relaxation in determining pore sizes. Nuclear magnetic resonance experiments on packed glass beads and sedimentary rock samples will be presented.     

NMR magnetization transfer as a tool for characterization of nanoporous materials

The application of nuclear magnetic resonance magnetization transfer experiments to probe the surface-to-volume ratio and pore morphology of porous materials with characteristic pore sizes of 1-100 nm is described. The method is based on the phenomenon of incomplete freezing of liquids in small pores where a few monolayers adjacent to the pore walls remain liquid. Sufficient difference between the transverse relaxation times in the solid frozen core and liquid surface layer allows the initial preparation and subsequent re-equilibration of a solid-liquid magnetization grating. The method is demonstrated using model nanoporous materials with known characteristics. The ensuing problems of the mechanism of the magnetization transfer through the interface and within the frozen core are discussed and elucidated by pulsed-field-gradient NMR experiments.     

Determination of the defining boundary in nuclear magnetic resonance diffusion experiments

While nuclear magnetic resonance diffusion experiments are widely used to resolve structures confining the diffusion process, it has been elusive whether they can exactly reveal these structures. This question is closely related to x-ray scattering and to Kac's "hear the drum" problem. Although the shape of the drum is not "hearable," we show that the confining boundary of closed pores can indeed be detected using modified Stejskal-Tanner magnetic field gradients that preserve the phase information and enable imaging of the average pore in a porous medium with a largely increased signal-to-noise ratio.     

Control of magnetic anisotropy of Co nanowires

Cobalt nanowires were fabricated by DC electrodeposition onto anodic aluminium oxide (AAO) templates. The effects of AAO pore diameter, current density, pH, annealing and deposition under external magnetic fields on the structure and magnetic properties of the nanowire arrays were studied. It is found that the smaller pore size produces high crystallinity, resulting in improved magnetic performance at low current density. The pH can transform fcc-Co phase to hcp-Co phase, with the easy axis along the nanowire axis switched over to the perpendicular direction. Annealing demonstrates excellent thermal stability of the magnetic nanowire arrays at high temperature. The application of external magnetic field during deposition influences the growth habit of the nanowires, leading to the change in the magnetic properties.     

Correlation functions for inhomogeneous magnetic field in random media with application to a dense random pack of spheres

In porous media subject to applied magnetic field, the internal field arises out of susceptibility contrast of the constituents. We have examined the spatial inhomogeneity of the internal fields in a random pack of spheres using numerical computation. We find that the pair-correlation function of the internal field (K2) is a close approximation to the structure factor of the material, thus K2 can be used to characterize pore geometry. The magnetic length scale LambdaM exhibited in K2 is shown to be related to the fluid transport in the medium.     

The dependence on magnetic field strength of correlated internal gradient relaxation time distributions in heterogeneous materials

Magnetic susceptibility differences in porous media produce local gradients within the pore space. At high magnetic fields, these inhomogeneities have the potential to greatly affect nuclear magnetic resonance measurements. We undertake a study using a new NMR technique to measure the internal gradients present in highly heterogeneous samples over a wide range of magnetic field strengths. Our results show that even at ultra-high fields there can exist signal at internal gradient strengths sufficiently small that techniques for suppressing unwanted side effects have the possibility to be used. Our findings encourage the use of these high and ultra-high field strengths for a broader range of samples. Our results also give experimental evidence to support the theory of internal gradient scaling as a function of field strength within pores.     

Proton spin-spin relaxation study of hydration of a model nanopore

The hydration pattern of controlled pore glass, with pore diameter of 237 Å, was investigated using nuclear magnetic resonance. Water proton spin–spin relaxation decay curves were monitored and modeled as two-component exponential decays as a function of hydration. The results are consistent with a geometric model involving a surface water layer and a bulk-like liquid fraction in the form of a plug. The amount of surface water increases as the sample hydrates, until hydration reached approximately a monolayer, at which point a water plug starts to form in the pore, and grow in length at the expense of the surface layer. The results are also analyzed in terms of, and compared to, a recently developed puddle pore-filling model [S.G. Allen, et al. J. Chem. Phys. 106 (1997) 7802–7809].     

Removal and recovery of mercury from aqueous solution using magnetic silica nanocomposites

Thiol-functionalized magnetic silica nanocomposite was synthesized and tested for its mercury pick-up capability in aqueous solution. Magnetic property was to be utilized upon the collection of the adsorbents and the recovery adsorbed Hg by subsequent separation process. Cobalt ferrite nanoparticle, the core of magnetic silica nanocomposite, was synthesized using a thermal decomposition method and grown to a particle having an average size of 13 nm. The dispersed nanoparticles were then further arranged into spherical groups using a nanoemulsion method to enhance the reactivity toward magnets followed by tetraethyl orthosilicate coating using a modified Stöber method. The pore structure was modified by an additional coating of cetyltrimethylammonium bromide and tetraethyl orthosilicate. Finally, the surface of the magnetic silica nanocomposite was functionalized with thiol group. When tested for mercury adsorption capacity, a sufficiently high Hg adsorption capacity of 19.79 mg per g of adsorbent was obtained at room temperature and a pH of 5.5.     

Observation of high density recording states using magnetic fine particles made by sputtering method

High density recording patterns were visualized by sputter-deposition of magnetic fine particles on recording media. Very clear patterns were formed when the magnetic particles were deposited under a weak magnetic field onto the sample surface covered with a thin oil layer. By using this process, the recorded patterns at a density of 100 k FCI (bit length 0.25 μm) were very clearly observed by a scanning electron microscope. This method gives very effective measures to investigate the recording states of magnetic and magneto-optical media.     

Internal magnetic gradient fields in glass bead packs from numerical simulations and constant time diffusion spin echo measurements

Internal magnetic field gradients in water saturated glass bead packs were studied by numerical simulations and a constant time spin echo (CTSE) experiment. The CTSE is comprised of two spin echo refocusing periods where each of the two evolution periods, tau1 and tau2, is varied so that the total evolution, 2(tau1 + tau2), is held constant. The experiment is similar to that introduced by Norwood and Quilter and allows the effects of dephasing due to diffusion in a magnetic field gradient to be separated from other relaxation mechanisms. In our experiments, the magnetic susceptibility difference between the pore fluid and glass beads creates the internal field gradient. CTSE measurements were performed at 7 T (300 MHz 1H) for water saturated in 50 microm diameter glass bead pack. We find that the internal gradients in the center of the pore bodies, where free diffusion applies, is in the range of 10 to 100 G/cm. This fluid volume accounts for < or =10% of the total pore volume. From direct numerical simulations of the internal magnetic field based on a first principles calculation, we find that the major fraction, >90%, of the pore volume has internal gradients of order 500 to 5,000 G/cm. Signals from water in these large gradients is not observed in our CTSE measurements.     

基于PASCO实验平台的地球磁场测量

基于PASCO实验平台的软件和计算机接口,利用高灵敏度磁场传感器对地球磁场的强度及磁倾角等相关参量进行测量与分析。实验结果表明,该测量方法操作简单,精确度较高,实用性很强。通过轻松的实验过程对地球磁场等不易感知的弱磁场有了一个清晰直观的认识。     

Estimation of pore size in a microstructure phantom using the optimised gradient waveform diffusion weighted NMR sequence

There has been increasing interest in nuclear magnetic resonance (NMR) techniques that are sensitive to diffusion of molecules containing NMR visible nuclei for the estimation of microstructure parameters. A microstructure parameter of particular interest is pore radius distribution. A recent in silico study optimised the shape of the gradient waveform in diffusion weighted spin-echo experiments for estimating pore size. The study demonstrated that optimised gradient waveform (GEN) protocols improve pore radius estimates compared to optimised pulse gradient spin-echo (PGSE) protocols, particularly at shorter length scales. This study assesses the feasibility of implementing GEN protocols on a small bore 9.4 T scanner and verifies their additional sensitivity to pore radius. We implement GEN and PGSE protocols optimised for pore radii of 1, 2.5, 5, 7.5, 10 μm and constrained to maximum gradient strengths of 40, 80, 200 mT m(-1). We construct microstructure phantoms, which have a single pore radius for each phantom, using microcapillary fibres. The measured signal shows good agreement with simulated signal, strongly indicating that the GEN waveforms can be implemented on a 9.4 T system. We also demonstrate that GEN protocols provide improved sensitivity to the smaller pore radii when compared to optimised PGSE protocols, particularly at the lower gradient amplitudes investigated in this study. Our results suggest that this improved sensitivity of GEN protocols would be reflected in clinical scenarios.     

Interpretation of restricted diffusion in sandstones with internal field gradients.

We report on experiments to characterize internal magnetic field gradients that are caused by magnetic susceptibility differences between the solid phase and the fluids filling the pore space. Our measurements focus on low-field relaxometry of brine and oil in sandstones from various reservoirs around the world. Our results show the need to understand the dependence of internal field gradients on diffusion length, pore size- and fluid distribution in order to predict the impact of internal gradients on the interpretation of NMR experiments.