An NMR-Based Analysis of Soil–Water Characteristics

Both direct and indirect methods for determining soil–water characteristic curves rely on determination of some empirical coefficients, which may not necessarily represent real microscopic mechanisms. Proton nuclear magnetic resonance (NMR) is a powerful tool for investigating water content and their interaction with solid particles in porous media. The NMR technique is widely used in food science and petroleum. In the present study, proton NMR spin–spin relaxation time (T ₂) distribution measurement is integrated with a Tempe apparatus to characterize the hydraulic processes of unsaturated soils, shedding insights into the microscopic mechanisms of pore water distribution and migration in the soil during hydraulic cycles. It is revealed that during a drying process the drainage of pore water occurs sequentially from larger pores to smaller pores, whereas in a wetting process the water invades into the soil sequentially from smaller pores to larger pores. A new procedure is developed which can be used to determine the pore size distribution of the soil based on the NMR T ₂ distribution measurements; compared to the traditional methods, the new method is rapid and non-destructive. The new procedure is validated by comparing the new result with the measurement of the mercury intrusion porosimetry.     

Microstructural features assessment of different waterlogged wood species by NMR diffusion validated with complementary techniques

Wood is a hygroscopic, multi-scale and anisotropic natural material composed of pores with different size and differently oriented. In particular, archaeologically excavated wood generally is waterlogged wood with very high moisture content (400%–800%) that need to have a rapid investigation at the microstructural level to obtain the best treatment with preservative agents. Time-dependent diffusion coefficient D(t) quantified by Pulse Field Gradient (PFG) Nuclear Magnetic Resonance (NMR) techniques provides useful information about complex porous media, such as the tortuosity (τ) describing pore connectivity and fluid transport through media, the average-pore size, the anisotropic degree (a_n). However, diffusion NMR is intrinsically limited since it is an indirect measure of medium microstructure and relies on inferences from models and estimation of relevant diffusion parameters. Therefore, it is necessary to validate the information obtained from NMR diffusion parameters through complementary investigations. In this work, the structures of five waterlogged wood species were studied by PFG of absorbed water. D(t) and τ of water diffusing along and perpendicular to vessels/tracheids main axes together with relaxation times and a_n were quantified. From these parameters, the pore sizes distribution and the wood microstructure characterization were obtained. Results among wood species were compared, validated and integrated by micro-imaging NMR (μ-MRI), environmental-scanning electron-microscope (ESEM) images, wood dry density and imbibition times measurement of all woods. The work suggests that a_n vs τ rather than the estimated pore size diversifies and characterize the different wood species. As a consequence diffusion-anisotropy vs tortuosity could be an alternative method to characterize and differentiate wood species of waterlogged wood when high resolution images (μ-MRI and ESEM) are not available. Moreover, the combined use of D(t) and micro-MRI expands the scale of dimensions observable by NMR covering all the interesting length scales of wood.     

Crystallization of carboxylic acids as studied by NMR Spectrometry

The temperature dependences of the narrow ¹H NMR signals, in the temperature range below phase transition point from the plastic to brittle crystal for pivalic acid (PA) confined in the controlled pore size glasses with mean diameters of 7.9 and 23.9 nm have been investigated in order to determine the depression of the crystallization temperature and the pore size distribution parameters. The obtained parameters and the temperature dependences of the narrow ¹H NMR signals in the solid phases of PA and other carboxylic acids (hexadecanoic (C₁₆), heptadecanoic (C₁₇), octadecanoic (C₁₈), nonadecanoic (C₁₉)) have been used for studying the pore size distributions appeared during the natural crystallization. It was found that the pore size distribution for the even-numbered acids (C₁₆ and C₁₈) is spread over much wider range of the sizes comparing with those for odd-numbered acids (C₁₇ and C₁₉). The maximal value of the pore radius R?=?40.4 nm has been found at the temperature just below the melting point of C₁₈, which is about eight times bigger than that found for C₁₇.     

岩心孔隙介质中流体的核磁共振弛豫

弛豫时间是核磁共振研究中的一个重要参数,岩心孔隙介质流体的弛豫过程是自由流体弛豫机制、表面弛豫机制和流体的扩散弛豫机制共同作用的结果,它包含了丰富的孔隙和流体本身的信息. 弛豫时间和自扩散系数的测量及对弛豫时间的分析是核磁共振技术应用于岩心分析和石油勘测的重要内容.     

Pore size distribution calculation from H NMR signal and N2 adsorption–desorption techniques

The pore size distribution (PSD) of nano-material MCM-41 is determined using two different approaches: N₂ adsorption–desorption and ¹H NMR signal of water confined in silica nano-pores of MCM-41. The first approach is based on the recently modified Kelvin equation [J.V. Rocha, D. Barrera, K. Sapag, Top. Catal. 54(2011) 121–134] which deals with the known underestimation in pore size distribution for the mesoporous materials such as MCM-41 by introducing a correction factor to the classical Kelvin equation. The second method employs the Gibbs–Thompson equation, using NMR, for melting point depression of liquid in confined geometries. The result shows that both approaches give similar pore size distribution to some extent, and also the NMR technique can be considered as an alternative direct method to obtain quantitative results especially for mesoporous materials. The pore diameter estimated for the nano-material used in this study was about 35 and 38 Å for the modified Kelvin and NMR methods respectively. A comparison between these methods and the classical Kelvin equation is also presented.     

Characterizing the Evolution of Porosity during Controlled Drug Release

Nuclear magnetic resonance (NMR) techniques have been successfully used to characterize the evolving pore structure of partially soluble pharmaceutical pellets as they absorb water and release soluble components. The restricted diffusivity of water trapped within pellets, which have been immersed in water for differing times, has been measured by pulsed field gradient NMR. These measurements have been used to calculate the surface-to-volume ratio and tortuosity of the pore structure. A one-shot Carr–Purcell–Meiboom–Gill sequence has been used to measure the spin–spin (T ₂) relaxation time of water trapped within the pellets. These data have been regularized and then analyzed by the Brownstein–Tarr model to provide a pore size distribution for the pellets as a function of increasing immersion time. It has been found that pore structure changes significantly as water enters the pellet matrix. Two pellet formulations (herein referred to as placebo and drug-loaded) were studied and showed the same trends of a decreasing surface-to-volume ratio and tortuosity with increasing immersion time. At an immersion time of 10 min, both of these parameters decreased to approximately 70% of their values compared to an immersion time of 2 min. The placebo material tested consistently had both a higher tortuosity and surface-to-volume ratio than the drug-loaded material. At an immersion time of 2 min, the tortuosity for the placebo and drug-loaded materials were about 18 and about 10, respectively, and surface-to-volume ratios of about 6 μm⁻¹ and about 5 μm⁻¹, respectively. The materials tested also show changes in their pore size distribution with immersion time. In both formulations the mean and modal pore sizes increase with immersion time. The placebo material maintains an approximately similar mean and modal pore size, about 2 μm over the timescales studied, suggesting a more symmetric pore size distribution. In the drug-loaded pellets the mean pore size is much higher than the modal pore size, their values being 6.5 and 2.1 μm after 10 min immersion time, respectively. Authors' address: Michael D. Mantle, Department of Chemical Engineering, University of Cambridge, Pembroke Street, Cambridge CB2 3RA, UK     

NMR in well logging and hydrocarbon exploration

Nuclear magnetic resonance (NMR) has become a versatile tool for the evaluation of underground hydrocarbon reservoirs. Formation attributes such as rock porosity and rock pore size distributions, as well as the relative concentrations of water, oil and gas, can be inferred from subsurface NMR. The hydrogen NMR signal encodes porosity as amplitude, pore sizes as relaxation times and fluid properties as a mixture of relaxation and diffusion rates. The paper describes the basic operating principles for NMR on cable (wireline), NMR on a drill string (logging-while-drilling) and NMR for downhole fluid sampling. The geometry of the borehole requires a magnet that projects its field into the surrounding rock, implying a grossly inhomogeneous field distribution. Experience shows that even under these circumstances, saturation-recovery and Carr-Purcell-Meiboom-Gill sequences can work well and yield meaningfulT ₁ andT ₂ information.     

Pore-Structure Determinations of Silica Aerogels byXe NMR Spectroscopy and Imaging

Silica aerogels represent a new class of open-pore materials with pore dimensions on a scale of tens of nanometers, and are thus classified as mesoporous materials. In this work, we show that the combination of NMR spectroscopy and chemical-shift selective magnetic resonance imaging (MRI) can resolve some of the important aspects of the structure of silica aerogels. The use of xenon as a gaseous probe in combination with spatially resolved NMR techniques is demonstrated to be a powerful, new approach for characterizing the average pore structure and steady-state spatial distributions of xenon atoms in different physicochemical environments. Furthermore, dynamic NMR magnetization transfer experiments and pulsed-field gradient (PFG) measurements have been used to characterize exchange processes and diffusive motion of xenon in samples at equilibrium. In particular, this new NMR approach offers unique information and insights into the nanoscopic pore structure and microscopic morphology of aerogels and the dynamical behavior of occluded adsorbates. MRI provides spatially resolved information on the nature of the flaw regions found in these materials. Pseudo-first-order rate constants for magnetization transfer among the bulk and occluded xenon phases indicate xenon-exchange rate constants on the order of 1 s⁻¹for specimens having volumes of 0.03 cm³. PFG diffusion measurements show evidence of anisotropic diffusion for xenon occluded within aerogels, with nominal self-diffusivity coefficients on the order ofD= 10⁻³cm²/s.     

In SituNMR Analysis of Fluids Contained in Sedimentary Rock

Limitations of resolution and absorption in standard chemical spectroscopic techniques have made it difficult to study fluids in sedimentary rocks. In this paper, we show that a chemical characterization of pore fluids may be obtainedin situby magic angle spinning (MAS) nuclear magnetic resonance (NMR), which is normally used for solid samples.¹H MAS–NMR spectra of water and crude oil in Berea sandstone show sufficient chemical shift resolution for a straightforward determination of the oil/water ratio.     

Diffusion-weighted spatial information from1H relaxation in restricted geometries

Summary NMR relaxation of water¹H confined in restricted geometries, whatever is the nature of the system (porous media saturated by water as well as biological tissues), exhibits common characteristics. Artificial microporous media saturated by water have been chosen as model systems to study the longitudinal and transverse relaxation of¹H magnetization of water molecules diffusing in restricted geometries. These systems are very stable, easy to prepare, with well-characterized pore size distribution and connections, and with highly homogeneous surface properties. The response was compared with that from more complex natural porous media. Scanning Electron Microscopy techniques demonstrated spatial characteristics and surface properties of the samples. The information content of longitudinal relaxation curves associated with spatial structure and due to restricted diffusion is shown in these samples. The effect on transverse relaxation of self-diffusion in the presence of spatially varying magnetic fields due to susceptibility differences is shown. A simple linear relationship has been found in all samples between the transverse relaxation rate and the interpulse delay in CPMG experiments, in spite of the variety of pore shapes and sizes. In general, one can say that relaxation curves beardiffusion-weighted information on the pore space framework. The role of the investigated relaxation mechanisms is important also in the response of biological tissues, including in the presence of MR Imaging contrast agents inducing microscopic magnetic-field gradients. Work partially supported by CNR and MURST Grants.     

NMR spectroscopy applied to the Cultural Heritage: a preliminary study on ancient wood characterisation

High and low resolution solid state NMR methods have been applied to characterise a few samples of ancient wood. In an ancient larch wood sample, by applying ¹H low resolution NMR methods as a function of the temperature, the average pore size and its distribution have been determined. In addition, high resolution NMR techniques have allowed addressing of the question of the proximity of water pools to cellulose and lignin. In particular, a model can be hypothesized in which water pools are surrounded by thin layers of amorphous cellulose and/or lignin while the crystalline domains of cellulose surround the layers of amorphous cellulose. Preliminary results obtained using a fully non invasive and portable NMR unilateral relaxometer, the Eureka-Mouse10 (EM10), are reported. This instrumentation is shown to be perfectly suitable for characterizing degradation in ancient wood samples. PACS 76.60 k     

<Superscript>1</Superscript>H NMR studies of cyclohexane confined in mesoporous solids: Melting point depression and pore size distribution

The pore size distributions of four controlled pore glasses and two silica gels with nominal diameters ranging from 6–24 nm were determined by measuring the¹H nuclear magnetic resonance (NMR) signal from the nonfrozen fraction of confined cyclohexane as a function of temperature, in steps of ca. 0.1–1 K. The intensity curves of the liquid component are well represented by a sum of two error functions. The mean melting point depression of cyclohexane confined in pores with radiusR follows the simplified Gibbs-Thompson equation δT=k _p/R with ak _p value of 72.4 Knm. To our knowledge, this is the first time that thek _p value of cyclohexane has been directly and accurately calibrated by NMR. As expected, thek _p value mainly determines the position of the pore size distribution curve, i.e., the mean pore radius. The overall pore size distributions determined by NMR are in reasonable agreement with the results specified by the manufacturer, or measured by us by the N₂ sorption technique. Although the melting point depression of confined cyclohexane is found to be less than previously assumed, this compound is still one of the most suitable candidates for NMR-based pore size determinations. However, pore sizes larger than approximately 50 nm in diameter will be difficult to determine accurately by NMR unless adsorbates undergoing larger melting point depressions than cyclohexane can be found.     

Pore-size determination of mesoporous materials by1H NMR spectroscopy

The pore-size distributions of a series of mesoporous silica materials were determined by measuring the¹H nuclear magnetic resonance (NMR) signal from the nonfrozen fraction of organic probe molecules as a function of temperature. The melting point distribution curves of confined benzene reveal 2–3 transition points. The high-temperature transition point, corresponding to the temperature at the first maximum of the melting point distribution curve, is interpreted as the average depressed melting point of the confined substance. However, the intensity data reveal that a measurable portion of the confined benzene apparently remains nonfrozen even 120 K below the bulk melting point in the 4–10 nm pore systems. The component at lowest temperature is largely attributed to the liquidlike molecules at the pore wall, while the component at the intermediate temperature might result from pockets in the solid matrix or even a bimodal pore-size distribution. The average pore-size distributions obtained by NMR agree fairly well with those obtained by N₂ sorption. However, NMR gives a more detailed picture of the distribution, revealing two or three well-defined peaks. The peak at the smallest pore size, however, reflects the surface layer rather than a pore-size distribution.     

1H and 2H NMR studies of benzene confined in porous solids: melting point depression and pore size distribution

The pore size distributions of four controlled pore glasses and three silica gels with nominal diameters in the range 4-24 nm were determined by measuring the 1H and 2H NMR signals from the non-frozen fraction of confined benzene and perdeuterated benzene as a function of temperature, in steps of ca. 0.1-1 K. The liquid and solid components of the adsorbate were distinguished, on the basis of the spin-spin relaxation time T2, by employing a spin-echo sequence. The experimental intensity curves of the liquid component are well represented by a sum of two error functions. The mean melting point depression of benzene and perdeuterated benzene confined in the four controlled pore glasses, with pore radius R, follows the simplified Gibbs-Thompson equation DeltaT=kp/R with a kp value of 44 K nm. As expected, the kp value mainly determines the position of the pore size distribution curve, i.e., the mean pore radius, while the transition width determines the shape of the pore size distribution curve. The excellent agreement between the results from the 1H and 2H measurements shows that the effect of the background absorption from protons in physisorbed water and silanol groups is negligible under the experimental conditions used. The overall pore size distributions determined by NMR are in reasonable agreement with the results specified by the manufacturer, or measured by us using the N2 sorption technique. The NMR method, which is complementary to the conventional gas sorption method, is particularly appropriate for studying pore sizes in the mesoporous range.     

Comparative analysis of heterogeneous solid and soft materials by adsorption, NMR and thermally stimulated depolarisation current methods

Structural characterisation of such bio-objects as fibrinogen solution, yeast cells, wheat seeds and bone tissues has been done using two versions of cryoporometry based on the integral Gibbs-Thomson (IGT) equation for freezing point depression of pore liquids and the measurements by ¹H NMR spectroscopy (180-200 < T < 273 K) and the thermally stimulated depolarisation current (TSDC) method (90 < T < 273 K) of structured water. The IGT equation was solved using a self-consisting regularization procedure including the maximum entropy principle applied to the distribution function of pore size (PSD). Both methods give clear pictures of changes in the structural characteristics caused, e.g., by hydration and swelling of wheat seeds and yeast cells, coagulation and interaction of fibrinogen with solid nanoparticles in the aqueous media, and the human bone tissue disease.     

Pore size distribution in porous glass: fractal dimension obtained by calorimetry

By differential Scanning Calorimetry (DSC), at low heating rate and using a technique of fractionation, we have measured the equilibrium DSC signal (heat flow) J _q ⁰ of two families of porous glass saturated with water. The shape of the DSC peak obtained by these techniques is dependent on the sizes distribution of the pores. For porous glass with large pore size distribution, obtained by sol-gel technology, we show that in the domain of ice melting, the heat flow J_q is related to the melting temperature depression of the solvent, ΔT _m , by the scaling law: J _q ⁰∼ΔT _m ^{- (1 + D)}. We suggest that the exponent D is of the order of the fractal dimension of the backbone of the pore network and we discuss the influence of the variation of the melting enthalpy with the temperature on the value of this exponent. Similar D values were obtained from small angle neutron scattering and electronic energy transfer measurements on similar porous glass. The proposed scaling law is explained if one assumes that the pore size distribution is self similar. In porous glass obtained from mesomorphic copolymers, the pore size distribution is very sharp and therefore this law is not observed. One concludes that DSC, at low heating rate ( q? 2^°C/min) is the most rapid and less expensive method for determining the pore distribution and the fractal exponent of a porous material. Received 23 July 1999 and Received in final form 16 February 2001     

Effect of drying technique on the physicochemical properties of sodium silicate-based mesoporous precipitated silica

The conventional drying (oven drying) method used for the preparation of precipitated mesoporous silica with low surface area (>300 m²/g) and small pore volume is often associated with a high production cost and a time consuming process. Therefore, the main goal of this study was to develop a cost-effective and fast drying process for the production of precipitated mesoporous silica using inexpensive industrial grade sodium silicate and spray drying of the precipitated wet-gel silica slurry. The precipitated wet-gel silica slurry was prepared from an aqueous sodium silicate solution through the drop-wise addition of sulfuric acid. Mesoporous precipitated silica powder was prepared by drying the wet-gel slurry with different drying techniques. The effects of the oven drying (OD), microwave drying (MD), and spray drying (SD) techniques on the physical (oil, water absorption, and tapping density), and textural properties (specific BET surface area, pore volume, pore size, and % porosity) of the precipitated mesoporous silica powder were studied. The dried precipitated mesoporous silica powders were characterized with field-emission scanning electron microscopy; Brunauer, Emmett and Teller and BJH nitrogen gas adsorption/desorption methods; Fourier-transform infrared spectroscopy; thermogravimetric and differential analysis; N₂ physisorption isotherm; pore size distribution and particle size analysis. There was a significant effect of drying technique on the textural properties, such as specific surface area, pore size distribution and cumulative pore volume of the mesoporous silica powder. Additionally, the effect of the microwave-drying period on the physicochemical properties of the precipitated mesoporous silica powder was investigated and discussed.     

核磁共振T2谱换算孔隙半径分布方法研究

岩芯核磁共振T2谱和压汞分析数据均在一定程度上反映了岩石的孔隙结构特征,理论分析和二者频率分布图对比表明,这两组数据有较好的相关性,核磁共振T₂谱能够换算为反映岩石孔隙结构特征的孔隙半径分布图. 本文应用最大相关性原理、最小二乘法及插值算法等数学方法,给出了一个改进的将T2谱换算为孔隙半径分布图的实用有效新方法,求得了T2弛豫时间与岩芯孔隙半径r之间的换算系数C,计算过程中着重对比了T₂谱与压汞数据的主要分布区间,并考虑了压汞进汞饱和度小于100%对换算结果的影响. 天然砂岩岩芯核磁共振T₂谱换算为孔隙半径分布图的实际应用效果表明,着重对比T₂谱与压汞数据的主要分布区间,同时考虑压汞进汞饱和度小于100%对换算结果的影响是必要的,换算结果更加真实可信.     

To the application of the emission Mössbauer and positron annihilation spectroscopies for detection of carcinogens

Being the main cause of cancer, almost all chemical carcinogens are strong electrophiles, that is, they have a high affinity for the electron. We have shown that positron annihilation lifetime spectroscopy (PALS) is able to detect chemical carcinogens by their inhibition of positronium (Ps) formation in liquid media. Electrophilic carcinogens intercept thermalized track electrons, which are precursors of Ps, and as a result, when they are present Ps atom does not practically form. Available biophysical data seemingly indicate that frozen solutions model better an intracellular medium than the liquid ones. So it is reasonable to use emission Mössbauer spectroscopy (EMS) to detect chemical carcinogens, measuring the yield of ⁵⁷Fe²⁺ions formed in reactions of Auger electrons and other secondary electrons they produced with ⁵⁷Fe³⁺. These reactions are similar to the Ps formation process in the terminal part the positron track: e⁺+ e^? =>Ps. So EMS and PALS are complementary methods for detection of carcinogenic compounds.     

MoO3/Al2O3催化剂中Mo分散的正电子研究

用浸渍法制备了一系列不同Mo含量的MoO₃/Al₂O₃催化剂.测量了这些样品的正电子湮没寿命谱(PALS)与符合多普勒展宽(CDB)谱,以研究其孔洞结构以及Mo分散.正电子寿命测量结果表明,Al₂O₃载体中存在两种不同尺寸的孔洞.掺入MoO₃之后,Mo原子主要进入Al₂O₃的大孔中,使孔洞体积减小.符合多普勒展宽谱结果表明,当MoO 关键词： 3/Al₂O₃催化剂')" href="#">MoO₃/Al₂O₃催化剂 正电子湮没寿命谱 符合多普勒展宽 Mo 分散