Fluid distribution and pore wettability of monolithic carbon xerogels measured by 1H NMR relaxation

The pore wettability of two types of carbon xerogels exhibiting micro- and mesopores with different sizes was investigated using ¹H NMR relaxation. These nanomaterials are great candidates as active material for gas diffusion electrodes in mobile energy storage devices. The distribution of fluids in these electrodes is a critical parameter determining the electrode performance. Using ¹H NMR relaxation information about the wettability of micro- as well as mesopores is determined simultaneously. Two important solvents for electrolytes, water and dimethyl sulfoxide (DMSO), were studied for different filling states inside the porous structure. While for water no discrimination between micro- and mesopores could be achieved because of its fast exchange rate between the pores, the measurements with DMSO allow for discriminating between solvent in micro- and mesopores. Thus, the wettability of DMSO in both pore regimes was determined by calculating the surface relaxation strength. It turned out that the wettability of the porous structure is dependent on the differences in the pore sizes between micro- and mesopores. At low filling states both pore regimes compete for the remaining fluid leading to a nonuniform distribution. The pores with the better wettability keep the complete surface in contact with the bulk fluid.     

NMR diffusion and relaxation studies during cement hydration—A non-destructive approach for clarification of the mechanism of internal post curing of cementitious materials

Internal post-curing of hardening cement pastes by addition of alginate spheres, which contain 98% of water, is studied by non-destructive ¹H NMR measurements of transverse relaxation time and self-diffusion. The onset and amount of water transition from the alginate gel used as additive with temporary delayed release of water to cement pastes was observed continuously during the dormant and accelerated period of cement hydration. During hydration, the water transition from the alginate into the cement matrix as well as the development of pore size is monitored quantitatively by studying the time dependence of characteristic peaks in the transverse relaxation time distribution. Comparison between samples without and with internal post curing shows that the addition of alginate gel does not influence the pore size in the micropore region. NMR diffusion studies demonstrate that the physically bound pore water has sufficient mobility to ensure homogeneous distribution of water from the alginate source into the surrounding cement matrix during the dormant and accelerated period.     

Characterization of fluid distributions in porous media by NMR techniques

Nuclear magnetic resonance (NMR) spin-lattice relaxation measurements are used to investigate pore structures and fluid phase distributions in porous media. A new method for estimating relaxation time distribution functions from measured relaxation data is presented using a B-spline basis to represent the distribution function and Tikhonov regularization to stabilize the estimation problem. Surface relaxivity, which is required to convert relaxation time distributions to pore-size distributions of fluid phase distributions at partial saturations, is determined using pore volume-to-surface-area ratios estimated by NMR diffusion measurements. This approach was validated by analyzing certain model porous media with known pore volume-to-surface-area ratios. The method is demonstrated by determining pore-size and fluid phase distributions of sandstone and carbonate samples, as well as by comparing the pore-size distributions of chalk samples obtained by this methodology with those estimated by mercury porosimetry.     

Nuclear magnetic resonance characterization of high- and ultrahigh-performance concrete: Application to the study of water leaching

In the present study, we show that high-resolution ²⁹Si and ²⁷Al magic angle spinning (MAS) nuclear magnetic resonance (NMR) can be a powerful tool for analyzing actual concrete mixes. The influence of the amount of silica fume and of the type of cement in high-performance concrete (HPC), as well as the influence of the type of silica fume and of the granular packing in ultrahigh-performance concrete (UHPC) were investigated. Significant effects on the amount and shape of C-S-H, on the incorporation of aluminum in the C-S-H structure, and on the distribution of aluminum-containing hydrates were observed. Nuclear magnetic relaxation of protons was also performed and it showed the fractal feature of the pore size distribution in UHPC and the higher amount of larger pores in HPC. The microstructure of the surface of these same formulations leached by mineral water for up to 1 year exhibits slight modifications.     

NMR relaxation of molecules confined inside the cement paste pores under partially saturated conditions

Nuclear Magnetic Resonance (NMR) relaxation studies of liquids confined inside cement samples mostly refer to water molecules and saturated pores. Here we extend these studies to the ethanol and cyclohexane molecules partially saturating a white cement paste. The two filling liquids were selected as representatives of polar and nonpolar molecules which should experience different interactions with the surface containing OH groups. The results on these two molecules are compared with those obtained on water filled sample. The transverse relaxation measurements, performed at different saturation degrees, clearly revealed three pore reservoirs in cement paste: intra-C-S-H sheet pores, inter-C-S-H gel pores and capillary pores. A two phase exchange model, describing the effective relaxation rate under partially saturated conditions, is also considered. The model allows finding of a relationship between the relaxation time distribution, the filling degree of the pores and the liquid morphology inside these pores.     

低场核磁法测定凝胶过滤介质的孔径分布

凝胶过滤介质在蛋白质、多糖等生物大分子的分离纯化过程中具有非常重要的作用,其中介质的孔径分布是决定分离纯化效果的关键因素。由于绝大部分凝胶过滤介质是软凝胶,因此很难用常规的方法如压汞法、低温氮吸附法等测定其孔径分布。本文探索了利用低场核磁共振测定凝胶过滤介质的孔径分布的方法。首先通过抽滤、自制琼脂糖凝胶块等实验确定了峰的归属,明确了介质孔内水、介质间隙水和自由水在核磁共振横向弛豫时间(T₂)图谱上的分布范围;随后与逆体积排阻层析法(ISEC)测定的结果相对比,得出层析介质孔径和介质孔内水弛豫时间的关系;最后通过高斯正态拟合得到了介质的孔径分布。实验结果证实了低场核磁共振法测定凝胶过滤介质孔径分布的可行性。该法操作简单、测定迅速,并可以为其他层析介质孔径分布的测定提供参考。     

Facile synthesis of hydrophobic microporous silica membranes and their resistance to humid atmosphere

The ethylene-modified silica membranes were prepared by the acid-catalyzed co-hydrolysis and condensation reaction of tetraethylorthosilicate (TEOS) and ethylenetriethoxysilane (TEVS) in ethanol and the final materials were characterized by scanning electron microscope (SEM), water contact angle measurement, solid-state ²⁹Si magic angle spinning nuclear magnetic resonance (²⁹Si MAS NMR), and N₂ adsorption. The modification leads to a transform from superhydrophilicity for the unmodified silica membranes to hydrophobicity for the modified materials. The ethylene-modified silica membranes are much less water sensitive than the unmodified materials because the hydrophobic ethylene groups replace a portion of the hydrophilic hydroxyl groups on the pore surface. The modified materials process a microporous structure with a narrow pore size distribution centered at 1.1 nm. Such a microporous structure can be stabilized after exposured to humid atmosphere for 450 h, in intense contrast to the collapse of the micropores in the unmodified silica membranes.     

Dielectric Relaxation in High-Silica Borosilicate Glasses

Borosilicate glasses with high silica and varying water content were made by a process similar to that of Vycor. Dielectric relaxation measurements show a de-conduction activation energy equal to that of fused silica, no apparent dependence of the dc conductivity on water content, and an unexpectedly narrow relaxation-time distribution equivalent to a simple RC circuit element. A single relaxation process is observed in all samples regardless of water content and neither the conductivity nor the activation energy are significantly altered by a 50-fold change in water content.     

Application of F NMR relaxometry to the determination of porosity and pore size distribution in hydrated cements and other porous materials

The potential to determine the porosity of cements and other porous materials by employing ¹⁹F NMR relaxometry was explored for samples of hydrated Portland cement, white cement and calcium aluminate, filled with Freon 11. The dependence of ¹⁹F signal amplitudes on the content of Freon in samples with completely filled pores was linear with a small (< 6%) intercept thus allowing a direct determination of total porosity. Additionally it was found that magnetic susceptibility (hence the content of paramagnetic compounds) of the solid can be evaluated from ¹⁹F NMR spectra of samples containing exterior liquid. Information concerning pore size distribution can be obtained from the analysis of multiexponential relaxation of ¹⁹F nuclei in samples with completely filled pores. Mathematical models employing sets of distributions of relaxation rates have been developed for this purpose. Distributions were assumed to be of a (fixed) square/triangular type allowing for the calculation of moments of any order from the estimated initial value, width of distribution and asymmetry factor. Longitudinal and transverse relaxation were characterised by either single or several continuous distributions of relaxation rates. One of the relaxating phases (assigned to fluid occupying throats connecting the pores) was found to selectively disappear when Freon was evaporated from samples. Another approach is to analyse the dependencies of means and variances of relaxation rates on Freon content. This has been done by employing the two-site relaxation model with a permanent adsorption layer and pore-dependent relaxation enhancement. Simultaneous fitting of dependencies of means and variances of relaxation rates on Freon content yields parameters of pore size distribution and of the dependence of relaxation enhancement on the pore radius. Analysis of experimental data shows agreement between these two approaches.     

Effects of Adsorbent Properties on Nuclear Magnetic Resonance Line Widths of Adsorbates

Abstract

An analytical NMR spectrometer has been used to measure line widths of molecules adsorbed on silica so as to investigate the capabilities and limitations of such measurements. Comparisons of line widths with transverse relaxation times (T ₂) for the same samples showed that the observed resonance lines were inhomogeneously broadened. Consequently, line widths are not a reliable way of obtaining T ₂ values or activation energies. The porosity of silica appeared to be an important factor governing adsorbate line widths, the narrowest lines being observed with adsorbents having the largest pore diameters. The narrow resonance lines observed for molecules adsorbed at low coverages on pyrogenic silica have been attributed to the nonporous surface, small particle size, and high purity of that adsorbent. Broadening of lines at high surface coverages on pyrogenic silica appeared to be due to slow exchange of molecules between surface and bulk states having different chemical shifts. Potential applications of high-resolution NMR to the study of gas-solid adsorption are outlined.     

缓凝剂对水泥浆中自由水状态演变的影响

用低场核磁共振技术考察了HN-1型缓凝剂对水泥浆体中可蒸发水的横向弛豫时间(T2)及状态演变过程的影响。结果表明:在初始水化阶段的150 min内,水泥浆GR(添加缓凝剂HN-1的水泥净浆)的弛豫峰峰形和峰顶位置均无明显变化,水泥浆G(纯水泥净浆)的弛豫峰峰形变窄且峰顶位置从2.15 ms迁移至0.95 ms,说明缓凝剂HN-1主要通过改变水泥浆体中不同状态水的存留时间来改变其水化进程。随养护时间的延长,硬化水泥石W0.44和WR0.5中可挥发水弛豫峰分布范围分别从0.11~4.75 ms变为0.08~0.58 ms、0.24~4.23 ms变为0.11~2.35 ms,总体趋向于短弛豫时间,表明水泥石中毛细水逐渐向凝胶水和物理结合水转化,水泥石养护龄期延长至25 d时,其内部凝胶结构水含量超过90%。利用XRD考察了缓凝剂对水泥浆水化产物的影响,结果表明:缓凝剂只改变水泥浆水化过程,对最终水化产物晶型及晶型结构不存在任何影响。     

碳化过程中大水灰比水泥浆体孔结构的变化(英文)

使用特殊的增黏剂与聚羧酸减水剂,制备了掺加石灰石粉、高炉矿渣、硅灰等混合材的普通波特兰水泥浆体和和低热硅酸盐水泥浆体(水粉比为1.0)。这些水泥浆体在20℃的水中养护4年后基本完全水化。这些硬化水泥浆体在5%(质量分数)CO2、相对湿度66%和温度20℃条件下进行碳化,对比研究碳化前后水泥浆体孔结构的变化。结果显示:碳化浆体内孔直径大于10nm的孔体积明显减少;碳化浆体的孔径分布向大孔径范围偏移;掺加混合材的硬化水泥浆体结构明显趋于松散;与不掺加任何混合材的水泥浆体相比,掺加混合材的水泥浆体的孔径更大。     

Petrophysical characterization of coals by low-field nuclear magnetic resonance (NMR)

Nuclear magnetic resonance (NMR) has been widely used in petrophysical characterization of sandstones and carbonates, but little attention has been paid in the use of this technique to study petrophysical properties of coals, which is essential for evaluating coalbed methane reservoir. In this study, two sets of NMR experiments were designed to study the pore types, pore structures, porosity and permeability of coals. Results show that NMR transverse relaxation (T₂) distributions strongly relate to the coal pore structure and coal rank. Three T₂ spectrum peaks identified by the relaxation time at 0.5-2.5 ms, 20-50 ms and >100 ms correspond to pores of <0.1 μm, >0.1 μm and cleats, respectively, which is consistent with results from computed tomography scan and mercury intrusion porosimetry. Based on calculated producible and irreducible porosities through a T₂ cutoff time method, we propose a new NMR-based permeability model that better estimates the permeability of coals. In combination with mercury intrusion porosimetry, we also propose a NMR-based pore structure model that efficiently estimates the pore size distribution of coals. The new experiments and modeling prove the applicability of NMR in petrophysical characterization of intact coal samples, which has potential applications for NMR well logging in coalbed methane exploration.     

孔结构测试技术及其在硬化水泥浆体孔结构表征中的应用

分别概述了压汞测孔法、同步加速X射线层析扫描测孔法、核磁共振弛豫时间测孔法和核磁共振冷冻干燥测孔法.压汞测孔法能直接获取硬化水泥浆体孔结构第一手信息,孔隙结构换算时无需大量、复杂的模型和假定.利用此特点,结合新报道的测孔技术有望实现硬化水泥浆体孔结构表征技术的新突破;同步加速X射线层析扫描测孔法和核磁共振弛豫时间测孔法适合于表征介观尺度的孔隙结构,而核磁共振冷冻干燥法适合于表征微观尺度的孔隙结构.无论是核磁共振弛豫时间测孔法还是核磁共振冷冻干燥测孔法,水泥浆体中铁磁性物质的存在可能会对测定精度产生影响,需要进一步研究.     

Solid-state NMR and ESR studies of activated carbons produced from pecan shells

A large number of solid-state NMR and ESR experiments were explored as potential tools to study chemical structure, mobility, and pore volume of activated carbon. We used a model system where pecan shells were activated with phosphoric acid, and carbonized at 450 °C for 4 h with varying amounts of air flow. Through the use of different NMR experiments (e.g., CP-MAS, SPE-MAS, and DD-MAS) several structural parameters were calculated such as mole fraction of bridgehead aromatic carbons, number of carbons per aromatic ring system, and number of phenolic carbons per aromatic ring system. The relaxation time measurements (T₁, T_CH, and ) were indicative of the relative mobility of different structural units. ESR spectra showed the presence of π-type aromatic free radicals in the carbonized samples with a slight shift in g value with increasing oxidation. The combined NMR and ESR data give a consistent picture of the carbon structure and the carbonization process, which is not easily available otherwise. In addition, the ¹H NMR data on adsorbed water are shown to be consistent with the trends in the amount of pore volumes for different samples of activated carbons.     

1H NMR Imaging Study of Molecular Mobility in Silica-Filled, TBBS-Sulfur Vulcanized Cis-Polyisoprene

The interactions of silica in zinc-activated, sulfur-vulcanized cis-1.4 polyisoprene were characterized at the 75% cure state using ¹H NMR imaging spectroscopy. Variables examined included silica loading, mixing conditions, and presence of additives, including a coupling agent and polyethylene glycol. Rheometer curves indicated a decrease in cure rate and cure state as silica was increased. ¹H NMR imaging showed an increase in the T₂ relaxation times, and a decrease in the proton spin density N(H) as the filler load increases. Mixing conditions did not affect the cure rate, cure state, or the average T₂ relaxation time; however, the distribution of relaxation times broadened with poor mixing. The presence of a coupling agent increased the cure rate and cure state, as well as decreased the T₂ relaxation times as compared with samples with the same silica level, but without coupling agent. Polyethylene glycol (PEG) had slightly higher average T₂ relaxation times, and a slightly broader distribution as compared with the sample without PEG added.     

Octadecyl grafted MCM-41 silica spheres using trifunctionalsilane precursors – preparation and characterization

MCM-41 silica spheres were prepared via the pseudomorphic route. Subsequent surface modification of the mesoporous silica spheres was achieved by two silylating agents, n-octadecyltrihydridosilane and n-octadecyltrimethoxysilane, which provided different surface coverages. The MCM-41 pore structure, surface properties and morphological features were examined by small angle X-ray scattering, nitrogen adsorption–desorption and scanning electron microscopy. The investigations revealed an influence of the silica source on the mesoporous structure, as reflected by a higher long-range order for the pores in MCM-41 spheres prepared from Kromasil silica. Surface modification is accompanied by a reduction of the surface area, pore diameter and pore volume of the MCM-41 materials, whereas the spherical morphology of the spheres is retained. The degree of grafting and cross-linking of the alkylsilanes was determined by ²⁹Si NMR spectroscopy. A higher degree of alkyl chain grafting was observed for the solvent extracted MCM-41 spheres and for samples prepared via surface polymerization.FTIR and ¹³C NMR spectroscopies were employed to study the conformational behaviour and mobility of the grafted octadecyl chains. The conformational order was found to strongly depend on the history of the MCM-41 supports (calcination, solvent extraction) and on the actual surface modification procedure. In general, a lower conformational order was observed for the present mesoporous alkyl modified silica spheres as compared to conventional C₁₈ modified silica gels which is mainly attributed to the lower surface coverage.     

纳米孔超级绝热材料气凝胶的制备与热学特性

以正硅酸四乙酯(TEOS)为硅源，通过溶胶–凝胶及超临界干燥过程制备了SiO2气凝胶. 同时，采用相对廉价的多聚硅(E–40)为硅源，以三甲基氯硅烷(TMCS)为表面修饰剂，硅油为干燥介质, 在常压条件下制备了同样具有纳米多孔结构的SiO2气凝胶. 用透射电镜、扫描电镜及孔径分布仪对其结构进行了表征，并用动态热线法对其热学特性进行了测试. 结果表明: 两种方法制备的气凝胶均是典型的纳米孔超级绝热材料，后者热导率略高但成本低许多，所以更具应用推广潜力.     

Quantitative Si MAS NMR spectroscopy of cement and silica fume containing paramagnetic impurities

The low natural abundance and the long spin lattice relaxation time of ²⁹Si lead to long measurement times and/or low signal-to-noise ratios using ²⁹Si magic angle spinning NMR spectroscopy. By contrast, samples containing paramagnetic iron ions have much shorter relaxation times, making measurements up to seven times more efficient, but at the same time making quantitative analysis unreliable. To solve the problem, the spin-lattice relaxation times of ordinary Portland cement (opc) and silica fume with and without iron content has been determined with inversion recovery experiments. The effect of varying the spectrum repetition time on the quantitative analysis is demonstrated for mixtures of opc with silica fume. For opc and silica fume with iron impurities repetition times as short as 5 s has permitted accurate quantitative analysis of the silicates present in these materials.     

The study of water behaviour in regenerated cellulosic fibres by low-resolution proton NMR

Regenerated cellulosic fibres and comparative materials were studied in the hydrated state by low-resolution proton NMR. Experiments at variable pH and temperatures have shown that the shortened T₂ relaxation times of water within fully swollen cellulosic fibres are dominated by proton exchange with accessible cellulose hydroxyl groups. Proton exchange is accelerated by both acid and base catalysis, with relaxation data used to estimate rate constants for acid, base and neutral mechanisms. Complementary deuterium exchange measurements suggest that accessible cellulose regions below the immediate water interface may not contribute effectively to the proton exchange relaxation mechanism, with two-site relaxation models sensitive only to the direct pore surface area. Differences between surface-relaxing water and deuterium-exchanging water can therefore be used to determine an apparent depth of the accessible cellulose, which is greater for viscose and modal compared to lyocell. However, from relaxation data lyocell has a higher pore surface area. This work also confirmed that water interacting with accessible cellulose experiences motional restriction, allowing an intra-molecular dipolar contribution to relaxation. However, in the fully swollen state water molecules are diffusing rapidly between all internal fibre environments and there is no evidence of specific binding.