Correlation effects during liquid infiltration into hydrophobic nanoporous media

To explain the thermal effects observed during the infiltration of a nonwetting liquid into a disordered nanoporous medium, we have constructed a model that includes correlation effects in a disordered medium. It is based on analytical methods of the percolation theory. The infiltration of a porous medium is considered as the infiltration of pores in an infinite cluster of interconnected pores. Using the model of randomly situated spheres (RSS), we have been able to take into account the correlation effect of the spatial arrangement and connectivity of pores in the medium. The other correlation effect of the mutual arrangement of filled and empty pores on the shell of an infinite percolation cluster of filled pores determines the infiltration fluctuation probability. This probability has been calculated analytically. Allowance for these correlation effects during infiltration and defiltration makes it possible to suggest a physical mechanism of the contact angle hysteresis and to calculate the dependences of the contact angles on the degree of infiltration, porosity of the medium, and temperature. Based on the suggested model, we have managed to describe the temperature dependences of the infiltration and defiltration pressures and the thermal effects that accompany the absorption of energy by disordered porous medium-nonwetting liquid systems with various porosities in a unified way.     

A study of porous silicon prepared under different HF concentrations by positron annihilation

Two-dimensional angular correlation of positron-electron annihilation radiation and positron-lifetime experiments have been performed on lightly doped porous silicons prepared under different HF concentrations. Positronium formation in the etched pores and positron trapped in voids are observed in both experiments. A surprising result is found that both positron lifetime and momentum spectra show a reduction in the size of the etched pores with decreasing HF concentration in the etching solution. This trend is different from the intuitive expectation that the pore size increases with increasing porosity. Our result can be explained in terms of the formation mechanism of porous film in lightly doped silicon.     

等离子喷涂层原生性孔隙几何结构的分形及统计特性

孔隙是等离子喷涂涂层原生性结构, 对涂层的耐磨损、耐腐蚀、耐高温等性能具有显著影响, 是涂层参数优化的重要指标之一. 因此, 对涂层孔隙结构特征参数的全面表征对于更加精确地评价涂层质量具有重要意义. 本文将概率统计方法、分形方法与数字图像分析技术相结合, 研究了等离子喷涂涂层原生性孔隙数量、形态、尺寸及其分布等结构特征参数表征方法及孔隙的成形机理. 首先通过改变喷涂功率得到不同孔隙状态的Fe基合金涂层, 随后采用数字图像分析技术对涂层截面孔隙的扫描电子显微形貌图进行处理, 最后通过Weibull统计模型分析了孔隙周长及面积的尺寸分布特征, 并利用基于分形思想的面积-周长幂率研究了孔隙不规则形态的定量表征方法. 在实验过程中, 为了分析涂层孔隙的成形机理, 采用Spraywatch在线监测喷涂粒子的飞行状态. 结果表明: 分形维数能够表征孔隙的不规则形态, 分形维数越大, 孔隙面积越大或边界形态越复杂, 并且其与孔隙的成形机理之间存在良好的映射关系; 孔隙面积及周长的尺寸分布均服从明显的两项Weibull分布特征, 孔隙尺寸较小时, 形状参数β 较大, 而孔隙尺寸较大时, 则反之; 喷涂功率对孔隙尺寸的聚集特点产生不同程度的影响, 随着喷涂功率的增加, 粒子的融化状态逐渐改善, 孔隙的尺寸明显降低; 而当孔隙面积(周长)小于特征值时, 相同尺寸的孔隙概率密度值则越来越接近, 说明孔隙功率的变化对小尺寸孔隙出现的概率影响较小.     

Densification study of ITO films during high temperature annealing by GISAXS

Three thermal routes were treated on the sol-gel ITO films, i.e. conventional thermal annealing (CTA), rapid thermal annealing (RTA) and thermal cycle annealing (TCA). The near surface and internal structures of films were characterized by grazing incidence small angle X-ray scattering (GISAXS) technique. It is found that slit-like pores show fractal structures laterally and the near surface is sparser with bigger pores. Ordered pore structure normal to the film appears when films are annealed at high heating rate. The shrinkage of pores is mainly owing to structural relaxation and diffusion during the superheating process. However, the supercooling process has no significant effect on the structures. Furthermore, CTA samples have the greatest porosity and surface roughness due to the prevailing crystallization as well as the coarsening procedure. However small pores inside the films are eliminated at low temperature.     

Atomic mobility in a ternary liquid Ga–In–Sn alloy of the eutectic composition

The nuclear spin–lattice relaxation and Knight shift of ⁷¹Ga, ⁶⁹Ga, and ¹¹⁵In nuclei in a ternary liquid gallium–indium–tin alloy of the eutectic composition, which was introduced into pores of an opal matrix and porous glasses with pore sizes of 18 and 7 nm, have been investigated and compared with those for the bulk melt. It has been found that longitudinal relaxation is accelerated and the Knight shift is decreased, depending on the size of pores. The correlation time of the atomic motion has been calculated for the nanostructured melt in porous matrices. It has been shown that the atomic mobility in the melt decreases with decreasing size of pores in the glasses.

     

Dependence of surface coverage on pore geometry in dispenser cathodes

This paper shows that the surface coverage of Ba/BaO on tungsten is more complete when the activator is supplied via slotted pores rather than circular pores. Both theoretical and experimental evidence is given to support this contention. The effect is primarily a geometrical one, since the surface diffusion in the case of circular pores is two-dimensional, whereas the surface diffusion for slotted pores is linear. The contrast becomes less pronounced as the circular pore size decreases. For dimensions of the order of those found on cathode surfaces (e.g., 10 μ m diameter pores), a hexagonal array of circular pores can be optimized to produce an emitting area of 88% of the total, with a pore open area of about 11%. For slotted pores, the slot widths can be made arbitrarily narrow, consequently, the emitting area approaches 100% while pore evaporation losses are minimized. A slotted-pore cathode should, therefore, be capable of higher and more uniform current density with less barium dispensation. When the pore geometry is controlled, either for round holes or slots, the cathode should be less prone to space-charge-limited slump than those based on random sintered pores     

The displacement correlation tensor: microstructure, ensemble anisotropy and curving fibers

Experiments with multiple diffusion wave vectors are known to carry more information than what is available from standard diffusion experiments. Here we consider a special case of this class of pulse sequences, the double wave vector diffusion experiment, and use the cumulant expansion of the signal to introduce the displacement correlation tensor. We discuss its physical interpretation and properties, noting in particular that its short time behavior allows determination of the surface to volume ratio of the pore space. We present a general expression for the displacement correlation tensor, and provide explicit expressions for a few model geometries. We then show that the scatter matrix characterizing the orientation distribution of an ensemble of cylinders is simply related to the displacement correlation tensor. This result is generalized to ensembles of pores with arbitrary shapes allowing a precise formulation of the influence of microstructural and ensemble anisotropy on the double wave vector diffusion signal in the Gaussian phase approximation. Finally, as a new application of the double wave vector diffusion signal, we analyze its behavior in a curving fiber, and suggest that the displacement correlation tensor may be used to estimate sub-voxel fiber curvature and deflection angle. The theoretical results are corroborated by computer simulations.     

Pore dynamics in lipid membranes

Transient circular pores can open in plasma membrane of cells due to mechanical stress, and failure to repair such pores lead to cell death. Similar pores in the form of defects also exist among smectic membranes, such as in myelin sheaths or mitochondrial membranes. The formation and growth of membrane defects are associated with diseases, for example multiple sclerosis. A deeper understanding of membrane pore dynamics can provide a more refined picture of membrane integrity-related disease development, and possibly also treatment options and strategies. Pore dynamics is also of great importance regarding healthcare applications such as drug delivery, gene or as recently been implied, cancer therapy. The dynamics of pores significantly differ in stacks which are confined in 2D compared to those in cells or vesicles. In this short review, we will summarize the dynamics of different types of pores that can be observed in biological membranes, which include circular transient, fusion and hemi-fusion pores. We will dedicate a section to floral and fractal pores which were discovered a few years ago and have highly peculiar characteristics. Finally, we will discuss the repair mechanisms of large area pores in conjunction with the current cell membrane repair hypotheses.     

Liquid–gas critical phenomena under confinement: small-angle neutron scattering studies of CO2 in aerogel

Small angle neutron scattering (SANS) is a well-established technique for investigating the behavior of confined binary liquid solutions, as it can probe the correlation length and susceptibility in pores on length scales 1 – 100 nm. We applied SANS to explore the influence of confinement on critical behavior of an individual fluid carbon dioxide (CO₂) in a highly porous aerogel. The results demonstrate that quenched disorder induced by aerogel significantly depresses density fluctuations. Despite the negligible volume occupied by aerogel (< 4%), the macroscopic phase separation of confined CO₂ into coexisting liquid and gaseous phases is suppressed and below the critical temperature of the bulk fluid frozen methastable microdomains are formed. Experimental data show that critical adsorption is as important as the effect of confinement in defining the behavior of confined fluids.     

Optical detection of pores in adipocyte membrane

Structures that can be interpreted as cytoplasm droplets leaking through the membrane are experimentally detected on the membranes of adipocytes using optical digital microscopy. The effect of an aqueous alcohol solution of brilliant green on the amount and sizes of structures is studied. It is demonstrated that the optical irradiation of the adipocytes that are sensitized with the aid of the brilliant green leads to an increase in the amount of structures (pores) after the irradiation. The experimental results confirm the existence of an earlier-proposed effect of photochemical action on the sensitized cells of adipose tissue that involves additional formation of pores in the membrane of the sensitized cell under selective optical irradiation. The proposed method for the detection of micropores in the membrane of adipose tissue based on the detection of the cytoplasm droplets leaking from the cell can be considered as a method for the optical detection of nanosized pores.     

Identifiable analysis of dispersed precipitates and porosity in ion-irradiated materials

Analytical formulas for the analysis of structural states in ion-irradiated materials, namely dispersed precipitates, gas-filled pores, and island films on a solid substrate are proposed. A method for revealing similarities and differences between the characteristics of the theoretical and experimental size distributions of particles is developed. This method for the identification of distributions allows a correlation to be determined between the features of the transformations of experimental distributions (histograms) and processes in a dispersed system.     

On the porosity of coldly condensed sers active Ag films: I. Characterization of the films by means of Xe adsorption

In this paper we report on the geometric structure of Ag films, deposited under UHV conditions and annealed at temperatures (T_an) ranging from 58 to 430 K, as deduced from UPS, AES, TDS and work function measurements of adsorbed xenon. The macroscopic work function of the bare films increases continuously from 4.25 eV (T_an = 60 K) to 4.72 eV (T_an = 330 K). Evidence is provided that coldly deposited Ag films are highly porous and that the pores persist up to T_an = 170 K, but are irreversibly healed between 170 and 250 K. The minimum thickness of the evaporated Ag films needed to develop these pores is found to be 50 Å. The width of the pores, which are most likely intercrystalline gaps, is estimated to be 5–15 Å. Besides the“macroscopic” pores the films contain atomic scale defects, which, in contrast to the pores, are healed continu- ously with increasing T_an. Films annealed at 330 K are composed of (111) grains with still a few percent of defect sites. The implications of these structural features on the adsorption properties of pyridine as well as on the interpretation of SERS results from such Ag films are dealt with in part II of this work.     

Freezing Phenomena in Adsorbed Water as Studied by NMR

The freezing of water adsorbed on high-surface-area materials such as silica gel, controlled-pore glass, and activated charcoal is investigated with NMR methods. Part of the pore water freezes at the temperature predicted by the Kelvin equation and the rest of the water does not freeze in the sense that it does not assume the structure of ice on cooling below this freezing point. This bound water exhibits a distribution of correlation times, and information about the width of this distribution is obtained. Values for the activation enthalpy of the bound water are also deduced. An alternative method for the determination of the pore volume of an adsorbent is proposed and it is shown that. for adsorbents with small pores (r < 100 Å), this method results in a much better estimate for the total pore volume than the more common mercury-intrusion method.     

Vortex nanoliquid in high-temperature superconductors

Using a differential magneto-optical technique to visualize the flow of transport currents, we reveal a new delocalization line within the reversible vortex liquid region in the presence of a low density of columnar defects. This line separates a homogeneous vortex liquid, in which all the vortices are delocalized, from a heterogeneous "nanoliquid" phase, in which interconnected nanodroplets of vortex liquid are caged in the pores of a solid skeleton formed by vortices pinned on columnar defects. The nanoliquid phase displays high correlation along the columnar defects but no transverse critical current.     

On the porosity of coldly condensed sers active Ag films: II. Comparison of adsorption and Raman scattering of pyridine

The adsorption of pyridine on coldly deposited Ag films annealed at temperatures ranging from 58 to 330 K, the porous surface topography of which has been investigated in part I of this work, has been studied by means of UPS, work function change and thermal desorption measurements. Pyridine induced work function changes have been employed to follow the surface diffusion of pyridine molecles into the pores of these Ag films. The surface diffusion is very slow below 60 K, but readily takes place at 130 K with an estimated activation energy of surface migration of E_m ≈ 4 kcal/mol. Preadsorption of Xe into the pores of the films causes inhibition of pyridine diffusion into the pores. The onset of pyridine desorption from porous films is detected at ≈ 200 K while from flat films the desorption begins already at 150 K. The careful analysis of our data on the structure of the coldly deposited Ag films and the adsorption behavior of pyridine on these films as well as a survey of published SERS data lead us to conclude that the SERS active sites of coldly deposited Ag films are within the pores. This conclusion is in agreement with recent theoretical calculations.     

Surface effects on liquid crystals constrained in nanoscaled pores investigated by field cycling NMR relaxometry and Monte Carlo simulations

Proton relaxation rates of nematic liquid crystals confined in nanoporous cavities were measured in a broad frequency range with the help of field cycling nuclear magnetic resonance relaxometry. The shape of relaxation dispersion curves in confined materials strongly deviates from the behavior in bulk, both above and below the bulk isotropization temperature. A strong increase in relaxation rates, exceeding by two orders of magnitude that of the bulk sample, is observed in the range of a few kilohertz. Relaxation rates in bigger pores decreased. Experimental findings are interpreted in terms of surface-induced orientational order and diffusion between sites with different orientations of local directors. With the aid of Monte Carlo simulations, two processes affecting low-frequency relaxation could be identified: (a) exchange losses of molecules from the surface-ordered phase to the bulk-like phase, and (b) Reorientations Mediated by Translational Displacements, which dominate the long-time scale and account for the recovery of correlation in molecular orientations as molecules probe different surface sites. It is shown that the width of the oriented layer may strongly affect the slope of dispersion curves and that cross-over between plateau and power law dispersion regimes shifts towards lower frequencies for bigger pores.     

NMR properties of petroleum reservoir fluids

NMR well logging of petroleum reservoir require the measurement of the NMR response of water, oil, and gas in the pore space of rocks at elevated temperatures and pressures. The viscosity of the oil may range from less than 1 cp to greater than 10,000 cp. Also, the oil and gas are not a single component but rather a broad distribution of components. The log mean T1 and T2 relaxation time of dead (gas free) crude oils are correlated with viscosity/temperature and Larmor frequency. The relaxation time of live oils deviate from the correlation for dead crude oils. This deviation can be correlated with the methane content of the oil. Natural gas in the reservoir has components other than methane. Mixing rules are developed to accommodate components such as ethane, propane, carbon dioxide, and nitrogen. Interpretation of NMR logs uses both relaxation and diffusion to distinguish the different fluids present in the formation. Crude oils have a broad spectrum of components but the relaxation time distribution and diffusion coefficient distribution are correlated. This correlation is used to distinguish crude oil from the response of water in the pores of the rock. This correlation can also be used to estimate viscosity of the crude oil.     

高质量规则多孔氧化铝模板的制备

在合适的条件下利用阳极氧化高纯铝片，可以获得多孔结构的氧化铝，其孔径大小和排列方式都很均匀.由于孔的深度不受限制，因此可以制备出孔深很大的多孔氧化铝.这种多孔结构可以用作制备纳米材料的模板.利用0.3mol/L的草酸溶液在40V的直流电压下，采用二步氧化法获得了高质量的氧化铝多孔模板，其典型孔径值为40—70nm，孔间距约110nm，深度可达毫米量级.分析了溶液温度对结果的影响，比较了单步法和两步法获得的样品的多孔结构，认为低温下的二步氧化法可以获得很好的多孔氧化铝模板. 关键词： 纳米材料 多孔氧化铝 二步氧化法