Magnetic resonance imaging of single- and two-phase flow in fixed-bed reactors

Magnetic resonance imaging and flow visualization techniques are increasingly used to study transport processes in chemical and biochemical reactors. Three recent case studies from our own research program are reported, each illustrating quite different applications of magnetic resonance techniques in such applications. First, two-phase flow in a trickle-bed reactor is considered. Images of the steady-state gas-liquid distribution are obtained which yield quantitative measures of liquid holdup and wetting efficiency. Second, a radiofrequency pulse sequence based on that for rapid acquisition with relaxation enhancement is used to perform ultrafast visualization of gas-liquid flow in individual channels within a ceramic monolith. Finally,¹H volume-selective nuclear magnetic resonance spectroscopy is employed to perform an in situ spatially resolved study of the extent of conversion of the liquid-phase esterification reaction of methanol and acetic acid, catalyzed by an acid catalyst (Amberlyst 15 ion exchange resin) in a fixed-bed reactor. In particular, the effect of the superficial flow rate of the feed on conversion is investigated.     

Magnetic resonance visualisation of single- and two-phase flow in porous media.

Three-dimensional MRI and flow visualisation data are presented for single and two-phase flow occurring within packed beds of glass spheres. The initial motivation for this work has been to understand the operation of fixed-bed reactors used in many chemical processing operations; these systems also serve as model porous media in which to investigate the effect of the structure of a pore space on the flow phenomena occurring within it. For the case of single-phase flow, maps of the liquid shear rate components are calculated from which forces on individual spheres within the bed are obtained. The velocity histogram for flow transverse to the direction of superficial flow is exponential in both negative and positive directions. This form of the velocity histogram implies an exponential form for the displacement propagator, in contrast to the Gaussian distribution obtained by pulsed gradient spin echo measurements. This difference arises because the spatially resolved velocity imaging sequence measures only the average velocity within each voxel and is insensitive to the effects of incoherent (diffusive) motion. Visualisations of air-water flow through a sphere pack are also reported and the capability of MRI to yield information on rivulet formation and surface wetting characteristics is illustrated.     

气粒两相流传热问题的光滑离散颗粒流体动力学方法数值模拟

在气粒两相流动问题中,颗粒间以及气体与颗粒间的传热问题不可忽略.光滑离散颗粒流体动力学(SDPH)模型作为一种新的求解气粒两相流动问题的方法,已经成功应用于模拟风沙运动等问题.在此基础上,提出了SDPH方法的热传导模型,模拟了气粒两相流动问题中的热传导过程以及颗粒蒸发过程.首先引入各相的能量方程,利用有限差分与光滑粒子流体动力学一阶导数相结合的方法,处理各相内部热传导项中的二阶导数问题,基于气粒两相间温度差及对流换热系数计算颗粒与气体间的热传导量,推导得到了含热传导模型的气粒两相流SDPH计算方程组,模拟计算了圆盘形颗粒团算例及鼓泡流化床内部热传导算例,并与双流体模型计算结果进行对比,结果基本符合;其次利用离散液滴模型中的颗粒蒸发传质传热定律计算颗粒的蒸发过程,数值模拟了颗粒射流蒸发过程,并与离散颗粒模型结果进行对比,两者符合得较好,验证了该方法的准确性及实用性.     

In situ magnetic hysteresis measurement of magnetic tips in magnetic force microscope

In situ magnetic hysteresis measurements of magnetic tips in a magnetic force microscope (MFM) are demonstrated using alternating gradient force magnetometry. The measured magnetic moments of MFM tips are estimated in the range from 10⁻⁶ to 10⁻⁵ emu by this technique and the whole MFM tips in cantilevers are considered to be measured from the value of measured magnetic moments. The relationship between the magnetic hysteresis loops of MFM tips and those of coated magnetic films is discussed.     

Noise estimation in single- and multiple-coil magnetic resonance data based on statistical models

Noise estimation is a challenging task in magnetic resonance imaging (MRI), with applications in quality assessment, filtering or diffusion tensor estimation. Main noise estimators based on the Rician model are revisited and classified in this article, and new useful methods are proposed. Additionally, all the surveyed estimators are extended to the noncentral chi model, which applies to multiple-coil MRI and some important parallel imaging algorithms for accelerated acquisitions. The proposed new noise estimation procedures, based on the distribution of local moments, show better performance in terms of smaller variance and unbiased estimation over a wide range of experiments, with the additional advantage of not needing to explicitly segment the background of the image.     

In situ observations by magnetic resonance imaging for formation and dissociation of tetrahydrofuran hydrate in porous media

Tetrahydrofuran (THF) hydrate has long been used as a substitute for methane hydrate in laboratory studies. This article investigated the formation and dissociation characteristics of THF hydrate in porous media simulated by various-sized quartz glass beads. The formation and dissociation processes of THF hydrate are observed using magnetic resonance imaging (MRI) technology. The hydrate saturation during the formation is obtained based on the MRI data. The experimental result suggests that the third surface has an effect on hydrate formation. THF hydrate crystals lean to form on the glass beads and in their adjacent area as well as from the wall of the sample container firstly. Furthermore, as the pore size diminishes, or as the formation temperature decreases, the nucleation gets easier and the formation processes faster. However, the dissociation rate is mostly dependent on the dissociation temperature rather than on the pore size.     

Hydrodynamics and heat and mass transfer at chemical conversions in slot reactors

In this paper, experimental and numerical investigations of the hydrodynamics and heat transfer in a disk slot heat exchanger-reactor for a radial flow of a gas mixture reacting on the channel walls are described. Data for the coefficients of heat transfer from the wall being heated to the gas flowing inside the reactor are presented. The temperature field of a catalytically active reactor plate at heat release on it has been investigated experimentally. Calculations of the flow and heat transfer in a slot reactor element for a catalytic reaction with heat release have been performed. Partial oxidation of methane in an oxygen medium with the formation of a hydrogen-containing synthesis gas in a two-dimensional microchannel has been investigated numerically. Data for the extent of the chemical conversion of methane versus the initial mixture consumption and reaction temperature are presented.     

In vivo magnetic resonance diffusion measurement in the brain of patients with multiple sclerosis.

Measurement of water self-diffusion in the brain in 25 patients with multiple sclerosis was performed by magnetic resonance imaging. Quantitative diffusion measurements were obtained using single spin-echo pulse sequences with pulsed magnetic field gradients of different magnitude. Twenty-two of these patients also underwent measurement of the transverse relaxation time (T2). Only one plaque was evaluated in each patient. Based on prior knowledge, 12 plaques were classified as being 3 mo or less in age, and 7 plaques were classified as being more than 3 mo old. In all 25 plaques, water self-diffusion was found to be higher than in apparently normal white matter. Furthermore, water self-diffusion was found to be higher in acute plaques compared with chronic plaques. Finally, a slight tendency toward a relationship between the diffusion capability and T2 was found. We believe that an increased diffusion capability signifies an increase of the extracellular water space, which probably is related to the degree of demyelination. Thus, measurement of water self-diffusion in multiple sclerosis plaques may contribute to the study of pathogenesis of demyelination.     

In situ spectroscopic measurement of structural change in SiO2 during femtosecond laser irradiation

Spectra of light transmitted through SiO₂ specimens were measured during irradiation of amplified 800 nm ultrashort (400 fs) laser with a repetition rate of 100 kHz. The spectra exhibit a broad dispersion including a peak at around 450 nm, and the peak wavelength and the intensity are found to significantly depend on the irradiation time. Positively charged oxygen vacancies (E center) and oxygen-deficiency centers (ODCs) with neutral charge were observed by electron spin resonance (ESR) and photoluminescence (PL), respectively, after irradiation. The formation of the E center and the subsequent transformation to ODCs significantly depend on the laser power density. The correlation between the intensity of the peak at around 450 nm and the ESR signal intensity of the E center, and also the observation of PL spectrum due to ODCs suggest that self-trapped excitons exhibiting the peak at around 450 nm are created through multi-photon absorption, followed by the formation of the E center, and this finally leads to the formation of ODCs. PACS 78.47.+p; 61.80.Ba; 76.30.Mi     

Deconvolution with simple extrapolation for improved cerebral blood flow measurement in dynamic susceptibility contrast magnetic resonance imaging during acute ischemic stroke

Magnetic resonance (MR) perfusion imaging is a clinical technique for measuring brain blood flow parameters during stroke and other ischemic events. Ischemia in brain tissue can be difficult to accurately measure or visualize when using MR-derived cerebral blood flow (CBF) maps. The deconvolution techniques used to estimate flow can introduce a mean transit time-dependent bias following application of noise stabilization techniques. The underestimation of the CBF values, greatest in normal tissues, causes a decrease in the image contrast observed in CBF maps between normally perfused and ischemic tissues; resulting in ischemic areas becoming less conspicuous. Through application of the proposed simple extrapolation technique, CBF biases are reduced when missing high-frequency signal components in the MR data removed during deconvolution noise stabilization are restored. The extrapolation approach was compared with other methods and showed a statistically significant increase in image contrast in CBF maps between normal and ischemic tissues for white matter (P<.05) and performed better than most other methods for gray matter. Receiver operator characteristic curve analysis demonstrated that extrapolated CBF maps better-detected penumbral regions. Extrapolated CBF maps provided more accurate CBF estimates in simulations, suggesting that the approach may provide a better prediction of outcome in the absence of treatment.     

Hole mass measurement in p-type InP and GaP by submillimetre cyclotron resonance in pulsed magnetic fields

The first observation of cyclotron resonance in p-type InP is reported. The holes were thermally excited at 110 K and the resonance was observed at 337μm wavelength (HCN laser) using a pulsed magnetic field of 0–350 kG. The effective masses of the light and heavy holes in the 〈111〉 direction were found to be $\text{m}{}^1{}_{\mathrm{<mtext>L</mtext>}}\text{= 0.12 ± 0.01 m}{}_0$, and in the 〈100〉 direction $\text{m}{}^1{}_{\mathrm{<mtext>L</mtext>}}\text{= 0.12 ± 0.01 m}{}_0$, $\text{m}{}^1{}_{\mathrm{<mtext>H</mtext>}}\text{= 0.56 ± 0.02 m}{}_0$. We obtain an estimate of the Dresselhaus parameters A = ?5.04, |B| = 3.12, C² = 6.57. We also report the effective masses for p-type GaP in the 〈111〉 direction as $\text{m}{}^1{}_{\mathrm{<mtext>L</mtext>}}\text{= 0.18 ± 0.02 m}{}_0$, $\text{m}{}^1{}_{\mathrm{<mtext>H</mtext>}}\text{= 0.56 ± 0.04 m}{}_0$.     

Magnetic resonance velocity imaging of liquid and gas two-phase flow in packed beds

Single-phase liquid flow in porous media such as bead packs and model fixed bed reactors has been well studied by MRI. To some extent this early work represents the necessary preliminary research to address the more challenging problem of two-phase flow of gas and liquid within these systems. In this paper, we present images of both the gas and liquid velocities during stable liquid–gas flow of water and SF₆ within a packing of 5 mm spheres contained within columns of diameter 40 and 27 mm; images being acquired using ¹H and ¹⁹F observation for the water and SF₆, respectively. Liquid and gas flow rates calculated from the velocity images are in agreement with macroscopic flow rate measurements to within 7% and 5%, respectively. In addition to the information obtained directly from these images, the ability to measure liquid and gas flow fields within the same sample environment will enable us to explore the validity of assumptions used in numerical modelling of two-phase flows.     

核磁共振实验测量方法的分析

对测量氢核、氟核的g因子等实验过程进行原理分析,给出了10 ms等间隔测量法和利萨如图形测量法的合理解释.     

In situ measurement of self-heating in intrinsic tunneling spectroscopy

Using advanced sample engineering we performed simultaneous measurements of interlayer tunneling characteristics and in situ monitoring of temperature in Bi(2)Sr(2)CaCu(2)O(8 + delta) (Bi-2212) mesas. Together with a systematic study of size dependence of interlayer tunneling, this allowed unambiguous discrimination between artifacts of self-heating and gaps in the electronic spectra of Bi-2212. Such a confident spectroscopic information, which is not affected by self-heating or surface deterioration, was obtained for the first time for a high-T(c) superconductor. We also derived general expressions and formulated main principles of self-heating valid for a large variety of materials.     

纳米结构中磁斯格明子的原位电子全息研究

斯格明子(skyrmion)磁序结构与晶体微观结构的关联是新型功能磁材料和器件研发的重要问题.本文利用微纳加工技术制备了形状、尺寸均可控的磁纳米结构,通过电子全息术观察定量地分析了斯格明子磁序结构,确定了材料晶格缺陷和空间受限效应对斯格明子磁结构形成和稳定机制的影响,系统地分析了斯格明子基元的磁功能与材料微结构的关联.文中主要探讨了两个问题:1)斯格明子在磁纳米结构中的空间受限效应.重点研究斯格明子磁序随外磁场和温度变化的演变规律,探索其演变过程的拓扑属性和稳定性;2)晶格缺陷对斯格明子磁结构的影响,重点考察晶界原子结构手性反转对斯格明子磁序的影响.这些研究结果可为研发以磁斯格明子为基元的磁信息存储器及自旋电子学器件提供重要实验基础.     

In situ measurement of pressure and strain effects in corundum ceramics

Abstract

An Equipement has been built for the generation of uniaxial pressure and of bending stress respectivety directly in the cavity of an X-band ESR spectrometer. Changes of the structure of paramagnetic centres (Fe³⁺ on Al³⁺ sites) could be detected in materials with a high content of corundum under the innuence of pressure and bending stress. The objects of investigation are not only suitable model system but also have practical relevance. The Fe³⁺-ions, incorporated in the materials react very sensitive on mechanically or thermally induced changes of the state of the matrix. They give insight into the materials at a microscopic level The interpretation of the observed intensity and shift effects is possible on the basis of an adequate spin-hamiltonian.     

EHD强化微槽道两相流传热动力学研究

以去离子水为工质,对当量直径分别为1.33mm和2mm的竖直矩形微槽道进行了EHD两相流饱和沸腾传热实验研究,运用分维数、关联维数和Kolmogorov熵对槽道进出口压差波动信号进行了动力学研究,分析了槽道尺寸和外加高压电场对传热系数和非线性特征量的影响规律,结果表明:有无电场情况下,各系统均具有非线性混沌特性,并且有外加高压电场系统的混沌程度比无外加高压电场系统的混沌程度更强烈,槽道尺寸越小,系统的混沌程度越强烈,混沌程度越强烈的系统对应的传热系数越大。     

The effect of magnetic fields on the stability of a cylindrical flow with mass and heat transfer

The effect of axial and radial magnetic fields on the Kelvin-Helmholtz stability of a cylindrical interface between the vapor and liquid phases of a fluid is studied when the vapor is hotter than the liquid and the two phases are enclosed between two cylindrical surfaces coaxial with the interface, and when there is mass and heat transfer across the interface. Both axisymmetric and asymmetric disturbances are considered. The linear dispersion relations are obtained and discussed. It is found that a uniform axial magnetic field has a stabilizing effect on the interface, while the effect of a radial magnetic field depends strongly on the choice of some physical parameters of the system. It is also found that the instability criterion is independent of heat and mass transfer coefficient, but it is different fromthat in the same problem without heat and mass transfer. Finally, the heat and mass transfer has a destabilizing influence on the system.     

Ultrafast velocity imaging of single- and two-phase flows in a ceramic monolith

Ceramic monoliths, comprising arrays of parallel channels, are increasingly being considered as an alternative to conventional packed beds for chemical processing operations involving both single- and two-phase flows. This paper reports results obtained using a technique based on the rapid acquisition with relaxation enhancement (RARE) pulse sequence in which multiple images are obtained from a single r.f. excitation. The technique is applied to study single- and two-phase flow in a monolith rated at 200 channels per square inch (cpsi). A single image frame, acquired in 156 ms, provides a characterization of the heterogeneity in the magnitude and direction of the flow within the monolith.     

Quantitative magnetic resonance flow and diffusion imaging in porous media

Quantitative flow and diffusion measurements have been made for water in model porous media, using magnetic resonance micro-imaging methods. The samples consisted of compacted glass beads of various sizes down to 1 mm diameter. Typical flow and diffusion images exhibited a spatial resolution of 117 μm × 117 μm and velocities in the range 1–2 mm/s. Comparison of volume flow rates calculated from the flow velocity maps with values measured directly yielded good agreement in all cases. There was also good agreement between the mean diffusion coefficient of water calculated from the diffusion maps and the bulk diffusion coefficient for pure water at the same temperature. In addition, the mean diffusion coefficient did not depend on the pore sizes in the bead diameter range of 1–3 mm. Our results also show that partial volume effects can be compensated by appropriate thresholding of the images prior to the final Fourier transformation in the flow-encoding dimension.