应用MRI研究CO2在癸烷中的扩散

应用核磁共振成像(MRI)技术可视化研究CO₂在癸烷中的扩散,在MRI系统采集图像的同时,应用双室压力衰减法（PVT法）监测压力,通过对MRI图像进行信号强度分析,可得到CO₂的无量纲浓度分布,然后基于菲克定律应用有限体积法可计算得出与扩散距离和扩散时间有关的扩散系数,并可得到任意扩散时间范围内的整体平均扩散系数,MRI方法得出的扩散平衡时间范围内的整体平均扩散系数与PVT法相比较误差为2.7%,并且与相似条件下的前人实验结论具有相同的数量级(10^–9)．根据实验结果得出,扩散系数沿扩散方向下降且随时间以指数形式降低,整体平均扩散系数随扩散时间的增加而减小．     

Evaluation of Restricted Diffusion in Cylinders. Phosphocreatine in Rabbit Leg Muscle

Interpretation of NMR diffusion data is complicated in the presence of diffusion barriers. In this study, restricted diffusion in cylinders is evaluated. A method is presented to determine the diameter of the cylinder and the unrestricted diffusion coefficient from the dependence of the trace of the diffusion tensor with diffusion time. This method is valid even if the orientation of the cylinders is unknown and varies within the sample. An example is given for the diffusion of phosphocreatine in the cylindrically shaped fibers of rabbit skeletal muscle.     

Simulation and experimental verification of the diffusion in an anisotropic fiber phantom

Diffusion weighted magnetic resonance imaging enables the visualization of fibrous tissues such as brain white matter. The validation of this non-invasive technique requires phantoms with a well-known structure and diffusion behavior. This paper presents anisotropic diffusion phantoms consisting of parallel fibers. The diffusion properties of the fiber phantoms are measured using diffusion weighted magnetic resonance imaging and bulk NMR measurements. To enable quantitative evaluation of the measurements, the diffusion in the interstitial space between fibers is modeled using Monte Carlo simulations of random walkers. The time-dependent apparent diffusion coefficient and kurtosis, quantifying the deviation from a Gaussian diffusion profile, are simulated in 3D geometries of parallel fibers with varying packing geometries and packing densities. The simulated diffusion coefficients are compared to the theory of diffusion in porous media, showing a good agreement. Based on the correspondence between simulations and experimental measurements, the fiber phantoms are shown to be useful for the quantitative validation of diffusion imaging on clinical MRI-scanners.     

氢气在多层球壳中扩散过程的模拟计算

从Fick第二定律出发,推导了氢气在多层球壳中,扩散过程的浓度分布表达式,即氢气浓度与扩散时间和扩散距离的关系。每层中,在一定的扩散时间内,一定量的氢气的扩散浓度与扩散深度之间近似为抛物线关系,说明渗透物沿着聚合物链段膨胀的方向进行扩散。在同一位置,一定量氢气的浓度,随着时间的延长而增加,说明渗透物使聚合物链段发生膨胀,自由体积增大,扩散路径增多,扩散系数随着浓度的增加而增大。     

异质原子在Cu（001）表面扩散的分子动力学模拟

采用分子动力学方法模拟单个增原子Ag,Pd和Cu在Cu（001）表面上的扩散过程.通过对自扩散和异质扩散过程中扩散机制的观察,统计三种不同的增原子在不同温度下的扩散频率,拟合给出扩散势垒和扩散频率的指前因子,并与扩散势垒的静力学计算结果进行比较.结果表明：在800 K以下时,三种增原子均以简单跳跃机制为主扩散,与衬底不互溶的Ag增原子的跳跃频率最大,与衬底互溶的Pd增原子的跳跃频率最小.同质增原子与异质增原子的扩散频率和温度的关系均较好地符合Arrhenius公式,由Arrhenius公式拟合给出的三种不同增原子的扩散势垒与表面结构和增原子表面结合能有关.Pd和Cu增原子从跳跃机制为主向交换机制为主的转换温度分别在825和937 K左右. 关键词： 表面扩散 分子动力学模拟     

Diffusion of nickel in single- and polycrystalline Cr2O3

Chromia protective layers are formed on many industrial alloys to prevent corrosion by oxidation. Their role is to limit the inward diffusion of oxygen and the outward diffusion of cations. A number of chromia-forming alloys contain nickel as a component, such as steels, FeNiCr and NiCr alloys. To ascertain if chromia is a barrier to outward diffusion, nickel diffusion in chromia was studied in both single crystals and polycrystals in the temperature range 900–1100°C at an oxygen pressure of 10^?4 atm (argon + 100 ppm O₂). A nickel film of ～35 nm thick was deposited on the chromia surface and, after diffusing treatment, nickel penetration profiles were established by secondary ion mass spectrometry (SIMS). Two diffusion domains appear in polycrystals, the first domain is assigned to bulk diffusion and the second is due to diffusion along grain boundaries. For the bulk diffusion domain and diffusion in single crystals, using a solution of Fick's second law for diffusion from a thick film, bulk diffusion coefficients were determined at 900 and 1000°C. At the higher temperature, a solution of Fick's second law for diffusion from a thin film could be used. For the second domain in polycrystals, Le Claire's model allowed the grain boundary diffusion parameter (αD _gb δ) to be established. Nickel bulk diffusion does not vary significantly according to the microstructure of chromia. The activation energy of grain boundary diffusion is slightly greater than the activation energy of bulk diffusion, probably on account of segregation phenomena. Nickel diffusion was compared with cationic self-diffusion and with literature data on Fe and Mn heterodiffusion in the bulk and along grain boundaries. All results were analyzed in relation to the oxidation process of stainless steel.     

Surface exchange reactions and fast grain boundary diffusion in polycrystalline materials: Application of a spherical grain model

Laplace transforms of the solution functions to the diffusion equations for surface exchange reactions and fast grain boundary diffusion in polycrystalline materials of finite thickness have been derived by applying a spherical grain model. Diffusion profiles have been calculated for semi-infinite diffusion systems as well as thin films by application of numerical Laplace inversion. The surface exchange reaction at the surface of the sample (e.g. oxide ceramics) in contact with the constant diffusion source (e.g. gas phase) is assumed to be fairly slow such that the diffusion source is not in equilibrium with the surface during the diffusion anneal. Two limiting cases for the surface conditions are taken into account, viz. fast surface diffusion and a uniform ratio of the surface exchange coefficient/diffusion coefficient. The calculated profiles refer to Harrison's type-A diffusion kinetics. Apart from expressions for the effective diffusion coefficient, analogous relations for the effective surface exchange coefficient are proposed. Relaxation curves for the total amount of diffusant exchanged with the diffusion source are discussed in terms of the diameter of the spherical grains (average grain size), surface exchange coefficient, bulk and grain boundary diffusion coefficient, respectively.     

氢气在多层球壳中扩散过程的模拟计算

 从Fick第二定律出发,推导了氢气在多层球壳中,扩散过程的浓度分布表达式,即氢气浓度与扩散时间和扩散距离的关系。每层中,在一定的扩散时间内,一定量的氢气的扩散浓度与扩散深度之间近似为抛物线关系,说明渗透物沿着聚合物链段膨胀的方向进行扩散。在同一位置,一定量氢气的浓度,随着时间的延长而增加,说明渗透物使聚合物链段发生膨胀,自由体积增大,扩散路径增多,扩散系数随着浓度的增加而增大。     

Diffusion in dislocation germanium and the model of a liquid dislocation core

Experimental data on the diffusion of ⁷¹Ge, ¹¹³Sn, ¹¹⁴In, and ¹²⁴Sb isotopes in dislocation germanium are discussed within the model of a liquid dislocation core and the filament model of diffusion along dislocations. The temperature dependences of the diffusion permeability along the dislocations are matched to the corresponding temperature dependences of the coefficient of diffusion in the melt in order to determine the absolute values of the coefficient of diffusion along dislocations and the effective diffusion radius of the dislocation core. The experimental results are discussed in terms of thermodynamic parameters of the liquid state and the parameters of diffusion in the melt. The results obtained are consistent with the cooperative diffusion mechanism and the mechanism of diffusion through relaxed vacancies.     

Photothermal deflection measurement of effective gas diffusion coefficient of a porous medium

In this work, an effective gas diffusion coefficient of a porous medium was measured using photothermal deflection (PD) technique. An in-house made Loschmidt diffusion cell with a photothermal-deflection probe were employed to measure the effective gas diffusion coefficient of a gas diffusion layer (GDL) with a porosity ε ≈ 0.7. The concentration evolutions of CO₂ in O₂ with and without the GDL were measured, respectively, using a transverse normal PD technique. The concentration variations were used to deduce the gas diffusion coefficients in the presence and absence of the GDL by solving mass diffusion equations. The effective gas diffusion coefficient of the GDL was calculated from the diffusion coefficients using a model of an equivalent resistance to diffusion and found to be 4.39 × 10^-6 m²s^-1, demonstrating that PD technique can be employed to determine the effective gas diffusion coefficient of a porous medium.     

Behavior of general one-dimensional diffusion processes

We develop simple rigorous techniques to estimate the behavior of general one-dimensional diffusion processes. Any one-dimensional diffusion process (with drift) can be mapped onto a symmetric diffusion through an explicit change of variable. For such processes we can estimate explicitly the diffusion exponent, the recurrence properties, and the large fluctuations. In a second part, we apply these results to different models (including the Sinaï random walk: diffusion in a random drift) and we show how the main features of the diffusion can be readily handled.     

有限时间尺度内分子指向相关的不对称扩散研究

传统的经典扩散理论常常将分子和物体假设为球形,这些分子和物体的扩散是无偏移各向同性的。然而,当我们在纳米尺度去看分子和物体时,这些分子和物体呈现出各种不对称的结构。进一步,当我们观察的时间有限到小于几十纳秒时,我们会看到这些分子和物体的自由扩散表现出与它们的初始方位相关的特性。对于像甲醇分子这样的小分子,在约100 ps的有限时间内,常温下,不对称扩散能占到总扩散的10%左右。这样的不对称扩散丰富了分子的扩散理论,对生命和其他自然界现象的理解具有重要的意义,同时也可能提供一种通过控制分子的方向来驱动分子的方法。     

Application of the Method of Secondary-Ion Mass Spectroscopy to the Study of Heterodiffusion in Alkali-Halide Crystals

The present paper gives the results of investigations of the high-temperature diffusion of Na and Mg ions into single crystals of potassium bromide by the method of secondary-ion mass spectrometry (SIMS). It is demonstrated that the diffusion profiles are nonelementary in character, and the diffusion in the near-surface layer is decelerated. To determine the volume diffusion coefficient, the diffusion profiles must be approximated for depths 1 m. The efficiency of the procedure for determining the diffusion coefficient is confirmed by a comparison of the diffusion coefficients for Na ions determined in the present work with their values obtained by other methods having high reliability and measurement accuracy. The diffusion coefficients of the magnesium impurity are determined for various initial chemical states.     

Simultaneous magnetic resonance imaging of diffusion anisotropy and diffusion gradient

The theory of diffusion gradient-weighted MRI (DGWI) is presented in this paper. The Bloch-Torrey equation was modified to include the effect of intravoxel spatial-location variation of water diffusion (diffusion gradient) on MRI signal, in addition to the effect of intravoxel spatial-direction variation of water diffusion (diffusion anisotropy). An analytical solution for a diffusion-encoding spin-echo pulse sequence was derived. Unlike water diffusion which attenuates the image signal intensity, this newly derived solution relates the spatial gradient of the water diffusion with the phase of the image signal. This novel MRI technique directly measures both the water diffusion and its spatial gradient, and thus offers a noninvasive imaging tool to simultaneously investigate the intravoxel inhomogeneity and anisotropy of tissue structures. In addition, as demonstrated with our preliminary data, this new method may be utilized to delineate the interfaces of tissues with different diffusion. This method is an extension of the successful diffusion tensor MRI (DTI), but requires no additional data acquisition. In addition to the measured diffusion tensor, this new method provides measurements of the spatial derivatives of the three principal diffusivities of the tensor, thereby providing additional information for improving white matter fiber tractography.     

Statistical calculations of tracer and intrinsic diffusion coefficients in concentrated alloys and estimates of microscopic parameters of diffusion from experimental data

The earlier-developed statistical theory of diffusion in concentrated alloys based on the master equation approach is generalized to treat tracer diffusion in binary alloys. The theory developed is used to describe concentration dependencies of both tracer and intrinsic diffusion coefficients and to estimate microscopic parameters of diffusion in alloys CuNi, CuZn and AgCd for which necessary experimental data are available. We show that all main features of strong and peculiar concentration dependencies of diffusion coefficients observed in these alloys are naturally explained by the theory. Signs and scales of interatomic interactions important for diffusion in these alloys are found to strongly depend on the ratio of atomic sizes of alloy components, and types of these dependencies agree with simple physical considerations. We also discuss physical reasons for sharp concentration dependencies of diffusion coefficients characteristic of real alloys.     

Diffusion driven concerted motion of surface atoms: Ge on Ge(001)

The diffusion of Ge dimers on the Ge(001) surface has been studied with scanning tunneling microscopy. We have identified three different diffusion pathways for the dimers: diffusion of on-top dimers over the substrate rows, diffusion across the substrate rows, and diffusion of dimers in the trough. We report on a heretofore unknown phenomenon, namely, diffusion driven concerted motion of substrate atoms. This concerted motion is a direct consequence of the rearrangement of substrate atoms in the proximity of the trough dimer adsorption site.     

Surface diffusion of adsorbates

The review covers studies of the surface diffusion of adsorbed species on single crystal substrates. Experimental techniques employed in investigations of the surface diffusion of adsorbates are discussed. Emphasis is placed on the analysis of data obtained at considerable degrees of coverage. These results demonstrate a close interrelation between surface diffusion and phase transitions in adsorbed layers. Possible mechanisms of surface diffusion are considered taking into account the structure of adsorbed layers. Findings on the effect of electric fields on surface diffusion processes are reviewed.     

On the investigation of the diffusion processes of photoexcited carriers in silicon by ps-reflectivity measurements

The optical excitation of non-equilibrium charge carriers in semiconductors results in a carrier distribution which gives rise to a diffusion process into the bulk of the semiconductor. The diffusion time depends on the absorption coefficient and on the ambipolar diffusion constant. These diffusion times are on a subnanosecond time scale for our experimental conditions. By time-resolved reflectivity measurements we have studied the dependence of the ambipolar diffusion constant on the density of excited carriers. Experimental results were compared with theoretical ones.     

Characterization of electrical charge separation at the interface of two aqueous solutions in the presence of concentration gradients and cation/anion mobility ratio asymmetry

Physical consequences of ionic diffusion processes play a major role on the outcome of electrophysiology experiments due to both their contribution to the ionic transmembrane transport and phenomena taking place at the measuring instruments interface. As most of the time heterogenities in biological media with respect to ionic diffusion constants are disregarded, we intended to look upon the general case of ionic diffusion at the interface of two liquids on which gradients of these diffusion constants no longer can be neglected. We developed a theoretical model for the diffusion potential which emerges at an aqueous interface under gradients of concentration and diffusion constants. The experimental validation of our model was achieved through potential difference measurements of the diffusion potential between two solutions containing sodium chloride (NaCl) and glycerine solutions of various concentrations. Within the studied domain of the electrical charge mobility ratio, we noticed that experimental results are in agreement with the theoretically inferred diffusion potential values. This demonstrates that the resulting relationship for the diffusion potential inferred from our model could be applied for other cases, as well. When the ionic solutions contains an indefinite quantity of glycerine or an unknown substance able to modify diffusion constants of sodium and chloride, it was shown that through measurements of the diffusion potential one can infer the unknown concentration of glycerine and the modified ionic mobility ratio. This, in turn, builds up the foundation for a novel yet simple and efficient analitycal sensing device for quantitative determination in the field.