Modes of multi-mechanistic gas diffusion in shale matrix at varied effective stresses:Observations and analysis

Gas diffusion in the shale matrix has a dominant effect on late-stage production from shale gas reservoirs.However,adequate research on the mechanisms and contributions of gas diffusion for varied pore size populations in shale matrix under recreated in situ stress is lacking.We report gas-diffusion measurements under constant in situ stress but variable gas pressures for contrasting non-adsorbent(helium(He))and adsorbed(methane(CH_(4)))gases to investigate the impact of effective stress on the evolution of dominant mechanisms of diffusion.An intact sample replicates true pore-network topology and diffusion paths.An integrated diffusion model is proposed that combines the effects of slip flow,Knudsen flow,and surface diffusion to constrain the evolution of these flow regimes and their respective contributions to the observational data.Finally,a probability density function(PDF)is employed to separate the gas content distributions of macropores and micropores from the total gas content and to investigate gas contributions in various pores.The results reveal that the diffusion coefficients of both He and CH_(4) in macropores and micropores increase with gas pressure but decrease with increasing effective stress.The diffusion coefficients of He and CH_(4) are different in macropores but remain nearly the same in micropores.The diffusion coefficients of slip flow and surface diffusion increase with decreasing effective stress except for CH_(4) diffusion in the micropores,while the evolution of Knudsen diffusion shows the opposite trend.Slip flow plays a dominant role in He and CH_(4) diffusion within macropores(pore size 45 nm).Knudsen diffusion gradually becomes significant for He diffusion in the micropores(pore size 4 nm),conversely,for CH_(4) diffusion in the micropores,surface diffusion becomes significant.Related to gas production from reservoirs,the contributions of the micropores will increase gradually with the duration of gas recovery,indicating the significant role of gas diffusion in micropores to steady supply during latestage production.

Diffusion tensor tractography studies on mechanisms of recovery of injured fornix

The fornix,which connects the medial temporal lobe and the medial diencephalon,is involved in episodic memory as an important part of the Papez circuit.The mechanisms of recovery of an injured fornix revealed by diffusion tensor tractography in the five studies are summarized as follows：1） recovery through the nerve tract from an injured fornical crus to the medial temporal lobe via the normal pathway of the fornical crus;2）recovery through the nerve tract originating from an ipsi-lesional fornical body connected to the ipsi-lesional medial temporal lobe via the splenium of the corpus callosum;3） recovery through the nerve tract from the ipsi-lesional fornical body extending to the contra-lesional medial temporal lobe via the splenium of the corpus callosum;4） recovery through the nerve tract originating from the ipsi-lesional fornical column connected to the ipsi-lesional medial temporal lobe;and 5） recovery through the nerve tract originating from the contra-lesional fornical column connected to the ipsi-lesional medial temporal lobe via the contra-lesional medial temporal lobe and the splenium of the corpus callosum.These diffusion tensor tractography studies on mechanisms of recovery of injured fornical crus appeared to provide useful information for clinicians caring for patients with brain injury,however,studies on this topic are still in the beginning stages.

Low-field, high-gradient NMR shows diffusion contrast consistent with localization or motional averaging of water near surfaces

Nuclear magnetic resonance(NMR)measurements of water diffusion have been extensively used to probe microstructure in porous materials,such as biological tissue,however primarily using pulsed gradient spin echo(PGSE)methods.Low-field single-sided NMR systems have built-in static gradients(SG)much stronger than typical PGSE maximum gradient strengths,which allows for the signal attenuation at extremely high b-values to be explored.Here,we perform SG spin echo(SGSE)and SG stimulated echo(SGSTE)diffusion measurements on biological cells,tissues,and gels.Measurements on fixed and live neonatal mouse spinal cord,lobster ventral nerve cord,and starved yeast cells all show multiexponential signal attenuation on a scale of b with significant signal fractions observed at b×Do>1 with b as high as 400 ms/um2.These persistent signal fractions trend with surface-to-volume ratios for these systems,as expected from porous media theory.An exception found for the case of fixed vs.live spinal cords was attributed to faster exchange or permeability in live spinal cords than in fixed spinal cords on the millisecond timescale.Data suggests the existence of multiple exchange processes in neural tissue,which may be relevant to the modeling of time-dependent diffusion in gray matter.The observed multi-exponential attenuation is from protons on water and not macromolecules because it remains proportional to the normalized signal when a specimen is washed with D20.The signal that persists to b×Do>1 is also drastically reduced after delipidation,indicating that it originates from lipid membranes that restrict water diffusion.The multiexponential or stretched exponential character of the signal attenuation at b×Do>1 appears mono-exponential when viewed on a scale of(b×Do)/3,suggesting it may originate from localization or motional averaging of water near membranes on sub-micron length scales.To try to disambiguate these two contributions,signal attenuation curves were compared at varying temperatures.While the curves align when normalizing them using the localization length scale,they separate on a motional averaging length scale.This supports localization as the source of non-Gaussian displacements,but this interpretation is still provisional due to the possible confounds of heterogeneity,exchange,and relaxation.Measurements on two types of gel phantoms designed to mimic extracellular matrix.one with charged functional groups synthesized from polyacrylic acid(PAC)and another with uncharged functional groups synthesized from polyacrylamide(PAM),both exhibit signal at b×Do>1,potentially due to water interacting with macromolecules.These preliminary finding motivate future research into contrast and attenuation mechanisms in tissue with low-field,high-gradient NMR。

Monte Carlo Simulations of Topological Properties in Two-Phase Polycrystalline Materials for Several Diffusion Mechanism

Numerical simulations by means of the Monte Carlo Potts model have been provided to simulate grain structures in two-phase polycrystalline materials. The topological features in the simulated microstructure analyzed for different diffusion mechanisms over a broad range of volume fractions for both phases. The topological properties include the average number of sides, grain topology distribution and the topological size relation function. It is found that the average number of sides depends proportionally on the volume fraction. It increases as the volumes fraction increases and vice versa. Moreover, it is shown that the grain topology distribution in the self-similar growth regime can be described by time unchanged function of the relative grain size. Additionally, topological size function in the simulated microstructure can be evaluated by a quadratic function.

Understanding the Li diffusion mechanism and positive effect of current collector volume expansion in anode free batteries

In anode free batteries(AFBs), the current collector acts as anode simultaneously and has large volume expansion which is generally considered as a negative effect decreasing the structural stability of a battery. Moreover, despite many studies on the fast lithium diffusion in the current collector materials of AFB such as copper and aluminum, the involved Li diffusion mechanism in these materials remains poorly understood. Through first-principles calculation and stress-assisted diffusion equations, here we study the Li diffusion mechanism in several current collectors and related alloys and clarify the effect of volume expansion on Li diffusion respectively. It is suggested that due to the lower Li migration barriers in aluminum and tin, they should be more suitable to be used as AFB anodes, compared to copper, silver, and lead. The Li diffusion facilitation in copper with a certain number of vacancies is proposed to explain why the use of copper with a thickness≤100 nm as the protective coating on the anode improves the lifetime of the batteries. We show that the volume expansion has a positive effect on Li diffusion via mechanical–electrochemical coupling. Namely, the volume expansion caused by Li diffusion will further induce stress which in turn affects the diffusion. These findings not only provide in-depth insight into the operating principle of AFBs, but also open a new route toward design of improved anode through utilizing the positive effect of mechanical–electrochemical coupling.

Numerical simulation of gas transport mechanisms in tight shale gas reservoirs

Due to the nanometer scale pore size and extremely low permeability of a shale matrix,traditional Darcy＇s law can not exactly describe the combined gas transport mechanisms of viscous flow and Knudsen diffusion.Three transport models modified by the Darcy equation with apparent permeability are used to describe the combined gas transport mechanisms in ultra-tight porous media,the result shows that Knudsen diffusion has a great impact on the gas transport and Darcy＇s law cannot be used in a shale matrix with a pore diameter less than 1 μm.A single porosity model and a double porosity model with consideration of the combined gas transport mechanisms are developed to evaluate the influence of gas transport mechanisms and fracture parameters respectively on shale gas production.The numerical results show that the gas production predicted by Darcy＇s law is lower than that predicted with consideration of Knudsen diffusion and the tighter the shale matrix,the greater difference of the gas production estimates.In addition,the numerical simulation results indicate that shale fractures have a great impact on shale gas production.Shale gas cannot be produced economically without fractures.

Diffusion Mechanism of Energy Flow in Multi-heat-source Synthesis of SiC

Through the experiments and the numerical simulation of temperature field in multi-heatsource synthesis Si C furnace, in order to research the feature point in multi-heat-source synthesis furnace, the variation law of heat fl ux was studied and the multi-directional energy fl ow diffusion mechanism was revealed. The results show that, due to the shielding action between the heat-source and the superposition effect of thermal fields, the insulating effect is best in multi-heat-source synthesis furnace. The heat emission effect is good outside the common area between heat-sources, but the heat storage is poor. Compared with the synthesis furnace that heat source is parallelly arranged, the furnace of stereoscopic arrangement has a more obvious heat stacking effect and better heat preservation effect, but the air permeability of heat source connecting regions is worse. In the case with the same ingredients, the resistance to thermal diffusion and mass diffusion is higher in heat source connecting regions.

Interface structure and formation mechanism of diffusion-bonded joints of TiAl-based alloy to titanium alloy

Vacuum diffusion bonding of a TiAl based alloy (TAD) to a titanium alloy (TC2) was carried out at 1 273 K for 15～120 min under a pressure of 25 MPa . The kinds of the reaction products and the interface structures of the joints were investigated by SEM, EPMA and XRD. Based on this, a formation mechanism of the interface structure was elucidated. Experimental and analytical results show that two reaction layers have formed during the diffusion bonding of TAD to TC2. One is Al rich α(Ti)layer adjacent to TC2,and the other is (Ti 3Al+TiAl)layer adjacent to TAD,thus the interface structure of the TAD/TC2 joints is TAD/(Ti 3Al+TiAl)/α(Ti)/TC2.This interface structure forms according to a three stage mechanism,namely(a)the occurrence of a single phase α(Ti)layer;(b)the occurrence of a duplex phase(Ti 3Al+TiAl)layer;and(c)the growth of the α(Ti)and (Ti 3Al+TiAl)layers.

Influence of anisotropy on the electrical conductivity and diffusion coefficient of dry K-feldspar： Implications of the mechanism of conduction

The electrical conductivities of single-crystal K-feldspar along three different crystallographic directions are investigated by the Solartron-1260 Impedance/Gain-phase analyzer at 873 K–1223 K and 1.0 GPa–3.0 GPa in a frequency range of 10-1 Hz–106 Hz. The measured electrical conductivity along the ⊥ [001] axis direction decreases with increasing pressure, and the activation energy and activation volume of charge carriers are determined to be 1.04 ± 0.06 e V and 2.51 ± 0.19 cm~3/mole, respectively. The electrical conductivity of K-feldspar is highly anisotropic, and its value along the⊥ [001] axis is approximately three times higher than that along the ⊥ [100] axis. At 2.0 GPa, the diffusion coefficient of ionic potassium is obtained from the electrical conductivity data using the Nernst–Einstein equation. The measured electrical conductivity and calculated diffusion coefficient of potassium suggest that the main conduction mechanism is of ionic conduction, therefore the dominant charge carrier is transferred between normal lattice potassium positions and adjacent interstitial sites along the thermally activated electric field.

Multi-electron reaction and fast Al ion diffusion of δ-MnO_(2) cathode materials in rechargeable aluminum batteries via first-principle calculations

Rechargeable aluminum batteries with multi-electron reaction have a high theoretical capacity for next generation of energy storage devices. However, the diffusion mechanism and intrinsic property of Al insertion into MnO_(2) are not clear. Hence, based on the first-principles calculations, key influencing factors of slow Al-ions diffusion are narrow pathways, unstable Al-O bonds and Mn^(3+) type polaron have been identified by investigating four types of δ-MnO_(2)(O3, O'3, P2 and T1). Although Al insert into δ-MnO_(2) leads to a decrease in the spacing of the Mn-Mn layer, P2 type MnO_(2) keeps the long(spacious pathways)and stable(2.007–2.030 A) Al-O bonds resulting in the lower energy barrier of Al diffusion of 0.56 e V. By eliminated the influence of Mn^(3+)(low concentration of Al insertion), the energy barrier of Al migration achieves 0.19 e V in P2 type, confirming the obviously effect of Mn^(3+) polaron. On the contrary, although the T1 type MnO_(2) has the sluggish of Al-ions diffusion, the larger interlayer spacing of Mn-Mn layer,causing by H_(2)O could assist Al-ions diffusion. Furthermore, it is worth to notice that the multilayer δ-MnO_(2) achieves multi-electron reaction of 3|e|. Considering the requirement of high energy density, the average voltage of P2(1.76 V) is not an obstacle for application as cathode in RABs. These discover suggest that layered MnO_(2) should keep more P2-type structure in the synthesis of materials and increase the interlayer spacing of Mn-Mn layer for providing technical support of RABs in large-scale energy storage.

CO_2 adsorption performance of different amine-based siliceous MCM-41 materials

A series of amine-based adsorbents were synthesized using siliceous MCM-41 individually impregnated with four different amines（ethylenediamine（EDA）,diethylenetriamine（DETA）,tetraethylenepentamine（TEPA） and pentaethylenehexamine（PEHA）） to study the effect of amine chain length and loading weight on their CO2 adsorption performances in detail.The adsorbents were characterized by FT-IR,elemental analysis,and thermo-gravimetric analysis to confirm their structure properties.Thermo-gravimetric analysis was also used to evaluate the CO2 adsorption performance of adsorbents.Longer chain amine-based materials can achieve higher amine loadings and show better thermal stability.The CO2 adsorption capacities at different temperatures indicate that the CO2 adsorption is thermodynamically controlled over EDAMCM41 and DETA-MCM41,while the adsorption over TEPA-MCM41 and PEHA-MCM41 is under kinetic control at low temperature.The chain length of amines affects the CO2 adsorption performance and the adsorption mechanism significantly.The results also indicate that CO2 adsorption capacity can be enhanced despite of high operation temperatures,if appropriate amines（TEPA and PEHA） are applied.However,adsorbents with short chain amine exhibit higher adsorption and desorption rates due to the collaborative effect of rapid reaction mechanisms of primary amines and less diffusion resistance of shorter chain length amines.

Simulation of the neck growth of non-isometric biosphere during initial sintering

Because powders are mostly non-isometric during the sintering process, copper powders were chosen to study the effects of four material transport mechanisms, including surface diffusion, grain-boundary diffusion, volume diffusion, and multi-couplings. These material transport mechanisms were studied with respect to sintering neck growth of a non-isometric biosphere during initial sintering. The evolution of the neck growth in the four transport mechanisms was simulated by Visual C＋＋ as well based on the model of different particles. The results show that the increase of the sintering temperature, both the grain-boundary diffusion and volume diffusion play primary roles in neck growth, while surface diffusion gradually becomes the secondary mechanism. Both the sintered neck and the shrinkage of the two centers increase with increasing temperature by means of the coupling diffusion mechanism. The radius of the sintering neck decreased, and the shrinkage rate of the two centers increased with an increase of the diameter ratio of the two spheres.

OBSERVATION OF EPITAXIAL OVERLAYER OF METALS AT ATOMIC LEVEL

Observation of epitaxial overlayer of metals at atomic level has been successfully observed in field ion microscope with 5 ns pulsed-laser heating.The condition of superlattice layer growth depends on the surface free energy and the lattice misfit.Many defects,such as vacancies,va- cancy clusters,voids,dislocations and twins are produced during epitaxial growth because of the lattice misfit even though the condition of surface free energy is satisfied.Alloying is ob- served to occur on the surface of the metal during the epitaxial growth.Diffusion is probably via the exchange mechanism.

Carbide Dissolution during Intercritical Austenitization in Bearing Steel

In order to investigate the carbide dissolution mechanism of high carbon-chromium bearing steel during the intercritical austenitization, the database of TCFE7 of Thermo-calc and MOBFE of DICTRA software were used to calculate the elements diffusion kinetic and the evolution law of volume fraction of carbide. DIL805 A dilatometer was used to simulate the intercritical heat treatment. The microstructure was observed by scanning electron microscopy（SEM）, and the micro-hardness was tested. The experimental results indicate that the dissolution of carbide is composed of two stages： initial austenite growth governed by carbon diffusion which sharply moves up the micro-hardness of quenched martensite, and subsequent growth controlled by diffusion of Cr elements in M3 C. The volume fraction of M3 C decreases with the increasing holding time, and the metallographic analysis shows a great agreement with values calculated by software.

INVESTIGATION ON MECHANICALLY ALLOYED SUPERSATURATED NANOCRYSTALLINE Al-Ti ALLOYS

The Al_(100-x)Ti_(x)(x = 5,10,15,35) mixed powders were mechanically alloyed in a planetary bull mill. It was found that the initial composition strongly affects the final productsi a mixture of supersaturated solid solution Al(Ti) and a fee phase for x = 5 and 10; and a single supersaturated solid solution Al(Ti)for x=15 and 35. With inereasing Ti contents from 5at% to 35at%, the grain size of solid solution Al(Ti) decreased from 40nm to 10nm. The results suggest that fast diffusion along nanocrystalline grain boundary is the main alloying process. DSC curves and TEM observation indicate that the solute atom segregation can thermally stabilize the nanocrvstalline solid solutions.

Diffusion mechanism of immiscible Fe-Mg system induced by high-density defects at the steel/Mg composite interface

Due to positive mixing heat between Fe and Mg,it is difficult to diffuse for Fe-Mg at the interface of steel/Mg laminated composites,resulting in the inability to achieve high-strength metallurgical bonding.In this paper,20#steel/Mg laminated composites were prepared by large deformation rolling and subse-quent diffusion heat treatment process.The interfacial bonding strength was improved by constructing high-density crystal defects at the interface to promote element diffusion.The mechanisms of interface morphology evolution and element diffusion were analyzed by finite element simulation and theoretical calculation.The results show after diffusion heat treatment,the bond strength of the large deformation rolled interface was increased from 14 to 30 MPa.Fe-Mg transition layer with about 80 nm thickness as well as high-density vacancies,dislocations and grain boundaries were formed in the large deforma-tion rolled interface region.During diffusion heat treatment,Mg elements diffused into grain interior and grain boundary regions of 20#steel under the effect of heat-force coupling,and the thickness of Fe-Mg transition layer increased to 150 nm,forming an Fe-based supersaturated solid solution.The in-terface with high-density defects constituted a non-equilibrium interface.The 20#steel internal energy in the non-equilibrium interface is able to overcome positive mixing heat of immiscible Fe-Mg system and provide the driving force for Mg elements diffusion.Promoting elemental diffusion by constructing high-density defects can be a new concept to achieve metallurgical bonding at the interface of immiscible metal laminated composites.

Variational Data Assimilation Method Using Parallel Dual Populations Particle Swarm Optimization Algorithm

In recent years,numerical weather forecasting has been increasingly emphasized.Variational data assimilation furnishes precise initial values for numerical forecasting models,constituting an inherently nonlinear optimization challenge.The enormity of the dataset under consideration gives rise to substantial computational burdens,complex modeling,and high hardware requirements.This paper employs the Dual-Population Particle Swarm Optimization(DPSO)algorithm in variational data assimilation to enhance assimilation accuracy.By harnessing parallel computing principles,the paper introduces the Parallel Dual-Population Particle Swarm Optimization(PDPSO)Algorithm to reduce the algorithm processing time.Simulations were carried out using partial differential equations,and comparisons in terms of time and accuracy were made against DPSO,the Dynamic Weight Particle Swarm Algorithm(PSOCIWAC),and the TimeVarying Double Compression Factor Particle Swarm Algorithm(PSOTVCF).Experimental results indicate that the proposed PDPSO outperforms PSOCIWAC and PSOTVCF in convergence accuracy and is comparable to DPSO.Regarding processing time,PDPSO is 40%faster than PSOCIWAC and PSOTVCF and 70%faster than DPSO.

Detailed Evolution Mechanism of Interfacial Void Morphology in Diffusion Bonding

Similar diffusion bonding of 1Cr11Ni2W2MoV stainless steel was conducted at different bonding tem- peratures. The interface characteristics and mechanical properties of joints were examined, and the evolution of interracial void morphology was analyzed in detail The results showed that there were four typical interfacial void shapes generating sequentially： the large scraggly voids, penny-shaped voids, ellipse voids and rounded voids. The variation of interracial void shape was dominated by surface diffusion, while the reduction of void volume was ascribed to the combined effects of plastic flow of materials around voids, interface diffusion and volume diffusion. Owing to the elimination of void from the bonding interface, the sound joint obtained could exhibit nearly full interracial contact, and present excellent mechanical properties, in which the microhardness and shear strength of joint matched those of base material.

Mn Diffusion at Early Stage of Intercritical Annealing of 5Mn Steel

Mn distribution and austenite morphology at the early stage of intercritical annealing of 5Mn steel were investigated. It was experimentally demonstrated that a newly formed 20 nm-thick austenite was formed without the partitioning of Mn. The elemental analysis confirmed that the growth of austenite should be controlled by the diffusion of C prior to the diffusion of Mn at a low heating rate. The austenite growth started under negligible-partitioning local equilibrium mode and then switched to partitioning local equilibrium mode. Mn segregation at the γ/α interface suggested that the collector plate mechanism was the essential way of Mn partitioning at the early stage of austenite growth.