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.

Effect of heating time on bonding interface, atom diffusion and mechanical properties of dissimilar titanium joints produced by thermal self-compressing bonding

Solid-state bonding between pure titanium and Ti6Al4V(TC4)alloy was conducted by a new bonding method named as rigid restraint thermal self-compressing bonding.Effects of heating time on bonding interface,atom diffusion and mechanical properties of the joints were studied.Results show that atom diffusion between pure titanium and TC4 alloy significantly takes place during bonding.The diffusion depths of Al and V in pure titanium side are increased with increasing heating time.Due to the enhancement of atom diffusion,bond quality of the bonding interface is improved along with the increase of heating time.The heating time seems to have little effect on microhardness distribution across the joint.However,the tensile strength and ductility of the joint have close relation to heating time.Prolonging heating time can improve the tensile strength and ductility of the joint,especially the latter.When the heating time increases to 450 s,solid-state joint with good combination of strength and ductility is attained.

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.

Effect of plastic deformation on diffusion-rolling bonding of steel sandwich plates

Diffusion bonding is one of the most important techniques for composite materials, while bonding temperature, holding time,and rolling reduction are the key parameters that affect the bonding strength of sandwich plates. To study the effect of plastic deformation on the bonding strength, laboratory experiments were carried on a Gleeble Thermal Simulator to imitate the diffusion-rolling bonding under different reductions for steel sandwich plates. The bonding strength and interlayer film thickness were measured, and the element diffusion was analyzed using line scanning. The relationship between the bonding strength and “diffused interlayer” thickness was investigated. It has been found that the bonding strength increases with reduction, whereas the interlayer film thickness decreases gradually as the reduction increases. The diffusion under plastic deformation is obviously enhanced in comparison with that of nil reduction. The mechanism of plastic deformation effect on the diffusion bonding and related models have been discussed.

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.

Lithium-ion diffusion path of tetragonal tungsten bronze(TTB)phase Nb_(18)W_(16)O_(93)

By taking tetragonal tungsten bronze(TTB)phase Nb_(18)W_(16)O_(93)as an example,an improved solid-state sintering method at lower temperature of 1000℃for 36 h was proposed via applying nanoscale raw materials.XRD,SEM and XPS confirm that the expected sample was produced.GITT results show that the lithium-ion diffusion coefficient of Nb_(18)W_(16)O_(93)(10−12 cm^(2)/s)is higher than that of the conventional titanium-based anode,ensuring a relatively superior electrochemical performance.The lithium-ion diffusion mechanism was thoroughly revealed by using density functional theory simulation.There are three diffusion paths in TTB phase,among which the interlayer diffusion with the smallest diffusion barrier(0.46 eV)has more advantages than other typical anodes(such as graphite,0.56 eV).The relatively smaller lithium-ion diffusion barrier makes TTB phase Nb_(18)W_(16)O_(93)become a potential highspecific-power anode material.

Simplification and Application of Boyd Membrane-diffusion Equation

The having-been-used-for-50-year Boyd membrane diffusion Equation-In(1 - F) = R t can be deduced into F = kt through using Maclanrin expansion equation and the Lagerange remainders. The latter is a simple membrane diffusion equation, which is available to judge if the exchanging course of the resin obeys the rules of membrane-diffusion mechanism more conveniently.

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.

Growth kinetics for intermetallic compound layer between molten In-Sn alloy and CuZr-based bulk metallic glass

The growth kinetics of intermetallic compound layer between molten In-Sn alloy and Cu40Zr44Al8Ag8 bulk metallic glass substrate was examined by solid state isothermal aging at the temperature range between 333 and 393 K.The aged samples were characterized by scanning electron microscopy and energy dispersive spectrometry.It is found that the intermetallic compound layer is composed of Zr,Cu and Sn.The layer growth of the intermetallic compound is mainly controlled by a diffusion mechanism over the temperature range and the value of the time exponent is approximately 0.5.The apparent activation energy for the growth of total intermetallic compound layers is 98.35 kJ /mol calculated by the Arrhenius equation.

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.

Microwave sintering of Mo nanopowder and its densification behavior

In order to prepare high-performance Mo with fine and homogeneous microstructure to meet the demand of high-technology applications such as metallurgical,mechanical,national defense,aerospace and electronics applications,the microwave sintering process and densification mechanism of Mo nanopowder were studied.In this experiment,Mo nanopowder and micropowder were used for conventional sintering and microwave sintering at different sintering temperatures and sintering time,respectively.The results showed that with the increase in the sintering temperature,the increase rates of the relative density and hardness increased rapidly at first and then slowed down.The relative density rapidly reached 95%,followed by a small change.Mo nanopowder with a relative density of 98.03% and average grain size of 3.6 μm was prepared by microwave sintering at 1873 K for30 min.According to the analysis of the sintering kinetics,its densification is attributed to the combination of volumetric diffusion and grain boundary diffusion mechanisms.The calculated sintering activation energy of Mo nanopowder was 203.65 kJ/mol,which was considerably lower than that in the conventional sintering,suggesting that the microwave sintering was beneficial to the enhancement in the atom diffusion and densification for the powder.The results confirm that the microwave sintering is a promising method to economically prepare molybdenum with high properties.

Kinetics and mechanism of adsorptive removal of copper from aqueous solution with poly(vinyl alcohol) hydrogel

Recently, a renewed interest in techniques for heavy metal removal of wastewater has been growing because of embarking opportunities for industrial applications. We investigated the adsorption capacity of the copper on the poly（vinyl alcohol） hydrogel from the aqueous solution. Chemical structure and water absorption of the hydrogel were studied using FTIR and water uptake measurement, respectively. The results showed that the poly（vinyl alcohol） was crosslinked with glutaraldehyde, and the hydrogel highly exhibited the equilibrium swelling ratio because of its hydrophilicity property. Additionally, it was found that the adsorption process followed the pseudo-second-order kinetics and the mechanism diffusion was controlled by particle and film diffusions.

Grain growth and thermal stability of nanocrystalline Ni-TiO_2 composites

The grain growth and thermal stability of nanocrystalline Ni-TiO2composites were systematically investigated.Thenanocrystalline Ni-TiO2composites with different contents of TiO2were prepared via electroplating method with the variation ofTiO2nano-particles concentration.The effect of TiO2content on the grain size,phase structure and microhardness was investigatedin detail.The corresponding grain growth and diffusion mechanisms during the heating process were also discussed.The optimalmicrohardness of HV50270was achieved for the composite with addition of20g/L TiO2nano-particles after annealing at400°C for90min.The calculation of the activation energy indicated that lattice diffusion dominated at high temperatures for thenanocrystalline Ni-TiO2composites.It was indicated that the increase of TiO2nano-particles content took effect on restricting thegrain growth at high temperatures by increasing the grain growth activation energy.

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.

Growth behavior and microstructure of intermetallics at interface of AuSn20 solder and metalized-Ni layer

The AuSn20/Ni joints were prepared by the reflow soldering technology and then annealed at solid-state temperature to form diffusion couples.The interfacial reactions and the growth kinetics of the intermetallic compounds(IMC)at the AuSn20/Ni soldering interface were investigated by scanning electron microscopy(SEM)and electron probe microanalysis(EPMA).The results show that,the(Ni,Au)3Sn2phases are formed at the AuSn20/Ni interface after soldering at583K.The thickness l of the IMC layer monotonically increases with increasing annealing time t according to the relationship l=k(t/t0)n,where the exponent n is0.527,0.476and0.471for393,433and473K annealing,respectively.This indicates that the volume diffusion contributes to the growth of the IMC layer at the AuSn20/Ni interface at solid-sate temperature.The pre-exponential factor K0=1.23×10?7m2/s and the activation enthalpy QK=81.8kJ/mol are obtained from the results of the parabolic coefficient K by a least-squares method.