Stoichiometry and Stability Constant Values for Copper (II) Chelates with Ethylene Diamine in Deep Eutectic Solvents (DES) (Ethaline) Solutions

In this study we used the deep eutectic solvents (ionic liquids) to investigate the reaction between copper (II) with ethylene diamine (en). Two of the existing methods for analyzing spectrophotometric measurements have been applied for establishing, the stoichiometry and whenever possible, the stability constants of the chelates formed. The method of continuous variations was necessary to determine first whether, the metal ion and the ligand ethylene diamine form one or more than one chelate, when more than one chelate formed, the results obtained depend on the wavelength and for meaningful conclusions the wavelengths were carefully selected. The empirical formulae of the chelates were further substantiated by the molar ratio method. The effect of time and temperature on the formation and stability of these chelates in solution is also studied. The stability constants, K1 and K2 for the copper (II) chelates were calculated, though reliable, and are comparable to literature values.

Granular behaviour under bi-directional shear with constant vertical stress and constant volume

This paper aims to investigate the role of bi-directional shear in the mechanical behaviour of granular materials and macro-micro relations by conducting experiments and discrete element method(DEM)modelling.The bi-directional shear consists of a static shear consolidation and subsequent shear under constant vertical stress and constant volume conditions.A side wall node loading method is used to exert bi-directional shear of various angles.The results show that bi-directional shear can significantly influence the mechanical behaviour of granular materials.However,the relationship between bidirectional shear and mechanical responses relies on loading conditions,i.e.constant vertical stress or constant volume conditions.The stress states induced by static shear consolidation are affected by loading angles,which are enlarged by subsequent shear,consistent with the relationship between bidirectional shear and principal stresses.It provides evidence for the dissipation of stresses accompanying static liquefaction of granular materials.The presence of bi-directional principal stress rotation(PSR)is demonstrated,which evidences why the bi-directional shear of loading angles with components in two directions results in faster dissipations of stresses with static liquefaction.Contant volume shearing leads to cross-anisotropic stress and fabric at micro-contacts,but constant vertical stress shearing leads to complete anisotropic stress and fabric at micro-contacts.It explains the differentiating relationship between stress-strain responses and fabric anisotropy under these two conditions.Micromechanical signatures such as the slip state of micro-contacts and coordination number are also examined,providing further insights into understanding granular behaviour under bi-directional shear.

Cyclic shear behavior of en-echelon joints under constant normal stiffness conditions

To reveal the mechanism of shear failure of en-echelon joints under cyclic loading,such as during earthquakes,we conducted a series of cyclic shear tests of en-echelon joints under constant normal stiffness(CNS)conditions.We analyzed the evolution of shear stress,normal stress,stress path,dilatancy characteristics,and friction coefficient and revealed the failure mechanisms of en-echelon joints at different angles.The results show that the cyclic shear behavior of the en-echelon joints is closely related to the joint angle,with the shear strength at a positive angle exceeding that at a negative angle during shear cycles.As the number of cycles increases,the shear strength decreases rapidly,and the difference between the varying angles gradually decreases.Dilation occurs in the early shear cycles(1 and 2),while contraction is the main feature in later cycles(310).The friction coefficient decreases with the number of cycles and exhibits a more significant sensitivity to joint angles than shear cycles.The joint angle determines the asperities on the rupture surfaces and the block size,and thus determines the subsequent shear failure mode(block crushing and asperity degradation).At positive angles,block size is more greater and asperities on the rupture surface are smaller than at nonpositive angles.Therefore,the cyclic shear behavior is controlled by block crushing at positive angles and asperity degradation at negative angles.

Mechanical Modeling and Analysis of Stability Deterioration of Production Well During Marine Hydrate Depressurization Production

Different from oil and gas production,hydrate reservoirs are shallow and unconsolidated,whose mechanical properties deteriorate with hydrate decomposition.Therefore,the formations will undergo significant subsidence during depressurization,which will destroy the original force state of the production well.However,existing research on the stability of oil and gas production wells assumes the formation to be stable,and lacks consideration of the force exerted on the hydrate production well by formation subsidence caused by hydrate decomposition during production.To fill this gap,this paper proposes an analytical method for the dynamic evolution of the stability of hydrate production well considering the effects of hydrate decomposition.Based on the mechanical model of the production well,the basis for stability analysis has been proposed.A multi-field coupling model of the force state of the production well considering the effect of hydrate decomposition and formation subsidence is established,and a solver is developed.The analytical approach is verified by its good agreement with the results from the numerical method.A case study found that the decomposition of hydrate will increase the pulling-down force and reduce the supporting force,which is the main reason for the stability deterioration.The higher the initial hydrate saturation,the larger the reservoir thickness,and the lower the production pressure,the worse the stability or even instability.This work can provide a theoretical reference for the stability maintaining of the production well.

Impact of spatially varying rock disturbance on rock slope stability

Degradation of rock mass produced by rock blasting,stress relief,and other causes is an important factor in the assessment of rock strength.Quantified as a disturbance factor,such degradation varies depending on blasting control,stress state and stress relief,and rock mass quality.This study focuses on the impact of disturbance on the safety of slopes.The disturbance in the rock mass is characterized by the geometry of the disturbed zone,its size,the magnitude,and the decaying rate with the distance away from the slope surface.A method accounting for decay of rock disturbance is presented.A study of the impact of rock disturbance characteristics on the quantitative stability measures of slopes was carried out.These characteristics included disturbed zone geometry,its thickness,the maximum magnitude of the disturbance factor,and the rate of disturbance decaying.The thickness of the disturbed zone and the maximum factor of disturbance were found to have the greatest impact.For example,the factor of safety for a 45slope in low-quality rock mass can decrease from 1.96 to 1.09 as the thickness of the disturbed zone increases from 1/4 of slope height H to the double of H and the maximum disturbance factor increases from 0.5 to 1.Uniform thickness of a disturbed zone was found to yield more conservative outcomes than the triangular zones did.The critical failure surfaces were found to be shallow for high rates of disturbance decay,and they were the deepest for spatially uniform disturbance factors.

Influence of variable viscosity and double diffusion on the convective stability of a nanofluid flow in an inclined porous channel

The influence of variable viscosity and double diffusion on the convective stability of a nanofluid flow in an inclined porous channel is investigated.The DarcyBrinkman model is used to characterize the fluid flow dynamics in porous materials.The analytical solutions are obtained for the unidirectional and completely developed flow.Based on a normal mode analysis,the generalized eigenvalue problem under a perturbed state is solved.The eigenvalue problem is then solved by the spectral method.Finally,the critical Rayleigh number with the corresponding wavenumber is evaluated at the assigned values of the other flow-governing parameters.The results show that increasing the Darcy number,the Lewis number,the Dufour parameter,or the Soret parameter increases the stability of the system,whereas increasing the inclination angle of the channel destabilizes the flow.Besides,the flow is the most unstable when the channel is vertically oriented.

Probabilistic analysis of tunnel face seismic stability in layered rock masses using Polynomial Chaos Kriging metamodel

Face stability is an essential issue in tunnel design and construction.Layered rock masses are typical and ubiquitous;uncertainties in rock properties always exist.In view of this,a comprehensive method,which combines the Upper bound Limit analysis of Tunnel face stability,the Polynomial Chaos Kriging,the Monte-Carlo Simulation and Analysis of Covariance method(ULT-PCK-MA),is proposed to investigate the seismic stability of tunnel faces.A two-dimensional analytical model of ULT is developed to evaluate the virtual support force based on the upper bound limit analysis.An efficient probabilistic analysis method PCK-MA based on the adaptive Polynomial Chaos Kriging metamodel is then implemented to investigate the parameter uncertainty effects.Ten input parameters,including geological strength indices,uniaxial compressive strengths and constants for three rock formations,and the horizontal seismic coefficients,are treated as random variables.The effects of these parameter uncertainties on the failure probability and sensitivity indices are discussed.In addition,the effects of weak layer position,the middle layer thickness and quality,the tunnel diameter,the parameters correlation,and the seismic loadings are investigated,respectively.The results show that the layer distributions significantly influence the tunnel face probabilistic stability,particularly when the weak rock is present in the bottom layer.The efficiency of the proposed ULT-PCK-MA is validated,which is expected to facilitate the engineering design and construction.

Evaluation of slope stability through rock mass classification and kinematic analysis of some major slopes along NH-1A from Ramban to Banihal, North Western Himalayas

The network of Himalayan roadways and highways connects some remote regions of valleys or hill slopes,which is vital for India’s socio-economic growth.Due to natural and artificial factors,frequency of slope instabilities along the networks has been increasing over last few decades.Assessment of stability of natural and artificial slopes due to construction of these connecting road networks is significant in safely executing these roads throughout the year.Several rock mass classification methods are generally used to assess the strength and deformability of rock mass.This study assesses slope stability along the NH-1A of Ramban district of North Western Himalayas.Various structurally and non-structurally controlled rock mass classification systems have been applied to assess the stability conditions of 14 slopes.For evaluating the stability of these slopes,kinematic analysis was performed along with geological strength index(GSI),rock mass rating(RMR),continuous slope mass rating(CoSMR),slope mass rating(SMR),and Q-slope in the present study.The SMR gives three slopes as completely unstable while CoSMR suggests four slopes as completely unstable.The stability of all slopes was also analyzed using a design chart under dynamic and static conditions by slope stability rating(SSR)for the factor of safety(FoS)of 1.2 and 1 respectively.Q-slope with probability of failure(PoF)1%gives two slopes as stable slopes.Stable slope angle has been determined based on the Q-slope safe angle equation and SSR design chart based on the FoS.The value ranges given by different empirical classifications were RMR(37-74),GSI(27.3-58.5),SMR(11-59),and CoSMR(3.39-74.56).Good relationship was found among RMR&SSR and RMR&GSI with correlation coefficient(R 2)value of 0.815 and 0.6866,respectively.Lastly,a comparative stability of all these slopes based on the above classification has been performed to identify the most critical slope along this road.

Reliability analysis of slope stability by neural network,principal component analysis,and transfer learning techniques

The prediction of slope stability is considered as one of the critical concerns in geotechnical engineering.Conventional stochastic analysis with spatially variable slopes is time-consuming and highly computation-demanding.To assess the slope stability problems with a more desirable computational effort,many machine learning(ML)algorithms have been proposed.However,most ML-based techniques require that the training data must be in the same feature space and have the same distribution,and the model may need to be rebuilt when the spatial distribution changes.This paper presents a new ML-based algorithm,which combines the principal component analysis(PCA)-based neural network(NN)and transfer learning(TL)techniques(i.e.PCAeNNeTL)to conduct the stability analysis of slopes with different spatial distributions.The Monte Carlo coupled with finite element simulation is first conducted for data acquisition considering the spatial variability of cohesive strength or friction angle of soils from eight slopes with the same geometry.The PCA method is incorporated into the neural network algorithm(i.e.PCA-NN)to increase the computational efficiency by reducing the input variables.It is found that the PCA-NN algorithm performs well in improving the prediction of slope stability for a given slope in terms of the computational accuracy and computational effort when compared with the other two algorithms(i.e.NN and decision trees,DT).Furthermore,the PCAeNNeTL algorithm shows great potential in assessing the stability of slope even with fewer training data.

Flow-Slip Stability Behavior of Calcareous Sand Treated by Microbially Induced Carbonate Precipitation Technology

Flow-slip damage commonly destabilizes coastal slopes.Finding a slope stabilization method for calcareous sands in the South China Sea is crucial.Microbially induced calcite precipitation is a promising,eco-friendly method for soil stabilization.This study investigates the effect of microbial treatments,initial relative density,initial cell pressure,and initial stress ratio on the flow-slip stability of calcareous sand specimens by using constant shear drained tests.These tests lay the foundation to study the mechanical instability of sand slopes.Results show that the microbial-treated specimens maintain stable stresses longer,take longer to reach the instability,and withstand larger volumetric strains.Microbial treatment effectively enhances sand stability under constant shear drainage,with improvements amplified by higher initial relative density and initial cell pressure.In addition,a smaller initial stress ratio reduces shear effects on the specimen and increases resistance to flow slides.Microanalysis reveals that the flow-slip stability of calcareous sand slopes is enhanced by contact cementation,particle coating,void filling,and mutual embedment of calcium carbonate crystals.

Insights into ionic association boosting water oxidation activity and dynamic stability

There have been reports about Fe ions boosting oxygen evolution reaction(OER)activity of Ni-based catalysts in alkaline conditions,while the origin and reason for the enhancement remains elusive.Herein,we attempt to identify the activity improvement and discover that Ni sites act as a host to attract Fe(Ⅲ)to form Fe(Ni)(Ⅲ)binary centres,which serve as the dynamic sites to promote OER activity and stability by cyclical formation of intermediates(Fe(Ⅲ)→Fe(Ni)(Ⅲ)→Fe(Ni)-OH→Fe(Ni)-O→Fe(Ni)OOH→Fe(Ⅲ))at the electrode/electrolyte interface to emit O_(2).Additionally,some ions(Co(Ⅱ),Ni(Ⅱ),and Cr(Ⅲ))can also be the active sites to catalyze the OER process on a variety of electrodes.The Fe(Ⅲ)-catalyzed overall water-splitting electrolyzer comprising bare Ni foam as the anode and Pt/Ni-Mo as the cathode demonstrates robust stability for 1600 h at 1000 mA cm^(-2)@~1.75 V.The results provide insights into the ioncatalyzed effects boosting OER performance.

Effect and mechanism of reductive polyaniline on the stability of nitrocellulose

The search for new green and efficient stabilizers is of great importance for the stabilization of nitrocellulose(NC). This is due to the shortcomings of traditional stabilizers, such as high toxicity. In this study, reduced polyaniline(r-PANI), which has a similar functional structure to diphenylamine(DPA) but is non-toxic, was prepared from PANI based on the action with N_(2)H_(4) and NH_(3)-H_(2)O, and used for the first time as a potential stabilizer for NC. XPS, FTIR, Raman, and SEM were used to characterize the reduced chemical structure and surface morphology of r-PANI. In addition, the effect of r-PANI on the stabilization of NC was characterized using DSC, VST, isothermal TG, and MMC. Thermal weight loss was reduced by 83% and 68% and gas pressure release by 75% and 49% compared to pure NC and NC&3%DPA, respectively.FTIR and XPS were used to characterize the structural changes of r-PANI before and after reaction with NO_(2). The 1535 cm^(-1) and 1341 cm^(-1) of the FTIR and the 404.98 eV and 406.05 eV of the XPS showed that the -NO_(2) was generated by the absorption of NO_(2). Furthermore, the quantum chemical calculation showed that NO_(2) was directly immobilized on r-PANI by forming -NO_(2) in the neighboring position of the benzene ring.

基于COMPASS iStability的浮船坞稳性计算

为比对分段建模与整体建模工作量及稳性计算结果,选取某浮船坞,采用命令流方法,对坞墙无开口,做5分段建模和整体建模稳性计算,对坞墙有开口,做7分段建模和借助体过渡整体建模稳性计算,结果表明,无论坞墙有无开口,整体建模比分段建模节省约一半工作量,两种建模方式稳性计算精度相同,建模过程表明,命令流方法整体建模计算稳性,高效快捷。

Effects of connected automated vehicle on stability and energy consumption of heterogeneous traffic flow system

With the development of intelligent and interconnected traffic system,a convergence of traffic stream is anticipated in the foreseeable future,where both connected automated vehicle(CAV)and human driven vehicle(HDV)will coexist.In order to examine the effect of CAV on the overall stability and energy consumption of such a heterogeneous traffic system,we first take into account the interrelated perception of distance and speed by CAV to establish a macroscopic dynamic model through utilizing the full velocity difference(FVD)model.Subsequently,adopting the linear stability theory,we propose the linear stability condition for the model through using the small perturbation method,and the validity of the heterogeneous model is verified by comparing with the FVD model.Through nonlinear theoretical analysis,we further derive the KdV-Burgers equation,which captures the propagation characteristics of traffic density waves.Finally,by numerical simulation experiments through utilizing a macroscopic model of heterogeneous traffic flow,the effect of CAV permeability on the stability of density wave in heterogeneous traffic flow and the energy consumption of the traffic system is investigated.Subsequent analysis reveals emergent traffic phenomena.The experimental findings demonstrate that as CAV permeability increases,the ability to dampen the propagation of fluctuations in heterogeneous traffic flow gradually intensifies when giving system perturbation,leading to enhanced stability of the traffic system.Furthermore,higher initial traffic density renders the traffic system more susceptible to congestion,resulting in local clustering effect and stop-and-go traffic phenomenon.Remarkably,the total energy consumption of the heterogeneous traffic system exhibits a gradual decline with CAV permeability increasing.Further evidence has demonstrated the positive influence of CAV on heterogeneous traffic flow.This research contributes to providing theoretical guidance for future CAV applications,aiming to enhance urban road traffic efficiency and alleviate congestion.

Enhanced High-Temperature Cycling Stability of Garnet-Based All Solid-State Lithium Battery Using a Multi-Functional Catholyte Buffer Layer

The pursuit of safer and high-performance lithium-ion batteries(LIBs)has triggered extensive research activities on solid-state batteries,while challenges related to the unstable electrode-electrolyte interface hinder their practical implementation.Polymer has been used extensively to improve the cathode-electrolyte interface in garnet-based all-solid-state LIBs(ASSLBs),while it introduces new concerns about thermal stability.In this study,we propose the incorporation of a multi-functional flame-retardant triphenyl phos-phate additive into poly(ethylene oxide),acting as a thin buffer layer between LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathode and garnet electro-lyte.Through electrochemical stability tests,cycling performance evaluations,interfacial thermal stability analysis and flammability tests,improved thermal stability(capacity retention of 98.5%after 100 cycles at 60℃,and 89.6%after 50 cycles at 80℃)and safety characteristics(safe and stable cycling up to 100℃)are demonstrated.Based on various materials characterizations,the mechanism for the improved thermal stability of the interface is proposed.The results highlight the potential of multi-functional flame-retardant additives to address the challenges associated with the electrode-electrolyte interface in ASSLBs at high temperature.Efficient thermal modification in ASSLBs operating at elevated temperatures is also essential for enabling large-scale energy storage with safety being the primary concern.

Origin of the Disparity between the Stability of Transmutated Mix-Cation and Mix-Anion Compounds

Transmutation is an efficient approach for material design. For example, ternary compound CuGaSe_(2) in chalcopyrite structure is a promising material for novel optoelectronic and thermoelectric device applications. It can be considered as formed from the binary host compound ZnSe in zinc-blende structure by cation transmutation(i.e., replacing two Zn atoms by one Cu and one Ga). While cation-transmutated materials are common, aniontransmutated ternary materials are rare, for example, Zn_(2)As Br(i.e., replacing two Se atoms by one As and one Br)is not reported. The physical origin for this puzzling disparity is unclear. In this work, we employ first-principles calculations to address this issue, and find that the distinct differences in stability between cation-transmutated(mix-cation) and anion-transmutated(mix-anion) compounds originate from their different trends of ionic radii as functions of their ionic state, i.e., for cations, the radius decreases with the increasing ionic state, whereas for anions, the radius increases with the increasing absolute ionic state. Therefore, for mix-cation compounds,the strain energy and Coulomb energy can be simultaneously optimized to make these materials stable. In contrast, for mix-anion systems, minimization of Coulomb energy will increase the strain energy, thus the system becomes unstable or less stable. Thus, the trend of decreasing strain energy and Coulomb energy is consistent in mix-cation compounds, while it is opposite in mix-anion compounds. Furthermore, the study suggests that the stability strategy for mix-anion compounds can be controlled by the ratio of ionic radii r3/r1, with a smaller ratio indicating greater stability. Our work, thus, elucidates the intrinsic stability trend of transmutated materials and provides guidelines for the design of novel ternary materials for various device applications.

Sodium Nitrate/Formamide Deep Eutectic Solvent as Flame-Retardant and Anticorrosive Electrolyte Enabling 2.6 V Safe Supercapacitors with Long Cyclic Stability

Safe operation of electrochemical capacitors(supercapacitors)is hindered by the flammability of commercial organic electrolytes.Non-flammable Water-in-Salt(WIS)electrolytes are promising alternatives;however,they are plagued by the limited operation voltage window(typically≤2.3 V)and inherent corrosion of current collectors.Herein,a novel deep eutectic solvent(DES)-based electrolyte which uses formamide(FMD)as hydrogen-bond donor and sodium nitrate(NaNO_(3))as hydrogen-bond acceptor is demonstrated.The electrolyte exhibits the wide electrochemical stability window(3.14 V),high electrical conductivity(14.01 mScm^(-1)),good flame-retardance,anticorrosive property,and ultralow cost(7%of the commercial electrolyte and 2%of WIS).Raman spectroscopy and Density Functional Theory calculations reveal that the hydrogen bonds between the FMD molecules and NO_(3)^(-)ions are primarily responsible for the superior stability and conductivity.The developed NaNO_(3)/FMD-based coin cell supercapacitor is among the best-performing state-of-art DES and WIS devices,evidenced by the high voltage window(2.6 V),outstanding energy and power densities(22.77 Wh kg^(-1)at 630 W kg^(-1)and 17.37 kW kg^(-1)at 12.55 Wh kg^(-1)),ultralong cyclic stability(86%after 30000 cycles),and negligible current collector corrosion.The NaNO_(3)/FMD industry adoption potential is demonstrated by fabricating 100 F pouch cell supercapacitors using commercial aluminum current collectors.

Rainfall-triggered waste dump instability analysis based on surface 3D deformation in physical model test

Landslide is the second largest natural disaster after earthquake. It is of significance to study the evolution laws and failure mechanism of landslides based on its surface 3D deformation information. Based on the rainfall-triggered waste dump instability model test, we studied the failure mechanisms of the waste dump by integrating surface deformation and internal slope stress and proposed novel parameters for identifying landslide stability. We developed a noncontact measurement device, which can obtain millimeter-level 3D deformation data for surface scene in physical model test;Then we developed the similar materials and established a test model for a waste dump. Based on the failure characteristics of slope surface, internal stress of slope body and displacement contours during the whole process, we divided the slope instability process in model test into four stages: rainfall infiltration and surface erosion, shallow sliding, deep sliding, and overall instability. Based on the obtained surface deformation data, we calculated the volume change during slope instability process and compared it with the point displacement on slope surface. The results showed that the volume change can not only reflect the slow-ultra acceleration process of slope failure, but also fully reflect the above four stages and reduce the fluctuations caused by random factors. Finally, this paper proposed two stability identification parameters: the volume change rate above the slip surface and the relative velocity of volume change rate. According to the calculation of these two parameters in model test, they can be used for study the deformation and failure mechanism of slope stability.

Functional nanolayers favor the stability of solid-electrolyteinterphase in rechargeable batteries

Rechargeable batteries have brought us lots of convenience and changed the way we live.However,the demand for higher energy density,longer cycle life,and more fast charging ability urges researchers to develop advanced battery material and chemistry[1,2].

Gedankenexperiment for Modified ZPE and Planck’s “Constant”, h, in the Beginning of Cosmological Expansion, Partly Due to NLED

We initially look at a non singular universe representation of entropy, based in part on what was brought up by Muller and Lousto. This is a gateway to bringing up information and computational steps (as defined by Seth Lloyd) as to what would be available initially due to a modified ZPE formalism. The ZPE formalism is modified as due to Matt Visser’s alternation of k (maximum) ~ 1/(Planck length), with a specific initial density giving rise to initial information content which may permit fixing the initial Planck’s constant, h, which is pivotal to the setting of physical law. The settings of these parameters depend upon NLED.