Heterogeneous information phase space reconstruction and stability prediction of filling body–surrounding rock combination

Traditional research believes that the filling body can effectively control stress concentration while ignoring the problems of unknown stability and the complex and changeable stress distribution of the filling body–surrounding rock combination under high-stress conditions.Current monitoring data processing methods cannot fully consider the complexity of monitoring objects,the diversity of monitoring methods,and the dynamics of monitoring data.To solve this problem,this paper proposes a phase space reconstruction and stability prediction method to process heterogeneous information of backfill–surrounding rock combinations.The three-dimensional monitoring system of a large-area filling body–surrounding rock combination in Longshou Mine was constructed by using drilling stress,multipoint displacement meter,and inclinometer.Varied information,such as the stress and displacement of the filling body–surrounding rock combination,was continuously obtained.Combined with the average mutual information method and the false nearest neighbor point method,the phase space of the heterogeneous information of the filling body–surrounding rock combination was then constructed.In this paper,the distance between the phase point and its nearest point was used as the index evaluation distance to evaluate the stability of the filling body–surrounding rock combination.The evaluated distances(ED)revealed a high sensitivity to the stability of the filling body–surrounding rock combination.The new method was then applied to calculate the time series of historically ED for 12 measuring points located at Longshou Mine.The moments of mutation in these time series were at least 3 months ahead of the roadway return dates.In the ED prediction experiments,the autoregressive integrated moving average model showed a higher prediction accuracy than the deep learning models(long short-term memory and Transformer).Furthermore,the root-mean-square error distribution of the prediction results peaked at 0.26,thus outperforming the no-prediction method in 70%of the cases.

Significantly enhanced thermal stability of HMX by phase-transition lysozyme coating

A new robust bio-inspired route by using lysozyme aqueous solution for surface modification on 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX)was described in this paper.HMX crystals were coated by in situ phase transition of lysozyme(PTL)molecules.The HMX decorated by PTL was characterized by SEM,XRD,FTIR and XPS,demonstrating a dense core-shell coating layer.The coverage of lysozyme on HMX crystal was calculated by the ratio of sulfur content.The surface coverage increased from 60.5% to 93.5% when the content of PTL was changed from 0.5 wt% to 2.0 wt%,indicating efficient coating.The thermal stability of HMX was investigated by in situ XRD and DSC.The thermal phase transition temperature of HMX(β to δ phase)was delayed by 42℃ with 2.0 wt% PTL coating,which prevented HMX from thermal damage and sensitivity by the effect of PTL coating.After heating at 215℃,large cracks appeared in the naked HMX crystal,while the PTL coated HMX still maintained intact,with the impact energy of HMX dropped dramatically from 5 J to 2 J.However,the impact energy of HMX with 1.0 wt% and 2.0 wt% coating content(HMX@PTL-1.0 and HMX@PTL-2.0)was unchanged(5 J).Present results potentially enable large-scale fabrication of polymorphic energetic materials with outstanding thermal stability by novel lysozyme coating.

Optimal parameter space for stabilizing the ferroelectric phase of Hf_(0.5)Zr_(0.5)O_(2) thin films under strain and electric fields

Hafnia-based ferroelectric materials, like Hf_(0.5)Zr_(0.5)O_(2)(HZO), have received tremendous attention owing to their potentials for building ultra-thin ferroelectric devices. The orthorhombic(O)-phase of HZO is ferroelectric but metastable in its bulk form under ambient conditions, which poses a considerable challenge to maintaining the operation performance of HZO-based ferroelectric devices. Here, we theoretically addressed this issue that provides parameter spaces for stabilizing the O-phase of HZO thin-films under various conditions. Three mechanisms were found to be capable of lowering the relative energy of the O-phase, namely, more significant surface-bulk portion of(111) surfaces, compressive c-axis strain,and positive electric fields. Considering these mechanisms, we plotted two ternary phase diagrams for HZO thin-films where the strain was applied along the in-plane uniaxial and biaxial, respectively. These diagrams indicate the O-phase could be stabilized by solely shrinking the film-thickness below 12.26 nm, ascribed to its lower surface energies. All these results shed considerable light on designing more robust and higher-performance ferroelectric devices.

Enhancing the crystallinity and stability of perovskite solar cells with 4-tert-butylpyridine induction for efficiency exceeding 24%

Perovskite solar cells(PSCs)have emerged as a promising photovoltaic technology because of their high light absorption coefficient,long carrier diffusion distance,and tunable bandgap.However,PSCs face challenges such as hysteresis effects and stability issues.In this study,we introduced a novel approach to improve film crystallization by leveraging 4-tert-butylpyridine(TBP)molecules,thereby enhancing the performance and stability of PSCs.Our findings demonstrate the effective removal of PbI_(2)from the perovskite surface through strong coordination with TBP molecules.Additionally,by carefully adjusting the concentration of the TBP solution,we achieved enhanced film crystallinity without disrupting the perovskite structure.The TBP-treated perovskite films exhibit a low defect density,improved crystallinity,and improved carrier lifetime.As a result,the PSCs manufactured with TBP treatment achieve power conversion efficiency(PCE)exceeding 24%.Moreover,we obtained the PCE of 21.39%for the 12.25 cm^(2)module.

Phase Stability and Reactions of Subducting CaCO_(3)under Upper Mantle Conditions

CaCO_(3)is an important component of marine sediments and one of the major deep-carbon carriers at subduction zones.Some subducted CaCO_(3)can be dissolved in subduction fluids and recycled back to the surface via arc volcanoes degassing.At the same time,there still remain large amounts of CaCO_(3)and its reaction products,which could be further transported into Earth's deep interior.These internal processes link atmosphere,hydrosphere and biosphere with the deep solid Earth,modifying the environments of our planet.In this review,we summarize current understanding from high pressure-temperature experiments and field petrological observations on the physical and chemical properties of CaCO_(3).In particular,the phase stability and reactions of CaCO_(3)largely control the migration and reservation of oxidized carbon in subducting slabs.Finally,we present several critical but unsolved questions on CaCO_(3)subducting in the deep mantle.

Ionic Liquid Assisted Imprint for Efficient and Stable Quasi-2D Perovskite Solar Cells with Controlled Phase Distribution

Although two-dimensional perovskite devices are highly stable,they also lead to a number of challenges.For instance,the introduction of large organic amines makes crystallization process complicated,causing problems such as generally small grain size and blocked charge transfer.In this work,imprint assisted with methylamine acetate were used to improve the morphology of the film,optimize the internal phase distribution,and enhance the charge transfer of the perovskite film.Specifically,imprint promoted the dispersion of spacer cations in the recrystallization process with the assistance of methylamine acetate,thus inhibited the formation of low-n phase induced by the aggregation of spacer cations and facilitated the formation of 3D-like phase.In this case,the corresponding quasi-2D perovskite solar cells delivered improved efficiency and exhibited superior stability.Our work provides an effective strategy to obtain uniform phase distribution for quasi-2D perovskite.

Additive Engineering for Stable and Efficient Dion-Jacobson Phase Perovskite Solar Cells

Because of their better chemical stability and fascinating anisotropic characteristics,Dion-Jacobson(DJ)-layered halide perovskites,which owe crystallographic two-dimensional structures,have fascinated growing attention for solar devices.DJ-layered halide perovskites have special structural and photoelectronic features that allow the van der Waals gap to be eliminated or reduced.DJ-layered halide perovskites have improved photophysical characteristics,resulting in improved photovoltaic performance.Nevertheless,owing to the nature of the solution procedure and the fast crystal development of DJ perovskite thin layers,the precursor compositions and processing circumstances can cause a variety of defects to occur.The application of additives can impact DJ perovskite crystallization and film generation,trap passivation in the bulk and/or at the surface,interface structure,and energetic tuning.This study discusses recent developments in additive engineering for DJ multilayer halide perovskite film production.Several additive-assisted bulk and interface optimization methodologies are summarized.Lastly,an overview of research developments in additive engineering in the production of DJ-layered halide perovskite solar cells is offered.

Experimental study on thermal and mechanical properties of tailings-based cemented paste backfill with CaCl_(2)·6H_(2)O/expanded vermiculite shape stabilized phase change materials

CaCl_(2)·6H_(2)O/expanded vermiculite shape stabilized phase change materials(CEV)was prepared by atmospheric impregnation method.Using gold mine tailings as aggregate of cemented paste backfill(CPB)material,the CPB with CEV added was prepared,and the specific heat capacity,thermal conductivity,and uniaxial compressive strength(UCS)of CPB with different cement-tailing ratios and CEV addition ratios were tested,the influence of the above variables on the thermal and mechanical properties of CPB was analyzed.The results show that the maximum encapsulation capacity of expanded vermiculite for CaCl_(2)·6H_(2)O is about 60%,and the melting and solidification enthalpies of CEV can reach 98.87 J/g and 97.56 J/g,respectively.For the CPB without CEV,the specific heat capacity,thermal conductivity,and UCS decrease with the decrease of cement-tailing ratio.For the CPB with CEV added,with the increase of CEV addition ratio,the specific heat capacity increases significantly,and the sensible heat storage capacity and latent heat storage capacity can be increased by at least 10.74%and 218.97%respectively after adding 12%CEV.However,the addition of CEV leads to the increase of pores,and the thermal conductivity and UCS both decrease with the increase of CEV addition.When cement-tailing ratio is 1:8 and 6%,9%,and 12%of CEV are added,the 28-days UCS of CPB is less than 1 MPa.Considering the heat storage capacity and cost price of backfill,the recommended proportion scheme of CPB material presents cement-tailing ratio of 1:6 and 12%CEV,and the most recommended heat storage/release temperature cycle range of CPB with added CEV is from 20 to 40℃.This work can provide theoretical basis for the utilization of heat storage backfill in green mines.

Effects of Ru on the microstructure and phase stability of a single crystal superalloy

Two experimental single crystal superalloys, the Ru-free alloy and the Ru-containing alloy with [001 ] orientation, were cast in a directionally solidified furnace, while other alloying element contents were kept unchanged. The effects of Ru on the microstructure and phase stability of the single crystal superalloy were investigated, y＇ directional coarsening and rafting were observed in the Ru-free alloy and Ru-containing alloy after long-term aging at 1070~C for 800 h. Needle-shaped o topologically close packed （TCP） phases precipitated and grew along the fixed direction in both the alloys. The precipitating rate and volume fraction of TCP phases decreased significantly by adding Ru. The compositions ofy and y＇ phases measured using an energy-dispersive X-ray spectroscope （EDS） in transmission electron microscopy （TEM） analysis showed that the addition of Ru lessened the partition ratio of TCP forming elements, Re, W and Mo, and decreased the satu- ration degrees of these elements in y phase, which can enable the Ru-containing alloy to be more resistant to the formation of TCP phases. It is indicated that the addition of Ru to the Ni-based single crystal superalloy with high content of the refractory alloying element can enhance phase stability.

Phase stability,elastic properties and electronic structures of Mg-Y intermetallics from first-principles calculations

The phase stability,elastic properties and electronic structures of three typical Mg-Y intermetallics including Mg_(24)Y_(5),Mg_(2)Y and MgY are systematically investigated using first-principles calculations based on density functional theory.The optimized structural parameters including lattice constants and atomic coordinates are in good agreement with experimental values.The calculated cohesive energies and formation enthalpies show that either phase stability or alloying ability of the three intermetallics is gradually enhanced with increasing Y content.The single-crystal elastic constants C_(ij) of Mg-Y intermetallics are also calculated,and the bulk modulus B,shear modulus G,Young's modulus E,Poisson ratio v and anisotropy factor A of polycrystalline materials are derived.It is suggested that the resistances to volume and shear deformation as well as the stiffness of the three intermetallics are raised with increasing Y content.Besides,these intermetallics all exhibit ductile characteristics,and they are isotropic in compression but anisotropic to a certain degree in shear and stiffness.Comparatively,Mg_(24)Y_(5) presents a relatively higher ductility,while MgY has a relatively stronger anisotropy in shear and stiffness.Further analysis of electronic structures indicates that the phase stability of Mg-Y intermetallics is closely related with their bonding electrons numbers below Fermi level.Namely,the more bonding electrons number below Fermi level corresponds to the higher structural stability of Mg-Y intermetallics.

Phase stability,electronic,elastic and thermodynamic properties of Al-RE intermetallics in Mg-Al-RE alloy:A first principles study

Electronic structure and elastic properties of Al_(2)Y,Al_(3)Y,Al_(2)Gd and Al_(3)Gd phases were investigated by means of first-principles calculations from CASTEP program based on density functional theory(DFT).The ground state energy and elastic constants of each phase were calculated,the formation enthalpy(ΔH),bulk modulus(B),shear modulus(G),Young's modulus(E),Poisson's ratio(ν)and anisotropic coefficient(A)were derived.The formation enthalpy shows that Al_(2)RE is more stable than Al_(3)RE,and Al-Y intermetallics have stronger phase stability than Al-Gd intermetallics.The calculated mechanical properties indicate that all these four intermetallics are strong and hard brittle phases,it may lead to the similar performance when deforming due to their similar elastic constants.The total and partial electron density of states(DOS),Mulliken population and metallicity were calculated to analyze the electron structure and bonding characteristics of the phases.Finally,phonon calculation was conducted,and the thermodynamic properties were obtained and further discussed.

Phase Behavior, Thermal Stability and Rheological Properties of PPEK/PC Blends

Phase behavior, thermal stability and rheological properties of the blends of poly(phthalazinone ether ketone) (PPEK) with bisphenol-A polycarbonate (PC) prepared by solution coprecipitation were studied using differential scanning calorimetry (DSC), Frourier-Transform IR spectroscopy (FT-IR), thermogravimetric analysis (TGA) and capillary rheometer. The DSC results indicated that PPEK/PC blends are almost immiscible in full compositions. FT-IR investigation showed that there were no apparent specific interactions between the constituent polymers. The blends keep excellent thermal stability and the addition of PC degrades the thermal stability of blends to some degree. The thermal degradation processes of the blends are much similar to that of PC. The studies on rheological properties of blends show that blending PPEK with PC is beneficial to reducing the melt viscosity and improving the appearance of PPEK.

Experimental and ab initio study of Ba_(2)Na_(3)(B_(3)O_(6))_(2)F stability in the pressure range of 0–10 GPa

Both numerical and experimental studies of the stability and electronic properties of barium–sodium metaborate Ba_(2)Na_(3)(B_(3)O_(6))_(2)F(P63/m) at pressures up to 10 GPa have been carried out. Electronic-structure calculations with HSE06 hybrid functional showed that Ba_(2)Na_(3)(B_(3)O_(6))_(2)F has an indirect band gap of 6.289 eV. A numerical study revealed the decomposition of Ba_(2)Na_(3)(B_(3)O_(6))_(2)F into the BaB_(2)O_(4),Na BO_(2), and NaF phases above 3.4 GPa at 300 K. Subsequent high-pressure high-temperature experiments performed using ‘Discoverer-1500’DIA-type apparatus at pressures of 3 and 6 GPa and temperature of 1173 K confirmed the stability of Ba_(2)Na_(3)(B_(3)O_(6))_(2)F at 3 GPa and its decomposition into BaB_(2)O_(4), NaBO_(2), and NaF at 6 GPa, which was verified by energy-dispersive X-ray analysis and Raman spectroscopy. The observed Raman bands of the Ba_(2)Na_(3)(B_(3)O_(6))_(2)F phase were assigned by comparing the experimental and calculated spectra. The experimental Raman spectra of decomposition reaction products obtained at 6 GPa suggest the origin of a new high-pressure modification of barium metaborate BaB_(2)O_(4).

Tailoring of thermal expansion and phase transition temperature of ZrW_(2)O_8 with phosphorus and enhancement of negative thermal expansion of ZrW_(1.5)P_(0.5)O_(7.75)

ZrW_(2)O_(8)is a typical isotropic negative thermal expansion material with cubic structure.However,quenching preparation,pressure phase transition and metastable structure influence its practical applications.Adopting P to part-substitute W for ZrW_(2-x)P_(x)O_(8-0.5x)has decreased the sintering temperature and avoided the quenching process.When x=0.1,ZrW_(1.9)P_(0.1)O_(7.95)with a stable cubic structure can be obtained at 1150℃.The thermal expansion coefficient is tailored with the P content,and phase transition temperature is lowered.When x=0.5,thermal expansion coefficient attains-13.6×10^(-6)℃^(-1),ZrW_(1.5)P_(0.5)O_(7.75)exhibits enhance negative thermal expansion property.The difference of electronegativity leads to the decrease of phase transition temperature with the increase of P content.The different radii of ions lead to new structure of materials when P substitutes more.The results suggest that the P atom plays the stabilization role in the crystal structure of ZrW_(2-x)P_(x)O_(8-0.5x).

Phase thermal stability and mechanical properties analyses of(Cr,Fe,V)–(Ta,W)multiple-based elemental system using a compositional gradient film

High-entropy alloys(HEAs)generally possess complex component combinations and abnormal properties.The traditional methods of investigating these alloys are becoming increasingly inefficient because of the unpredictable phase transformation and the combination of many constituents.The development of compositionally complex materials such as HEAs requires high-throughput experimental methods,which involves preparing many samples in a short time.Here we apply the high-throughput method to investigate the phase evolution and mechanical properties of novel HEA film with the compositional gradient of(Cr,Fe,V)-(Ta,W).First,we deposited the compositional gradient film by co-sputtering.Second,the mechanical properties and thermal stability of the(Cr0.33Fe0.33V0.33)x(Ta0.5W0.5)100−x(x=13-82)multiplebased-elemental(MBE)alloys were investigated.After the deposited wafer was annealed at 600℃for 0.5 h,the initial amorphous phase was transformed into a body-centered cubic(bcc)structure phase when x=33.Oxides were observed on the film surface when x was 72 and 82.Finally,the highest hardness of as-deposited films was found when x=18,and the maximum hardness of annealed films was found when x=33.

Exceptional thermal stability and enhanced hardness in a nanostructured Mg-Gd-Y-Zn-Zr alloy processed by high pressure torsion

A Mg-8.2Gd-3.8Y-1.0Zn-0.4Zr(wt.%) alloy is processed by solution treatment and high pressure torsion(HPT) at room temperature to produce a nanostructured light material with high hardness. The stability of this alloy is subsequently tested through isochronal annealing for 0.5 h at 373 K to 673 K. The results reveal a thermal stability that is vastly superior to that of conventional Mg-based alloys processed by severe plastic deformation: the grain size remains at around 50 nm on heating to 573 K, and as the temperature is increased to 673 K,grain growth is restricted to within 500 nm. The stability of grain refinement of the present alloy/processing combination allowing grain size to be limited to 55 nm after exposure at 573 K, appears to be nearly one order of magnitude better than for the other SPD processed Mg-RE type alloys, and 2 orders of magnitude better than those of SPD processed RE-free Mg alloys. This superior thermal stability is attributed to formation of co-clusters near and segregation at grain boundaries, which cause a thermodynamic stabilization of grain size, as well as formation of β-Mg_(5)RE equilibrium phase at grain boundaries, which impede grain growth by the Zener pinning effect. The hardness of the nanostructured Mg-Gd-Y-Zn-Zr alloy increases with increasing annealing temperature up to 573 K, which is quite different from the other SPD-processed Mg-based alloys. The high hardness of 136 HV after annealing at 573 K is mainly due to solute segregation and solute clustering at or near grain boundaries.

Unexpected Li displacement and suppressed phase transition enabling highly stabilized oxygen redox in P3-type Na layered oxide cathode

Oxygen redox is considered a new paradigm for increasing the practical capacity and energy density of the layered oxide cathodes for Na-ion batteries. However, severe local structural changes and phase transitions during anionic redox reactions lead to poor electrochemical performance with sluggish kinetics.Here, we propose a synergy of Li-Cu cations in harnessing the full potential of oxygen redox, through Li displacement and suppressed phase transition in P3-type layered oxide cathode. P3-type Na_(0.7)[Li_(0.1)Cu_(0.2)Mn_(0.7)]O_(2) cathode delivers a large specific capacity of ~212 mA h g^(-1)at 15 mA g^(-1). The discharge capacity is maintained up to ~90% of the initial capacity after 100 cycles, with stable occurrence of the oxygen redox in the high-voltage region. Through advanced experimental analyses and first-principles calculations, it is confirmed that a stepwise redox reaction based on Cu and O ions occurs for the charge-compensation mechanism upon charging. Based on a concrete understanding of the reaction mechanism, the Li displacement by the synergy of Li-Cu cations plays a crucial role in suppressing the structural change of the P3-type layered material under the oxygen redox reaction, and it is expected to be an effective strategy for stabilizing the oxygen redox in the layered oxides of Na-ion batteries.

Effects of temperature and point defects on the stability of C15 Laves phase in iron:A molecular dynamics investigation

Molecular dynamics simulations are used to investigate the stabilities of C15 Laves phase structures subjected to temperature and point defects. The simulations based on different empirical potentials show that the bulk perfect C15 Laves phase appears to be stable under a critical temperature in a range from 350 K to 450 K, beyond which it becomes disordered and experiences an abrupt decrement of elastic modulus. In the presence of both vacancy and self-interstitial, the bulk C15 Laves phase becomes unstable at room temperature and prefers to transform into an imperfect body centered cubic（BCC）structure containing free vacancies or vacancy clusters. When a C15 cluster is embedded in BCC iron, the annihilation of interstitials occurs due to the presence of the vacancy, while it exhibits a phase transformation into a（1/2） 111 dislocation loop due to the presence of the self-interstitial.

Moisture-Induced Non-Equilibrium Phase Segregation in Triple Cation Mixed Halide Perovskite Monitored by In Situ Characterization Techniques and Solid-State NMR

Environmental stability is a major bottleneck of perovskite solar cells.Only a handful of studies are investigating the effect of moisture on the structural degradation of the absorber.They mostly rely on ex situ experiments and on completely degraded samples,which restrict the assessment on initial and final stage.By combining in situ X-ray diffraction under controlled 85%relative humidity,and live observations of the water-induced degradation using liquid-cell transmission electron microscopy,we reveal two competitive degradation paths leading on one hand to the decomposition of state-of-theart mixed cation/anion(Cs_(0.05)(MA_(0.17)FA_(0.83))_(0.95)Pb(Br_(0.17)I_(0.83))_(3)(CsMAFA)into PbI_(2) through a dissolution/recrystallization mechanism and,on the other hand,to a non-equilibrium phase segregation leading to CsPb_(2)Br_(5) and a Cesium-poor/iodide-rich Cs_(0.05)-x(MA_(0.17)FA_(0.83))_(0.95)Pb(Br_(0.17-2y)I_(0.83)+2y)_(3) perovskite.This degradation mechanism is corroborated at atomic-scale resolution through solid-state ^(1)H and ^(133)Cs NMR analysis.Exposure to moisture leads to a film containing important heterogeneities in terms of morphology,photoluminescence intensities,and lifetimes.Our results provide new insights and consensus that complex perovskite compositions,though very performant as champion devices,are comparatively metastable,a trait that limits the chances to achieve long-term stability.

Cr doping effect in B-site of La_(0.75)Sr_(0.25)MnO_3 on its phase stability and performance as an SOFC anode

La0.75Sr0.25CryMn1-yO3 （LSCM） （y = 0.0-0.6） composite oxides were synthesized by a complexing process of combining ethylene diamine tetraacetic acid （EDTA） and citrate. X-ray diffraction （XRD）, temperature-programmed reduction, electrical conductivity, I-V polarization, and impedance spectroscopy were conducted to investigate the Cr doping effect of La0.75Sr0.25MnO3 on its phase stability and electrochemical performance as a solid-oxide fuel cell （SOFC） anode. The chemical and structural stabilities of the oxides increased steadily with increasing Cr doping concentration, while the electrical conductivity decreased on the contrary. At y 〉 0.4, the basic perovskite structure under the anode operating condition was sustained. A cell with 0.5-ram-thick scandia-stabilized zirconia electrolyte and La0.75Sr0.25CryMn1-yO3 anode delivered a Dower density of -15 mW-cm^-2 at 850℃.