Gemological-Mineralogical Characteristic of Spinels from Sri Lanka

Detailed mineralogical and gemological records were conducted on 340 unheated spinels from the Horana, Eheliyagoda, Ratnapura, and Okkampatiya mining areas in Sri Lanka. The color of Sri Lankan spinel varies greatly: in addition to the mainstream pink to purple pink, green and blue can also be seen. Compared with spinel from other regions such as Myanmar, Vietnam, and Tanzania, Sri Lanka's spinel has more abundant inclusions: several mining areas generally have inclusions such as dolomite, apatite, zircon, and chondrodite. Minerals such as graphite and forsterite are also found in spinel produced in the Horana region;graphite and rutile have been found in spinel produced in the Okkamptiya region. Partially healed fissures are most common in spinel in the Okkampatiya mining area;Unlike Vietnamese spinel, dislocations and growth structures are almost absent in Sri Lankan spinel. The LA-ICP-MS analysis results showed that there were no significant differences among the mining areas. LA-ICP-MS analysis of 5 Sri Lankan cobalt blue spinels showed a variation of 11 to 120 ppm in this chromogenic element. The UV visible absorption spectrum results show that Sri Lankan spinel has a combination spectra with variable ratios of the spectral components Cr 3+ , V 3+ and Fe 2+ from pink to red, orange, purple to purple, and blue-green. The results of infrared spectroscopy and laser Raman spectroscopy analysis showed that all samples showed no indications for heat treatment.

Computational study of inverse ferrite spinels

The magnetic properties of inverse ferrite Fe_(3+) Fe_(3+)Co_(2+) O^(2-)_4, Fe^(3+) Fe^(3+)Cu^(2+) O^2_(-4), Fe^(3+) Fe^(3+)Fe^(2+) O^2_(-4),and Fe^(3+) Fe^(3+)Ni^(2+) O^(2-)_4spinels have been studied using Monte Carlo simulation. We have also calculated the critical and Curie Weiss temperatures from the thermal magnetizations and inverse of magnetic susceptibilities for each system.Magnetic hysteresis cycles have been found for the four systems. Finally, we found the critical exponents associated with magnetization, magnetic susceptibility, and external magnetic field. Our results of critical and Curie Weiss temperatures are similar to those obtained by experiment results. The critical exponents are similar to those of known 3 D-Ising model.

A New Perspective on the 5 V Discharge Capacity of Li/Al Doped Manganese Spinels

A series of manganese spinels LiMn2-yMeyO4 （Me = Li, A1, Mg） were prepared and examined by XRD and electrochemical methods. The spinels doped with Li or high content of A1 can exhibit discharge capacity in the 5 V region, but spinels doped with Mg do not exhibit any 5 V discharge capacity. It is also observed that the 5 V discharge capacity of Li/A1 doped spinels will be greatly suppressed once calcinated at temperatures above 900 ℃ in preparation. It is suggested that the 5 V discharge capacity of Li/A1 doped spinels may be originated from the special chemical/structural characteristics of spinel phases containing Li or high content of A1 prepared at temperatures below 900 ℃.

Chromian Spinels in Listwaenite and Related Rocks in the Sartohay Ophiolitic Mélange, Xinjiang, NW China

Listwaenite,carbonate-talc schist,and serpentinite of Sartohay ophioliticmélange,Xinjiang,northwestern China,contain variably altered chromian spinels.During the hydrothermal alteration from serpentinite to listwaenite

Synthesis and electrochemical properties of dual doped spinels LiNi_xAl_yMn_(2-x-y)O_4 via facile novel chelated sol–gel method as possible cathode material for lithium rechargeable batteries

LiMnOand LiNiAlyMnO（x= 0.50;y = 0.05-0.50） powders have been synthesized via facile solgel method using Behenic acid as active cheiating agent.The synthesized samples are subjected to physical characterizations such as thermo gravimetric analysis（TG/DTA）,X-ray diffraction（XRD）,Fourier transform infrared spectroscopy（FT-IR）,field-emission scanning electron microscopy（FESEM）,transmission electron microscopy（TEM） and electrochemical studies viz.,galvanostatic cycling properties,electrochemical impedance spectroscopy（EIS） and differential capacity curves（dQ/dE）.Finger print XRD patterns of LiMnOand LiNiAlMnOfortify the high degree of crystallinity with better phase purity.FESEM images of the undoped pristine spinel illustrate uniform spherical grains surface morphology with an average particle size of 0.5 μm while Ni doped particles depict the spherical grains growth（50nm） with ice-cube surface morphology.TEM images of the spinel LiMnOshows the uniform spherical morphology with particle size of（100 nm） while low level of Al-doping spinel（LiNio.5Alo.05Mn1.45O4） displaying cloudy particles with agglomerated particles of（50nm）.The LiMnOsamples calcined at 850℃ deliver the discharge capacity of 130 mAh/g in the first cycle corresponds to 94%coiumbic efficiency with capacity fade of 1.5 mAh/g/cycle over the investigated 10 cycles.Among all four dopant compositions investigated,LiNiAlMnOdelivers the maximum discharge capacity of 126 mAh/g during the first cycle and shows the stable cycling performance with low capacity fade of 1 mAh/g/cycle（capacity retention of 92%） over the investigated 10 cycles.Electrochemical impedance studies of spinel LiMnOand LiNiAlMnOdepict the high and low real polarization of 1562 and 1100 Ω.

The Characteristics of Spinels in Mantle-derivedXenoliths in Cenozoic Basalts from Eastern Chinaand Their Thermal States

The colours and chemical composition variations of 160 spinels in peridotite and pyroxenite xenoliths from Cenozoic basalts in eastern China and their petrogeneses have been studied in detail. The relationships between major elements of spinels are discussed. The equilibrium temperatures, pressures and oxygen fugacities of spinels and their coexisting olivines, orthopyroxenes and clinopyroxenes have been determined using the Brey—kohler's T—P calculation methods (1990) and Ballhaus' fo2 calculation method (1991). The relationships between the composition and the equilibrium temperatures, pressures or oxygen fugacities of spinels in peridotite xenoliths from the basalts and the stable field of the spinels in the upper mantle have been shown.

Effect of Spinels on Properties of MgO-Al_(2)O_(3) Refractories for RH Snorkels

With satisfactory high temperature properties,thermal shock resistance and mechanical properties,refractories in the MgO-Al_(2)O_(3) system have become promising alternative to MgO-Cr_(2)O_(3) counterpart used as RH snorkel lining.High purity dead burned magnesia,fused magnesia and sintered spinel were used as raw materials and sulfite pulp waste as the binder,specimens of the refractories in the Mg0-Al_(2)O_(3) system were prepared for the purpose of investigating the influences in terms of the addition of three kinds of spinels,with Al_(2)O_(3) 50%,66% and 78%,by mass,respectively,and the size of MA50 spinel on properties of the specimens.Relatively superior comprehensive properties can be achieved when 16%of MA50 spinel with sizes under 1mm is adopted.

DFT investigation of half-metallic ferromagnetic rare earth based spinels MgHo_(2)Z_(4)(Z=S,Se)

Half-metallic ferromagnetism,mechanical as well as thermoelectric properties for rare earth-based spinels MgHo_(2)Z_(4)(Z=S,Se)were investigated using density functional theory(DFT).Structural optimization was done with Perdew-Burke-Ehrenzorf(PBE)sol-generalized gradient approximation(GGA)to calculate the lattice constant of both spinels comparable to experimental data.In addition,Born stability criteria and negative formation energy show that our studied spinels are also structurally and dynamically stable in the cubic phase.For ferromagnetic(FM)state stability,we also calculated the energy differences among FM,antiferromagnetic(AFM),and non-magnetic(NM)states.Additionally,Curie temperatures of ferromagnetic phases were also estimated.We used Trans-Blaha improved BeckeJohnson(TB-mBJ)potential functional for electronics as well as magnetic characteristics,which lead to the consistent explanation of half-metallic ferromagnetism,representing the whole band-occupancy in material with exact detail of density of states(DOS).The stable FM state was examined in spinels due to the exchange splitting of Ho cation consisting of p-d hybridizations compatible with the result achieved for electronics band structure and DOS.Further,spin magnetic moment was explained in terms of anion,cation,and sharing charge on studied spinels.In addition,the calculated thermoelectric properties clearly show that operation range of these systems may be utilized by future experimental works for identifying the potential applications of these systems.

Effects of iron oxide on crystallization behavior and spatial distribution of spinel in stainless steel slag

Chromium plays a vital role in stainless steel due to its ability to improve the corrosion resistance of the latter.However,the re-lease of chromium from stainless steel slag(SSS)during SSS stockpiling causes detrimental environmental issues.To prevent chromium pollution,the effects of iron oxide on crystallization behavior and spatial distribution of spinel were investigated in this work.The results revealed that FeO was more conducive to the growth of spinels compared with Fe2O3 and Fe3O4.Spinels were found to be mainly distrib-uted at the top and bottom of slag.The amount of spinel phase at the bottom decreased with the increasing FeO content,while that at the top increased.The average particle size of spinel in the slag with 18wt%FeO content was 12.8μm.Meanwhile,no notable structural changes were observed with a further increase in FeO content.In other words,the spatial distribution of spinel changed when the content of iron oxide varied in the range of 8wt%to 18wt%.Finally,less spinel was found at the bottom of slag with a FeO content of 23wt%.

Microwave-assisted exploration of the electron configuration-dependent electrocatalytic urea oxidation activity of 2D porous NiCo_(2)O_(4) spinel

Urea holds promise as an alternative water-oxidation substrate in electrolytic cells.High-valence nickelbased spinel,especially after heteroatom doping,excels in urea oxidation reactions(UOR).However,traditional spinel synthesis methods with prolonged high-temperature reactions lack kinetic precision,hindering the balance between controlled doping and highly active two-dimensional(2D)porous structures design.This significantly impedes the identification of electron configuration-dependent active sites in doped 2D nickel-based spinels.Herein,we present a microwave shock method for the preparation of 2D porous NiCo_(2)O_(4)spinel.Utilizing the transient on-off property of microwave pulses for precise heteroatom doping and 2D porous structural design,non-metal doping(boron,phosphorus,and sulfur)with distinct extranuclear electron disparities serves as straightforward examples for investigation.Precise tuning of lattice parameter reveals the impact of covalent bond strength on NiCo_(2)O_(4)structural stability.The introduced defect levels induce unpaired d-electrons in transition metals,enhancing the adsorption of electron-donating amino groups in urea molecules.Simultaneously,Bode plots confirm the impact mechanism of rapid electron migration caused by reduced band gaps on UOR activity.The prepared phosphorus-doped 2D porous NiCo_(2)O_(4),with optimal electron configuration control,outperforms most reported spinels.This controlled modification strategy advances understanding theoretical structure-activity mechanisms of high-performance 2D spinels in UOR.

Unveiling the geometric site dependent activity of spinel Co_(3)O_(4)for electrocatalytic chlorine evolution reaction

Spinel cobalt oxide(Co_(3)O_(4)),consisting of tetrahedral Co^(2+)(CoTd)and octahedral Co^(3+)(CoOh),is considered as promising earth-abundant electrocatalyst for chlorine evolution reaction(CER).Identifying the catalytic contribution of geometric Co site in the electrocatalytic CER plays a pivotal role to precisely modulate electronic configuration of active Co sites to boost CER.Herein,combining density functional theory calculations and experiment results assisted with operando analysis,we found that the Co_(Oh) site acts as the main active site for CER in spinel Co_(3)O_(4),which shows better Cl^(-)adsorption and more moderate intermediate adsorption toward CER than CoTd site,and does not undergo redox transition under CER condition at applied potentials.Guided by above findings,the oxygen vacancies were further introduced into the Co_(3)O_(4) to precisely manipulate the electronic configuration of Co_(Oh) to boost Cl^(-)adsorption and optimize the reaction path of CER and thus to enhance the intrinsic CER activity significantly.Our work figures out the importance of geometric configuration dependent CER activity,shedding light on the rational design of advanced electrocatalysts from geometric configuration optimization at the atomic level.

Development of bimetallic spinel catalysts for low-temperature decomposition of ammonium dinitramide monopropellants

Ammonium dinitramide(ADN)based liquid monopropellants have been identified as environmentally benign substitutes for hydrazine monopropellant.However,new catalysts are to be developed for making ADN monopropellants cold-start capable.In the present study,performance of Co and Ba doped CuCr_2O_4 nanocatalysts prepared by hydrothermal method was evaluated on the decomposition of aqueous ADN solution and ADN liquid monopropellant(LMP103X).The catalysts were characterized by PXRD(Powder X-ray Diffraction),FTIR(Fourier Transform Infrared spectroscopy),SEM(Scanning Electron Microscopy),TEM(Transmission Electron Microscopy),EDS(Energy Dispersive X-ray Spectroscopy),and XPS(X-ray Photoelectron Spectroscopy).The nanosize was confirmed by SEM and TEM,while the nanoflake morphology was confirmed by the SEM analysis.Further,we obtained the elemental composition from the EDS analysis.We investigated the catalytic activity of the catalysts by thermogravimetric(TG)analysis and the developed catalysts lowered the decomposition temperature of ADN monopropellant by about 55℃.The XPS analysis confirmed the presence of metal ions with different chemical states.Apparently,increase in the surface area of the catalysts and the mixed active sites as well as the development of oxygen vacancy on the catalyst surface introduced by metal doping are influencing the decomposition temperature of ADN samples.

Enabling structural and interfacial stability of 5 V spinel LiNi0.5Mn1.5O4 cathode by a coherent interface

Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO),a 5 V class high voltage cathode,has been regarded as an attractive candidate to further improve the energy density of lithium-ion battery.The issue simultaneously enabling side stability and maintaining high interfacial kinetics,however,has not yet been resolved.Herein,we design a coherent Li_(1.3)A_(l0.3)Ti_(1.7)(PO)_(4)(LATP)layer that is crystally connected to the spinel LNMO host lattices,which offers fast lithium ions transportation as well as enhances the mechanical stability that prevents the particle fracture.Furthermore,the inactive Li_(3)BO_(3)(LBO)coating layer inhibits the corrosion of transition metals and continuous side reactions.Consequently,the coherent-engineered LNMO-LATPLBO cathode material exhibits superior electrochemical cycling stability in a window of 3.0–5.0 V,for example a high-capacity retention that is 89.7%after 500 cycles at 200 m A g-1obtained and enhanced rate performance(85.1 m A h g^(-1)at 800 m A g^(-1))when tested with a LiPF6-based carbonate electrolyte.Our work presents a new approach of engineering 5 V class spinel oxide cathode that combines interfacial coherent crystal lattice design and surface coating.

Effects of ZnO,FeO and Fe_(2)O_(3)on the spinel formation,microstructure and physicochemical properties of augite-based glass ceramics

Augite-based glass ceramics were synthesised using ZnO,FeO,and Fe_(2)O_(3)as additives,and the spinel formation,matrix structure,crystallisation thermodynamics,and physicochemical properties were investigated.The results showed that oxides resulted in numerous preliminary spinels in the glass matrix.FeO,ZnO,and Fe_(2)O_(3)influenced the formation of spinel,while FeO simplified the glass network.FeO and ZnO promoted bulk crystallisation of the parent glass.After adding oxides,the grains of augite phase were refined,and the relative quantities of augite crystal planes were also influenced.All samples displayed good mechanical properties and chemical stability.The 2wt%ZnO-doping sample displayed the maximum flexural strength(170.3 MPa).Chromium leaching amount values of all the samples were less than the national standard(1.5 mg/L),confirming the safety of the materials.In conclusion,an appropriate amount of zinc-containing raw material is beneficial for the preparation of augite-based glass ceramics.

Analysis on the cation distribution of Mg_(x)Ni_(1-x)Fe_(2)O_(4)(x=0,0.25,0.5,0.75,1)using Mössbauer spectroscopy and magnetic measurement

MgxNi1-xFe_(2)O_(4)(x=0,0.25,0.5,0.75,1)spinel ferrite material was analyzed to determine its magnetic properties and structure.X-ray diffraction(XRD),Mössbauer spectroscopy,and vibrating sample magnetometer(VSM)characterization were performed on the samples prepared using the sol-gel method.The results from XRD confirmed the existence of the single-phase cubic spinel structures Fd3m,as well as the evolution of the crystalline size(D),the lattice parameter(a)and cell volume in compounds.The Mössbauer spectra showed the distribution of cations and changes in the magnetic properties of the sample.VSM measurement revealed that the samples were room-temperature ferromagnetic.Moreover,the saturation magnetization(Ms)of the samples changed with the Mg^(2+)ion content x,and a maximum occured at x=0.5.Doping with Mg^(2+)ions increased the transfer of Ni^(2+)ions to tetrahedral sites,thus increasing the magnetic moment difference between tetrahedral(A)and octahedral(B)sites.Specifically,doping NiFe_(2)O_(4) with Mg^(2+)ions can enhance its magnetic properties and enhance its saturation magnetization.

Super-exchange effect induced by early 3d metal doping on NiFe_(2)O_(4)(001)surface for oxygen evolution reaction

Understanding the intrinsic activity of oxygen evolution reaction(OER) is crucial for catalyst design.To date,different metal-doping strategies have been developed to achieve this,but the involving mechanisms remain unclear.Here,the electronic structure of the transition metal-doped NiFe_(2)O_(4)(001) surface is scrutinized for OER intrinsic activity using density functional theory calculations.Five 3d-orbital filling metals(Ti,V,Cr,Mn,and Co) are introduced as dopants onto A-and B-layers of the NiFe_(2)O_(4)(001) surface,and variation of oxidation states over Fe sites is observed on B-layer.Analyzing the magnetic moment and charge transfer of surface cation sites reveals that the variation of Fe oxidation states originates from the super-exchange effect and is influenced by the t2g-electron configuration of 3d metal dopants.This trend governs the generation of highly-active Fe3+sites on the B-layer,the adsorption strength of OER intermediates,i.e.,*O and*OH,and therefore the intrinsic activity.The finding of super-exchange mechanism induced by 3d early metal doping offers insights into electronic structure tailoring strategies for improving the intrinsic activity of OER electrocatalysts.

Effects of Al and Co doping on the structural stability and high temperature cycling performance of LiNi_(0.5)Mn_(1.5)O_(4) spinel cathode materials

The poor structural stability and capacity retention of the high-voltage spinel-type LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)limits their further application.Herein,Al and Co were doped in LNMO materials for a more stable structure and capacity.The LNMO,LiNi_(0.45)Al_(0.05)Mn_(1.5)O_(4)(LNAMO)and LiNi_(0.45)Co_(0.05)Mn_(1.5)O_(4)(LNCMO)were synthesized by calcination at 900℃ for 8 h,which was called as solid-phase method and applied universally in industry.XRD,FT-IR and CV test results showed the synthesized samples have cation disordering Fd-3m space group structures.Moreover,the incorporation of Al and Co increased the cation disordering of LNMO,thereby increasing the transfer rate of Li+.The SEM results showed that the doped samples performed more regular and ortho-octahedral.The EDS elemental analysis confirmed the uniform distribution of each metal element in the samples.Moreover,the doped samples showed better electrochemical properties than undoped LNMO.The LNAMO and LNCMO samples were discharged with specific capacities of 116.3 mA·h·g^(-1)and 122.8 mA·h·g^(-1)at 1 C charge/discharge rate with good capacity retention of 95.8% and 94.8% after 200 cycles at room temperature,respectively.The capacity fading phenomenon of the doped samples at 50℃ and 1 C rate was significantly improved.Further,cations doping also enhanced the rate performance,especially for the LNCMO,the discharge specific capacity of 117.9 mA·h·g^(-1)can be obtained at a rate of 5 C.

Facile construction of a multilayered interface for a durable lithium‐rich cathode

Layered lithium-rich manganese-based oxide(LRMO)has the limitation of inevitable evolution of lattice oxygen release and layered structure transformation.Herein,a multilayer reconstruction strategy is applied to LRMO via facile pyrolysis of potassium Prussian blue.The multilayer interface is visually observed using an atomic-resolution scanning transmission electron microscope and a high-resolution transmission electron microscope.Combined with the electrochemical characterization,the redox of lattice oxygen is suppressed during the initial charging.In situ X-ray diffraction and the high-resolution transmission electron microscope demonstrate that the suppressed evolution of lattice oxygen eliminates the variation in the unit cell parameters during initial(de)lithiation,which further prevents lattice distortion during long cycling.As a result,the initial Coulombic efficiency of the modified LRMO is up to 87.31%,and the rate capacity and long-term cycle stability also improved considerably.In this work,a facile surface reconstruction strategy is used to suppress vigorous anionic redox,which is expected to stimulate material design in high-performance lithium ion batteries.

Effect of Al Powder and Si Powder Additions on Structure and Properties of Unburned Magnesium Aluminate Spinel Refractories

Unburned magnesium aluminate spinel refractories were prepared using sintered magnesium aluminate spinel as the main raw material,phenolic resin as the binder,aluminum powder(2%,4%,and 6%by mass)and silicon powder(when Al powder addition is 4%,Si powder addition varies:1%and 2%,by mass)as additives.The effects of the Al powder and Si powder additions on the properties and microstructure of the refractories heat treated at different temperatures(1000,1400,and 1600℃for 3 h)were studied.The results show that the Al powder addition can greatly enhance the cold modulus of rupture of the samples fired at 1000 or 1400℃,and meanwhile AlN reinforcement phase forms in the matrix,which greatly improves the hot modulus of rupture of the samples at 1400℃;however,the heat treatment at 1600℃has little influence on the strength;the addition of Al powder and Si powder results in the formation of low melting point phases,greatly reducing the hot modulus of rupture.However,the low melting point phases promote sintering,which enhances the density and the cold modulus of rupture,and decreases the volume change during heating.The samples added with Al and Si all have higher cold modulus of rupture than those added with Al powder only.

Binder Effect on Properties of Cr_(2)O_(3)-bearing Corundum-based Refractory Castables

Cr_(2)O_(3)-bearing castables bonded with reactive MgO(RM)or calcium aluminate cement(CAC)were studied to evaluate the binder effect on their performance in corrosive environments.The properties of the as-prepared castables were compared with respect to the differences in phase composition and microstructure.The corrosion behavior of the as-prepared castables by CaO-Al_(2)O_(3)-Fe_(2)O_(3)-SiO_(2)-based slag was systematically compared viarefractory cup testing at 1600℃with respect to the differences in phase composition and microstructure.The analysis indicates that RM bonded castables show higher apparent porosity,lower bulk density and strengths after drying at 110℃and firing at 1300℃,and higher permanent linear change after firing at 1300℃,but better slag corrosion and infiltration resistance compared with CAC bonded castables.