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.

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.

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.

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.

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.

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.

固体废弃物铝灰和粉煤灰原位合成Spinel-Sialon复相材料的研究

本文利用铝灰和粉煤灰为原料,经原位铝热还原氮化法合成了Spinel-Sialon复相材料。通过XRD、SEM、EDS等分析手段,研究了合成温度和还原剂铝的添加量对合成产物物相及微观形貌的影响。结果表明:合成Spinel-Sialon的优化工艺参数为铝的添加量为过量100%、合成温度为1550℃,保温时间3 h,合成得到发育良好的柱状β-Sialon及八面体形的镁铝尖晶石。合成温度、还原剂铝的添加量均是影响氮化产物的重要因素。随着温度的升高或还原剂铝的添加量增多,Al2O3越来越少,β-Sialon和镁铝尖晶石均增多,且β-Sialon的Z值增大,MgAl2O4转变成富铝尖晶石。

活性CP-Spinel复合生物材料的研究

采用Ｘ射线衍射、扫描电镜和差热分析等手段，研究了钙磷化合物－镁铝尖晶石（ＣＰ－Ｓｐｉｎｅｌ）复合生物材料的微观结构、力学性能和生物学特性。结果表明，Ｓｐｉｎｅｌ的加入显著地提高ＣＰ材料的力学性能，在高温下它还阻止磷酸钙发生相转变，从而保证了该材料的生物活性及适合于人体骨需求的力学性能．ＣＰ－Ｓｐｉｎｅｌ材料具有很好的生物相容性，无毒无刺激性，溶血指数小于２％。

Spinel增强HAP·TCP复合生物材料研究

采用化学共沉淀法制得羟基磷灰石(HAP)粉和铝镁尖晶石(Spinel)粉,并以HAP粉体和Spinel粉体为原料采用粉末冶金方法制得HAP·TCF-Spinel复合生物材料。采用红外光谱分析、X射线衍射、透射电镜、扫描电镜、金相、力学性能测试和蛋白质吸附实验等对上述合成的材料进行了表征。微观结构表明HAP·TCP与Spinel两相分布均匀,且界面结合良好。该复合材料具有良好的抗弯强度(σ抗弯)和抗压强度(σ抗压)。当HAP的含量为62.5wt％时其抗弯强度和抗压强度分别达到σ抗弯=212MPa,σ抗压=352MPa。蛋白质吸附实验表明,HAP·TCP-S-Spinel复合生物材料对白蛋白和血清蛋白具有较强的吸附能力。

Spinel Castables for Steel Ladle Lining:In-Situ Versus Preformed

The paper discusses the difference in the formulation concepts of alumina - spinel （spinel containing ） and alumina - magnesia （ spin, el forming） castables and the influence on their physical properties. The individual property profile is discussed with respect to the requirements of refactory lining materials for the different zones of a steel ladle.

Effect of Ultrafine Spinel Sources on Slag Resistance and Microstructure of Alumina-spinel Castables

In order to clarify the effect of ultrafine spinel sources on slag resistance and microstructure of alumina -spinel castables,using tabular alumina and spinel as coarse aggregates,tabular alumina powders,spinel powders,calcium aluminate cement,spinel containing cement,spinel micro-powder and reactive alumina ultrafines as matrix,alumina-spinel castables used for RH snorkels were prepared by changing the particle size and sources of preformed spinel.The effects of different ultrafine spinel sources (CMA72,spinel micro-powder) on the properties of alumina-spinel castables were investigated.Thermal shock resistance and slag resistance of specimens were compared by the residual strength rate (1 100 ℃,air cooling 1 cycle) and static crucible method.The microstructure and the slag corrosion resistance mechanism of the specimens were analyzed by SEM and EDS.The result shows that slag resistance of alumina-spinel castables can be improved by adding ultrafine preformed spinel,such as CMA72,and spinel micro-powder.The introduction of ultra-fine preformed spinel has little effect on HMOR of alumina-spinel castables,but has negative effect on TSR.ultra-fine and dispersive preformed spinel in the matrix and fine microstructure are the main reasons for the improvement of slag resistance of castables.

Effect of FeO on the formation of spinel phases and chromium distribution in the CaO-SiO_2-MgO-Al_2O_3-Cr_2O_3 system

Synthetic slag samples of the CaO-SiO2-MgO-A1203-Cr203 system were obtained to clarify the effect of FeO on the formation of spinel phases and Cr distribution. X-ray diffraction （XRD） and scanning electron microscopy （SEM） equipped with energy-dispersive spectroscopy （EDS）, as well as the thermodynamic software FactSage 6.2, were used for sample characterization. The results show that the addition of FeO can decrease the viscosity of molten slag and the precipitation temperatures of melilite and merwinite. The solidus temperature significantly decreases from 1400 to 1250℃ with the increase of FeO content from 0wt% to 6wt%. The addition of FeO could enhance the content of Cr in spinel phases and reduce the content of Cr in soluble minerals, such as merwinite, melilite, and dicalcium silicate. Hence, the addition of FeO is conducive to decreasing Cr leaching.

Feasibility of aluminum recovery and MgAl_2O_4 spinel synthesis from secondary aluminum dross

The feasibility of aluminum recovery from secondary aluminum dross by extraction with NaOH solution and the subsequent synthesis of MgAl_2O_4 spinel by sintering the extracted slag were studied. The extraction percentage of soluble aluminum from the dross reached 80% at a temperature of 353 K, liquid-to-solid ratio of 12 mL·g^(-1), stirring speed of 300 r·min^(-1), and an extraction time of 15 min; the hydrolysis percentage of AlN reached 40% with an extraction time of 30 min. The activation energies of the soluble aluminum and AlN extracted from the dross were 7.15 and 8.98 kJ·mol^(-1), respectively, indicating that their kinetics were controlled by outer diffusion without a product layer. The extracted slag was sintered in the temperature range 1373–1773 K; MgAl_2O_4 spinel with a compressive strength as high as 69.4 MPa was produced in the sample sintered at 1673 K for 3 h. This value exceeds the threshold(40 MPa) prescribed by the National Standard for the Magnesia and Magnesia-alumina Refractory Bricks of China(GB/T 2275-2007). These results establish the effectiveness of aluminum recovery from secondary aluminum dross and subsequent MgAl_2O_4 spinel synthesis.

Spinel lithium titanate (Li_4Ti_5O_(12)) as novel anode material for room-temperature sodium-ion battery

This is the first time that a novel anode material, spinel Li4Ti5O12 which is well known as a ＂zero-strain＂ anode material for lithium storage, has been introduced for sodium-ion battery. The Li4Ti5O12 shows an average Na storage voltage of about 1.0 V and a reversible capacity of about 145 mAh/g, thereby making it a promising anode for sodiumion battery. Ex-situ X-ray diffraction （XRD） is used to investigate the structure change in the Na insertion/deinsertion process. Based on this, a possible Na storage mechanism is proposed.

Studies on the Influence of Sintering Temperature on Crystalline Structures of Mg-Al Spinel Synthesized by Waste Aluminum Slag

Mg-Al spinel is synthesized by using industrial waste-residue and basic magnesium carbonate in the aluminum factory as the main raw materials. The influence of sintering temperature on crystalline structure and microstructure of Mg-Al spinel has been mainly discussed. The crystalline structure of sample is characterized by using XRD, SEM and relevant analytical software. The experimental results show that compared to the conventional synthetic method, the application of waste aluminum slag as the raw material can greatly decrease the synthetic tem-perature. The content of Mg-Al spinel first increases and then decreases with the rise of sintering temperature, and its purity can reach as high as 96wt% at 1550 ℃, which is therefore determined to be the optimum synthetic temperature. SEM observations demonstrate that as the rise of sintering temperature, the grain of Mg-Al spinel grows up obviously with typical octahedral characteristic appearance.

Nickel ferrite spinel as catalyst precursor in the dry reforming of methane:Synthesis,characterization and catalytic properties

Dry reforming of methane by CO2 using nickel ferrite as precursor of catalysts was investigated.Nickel ferrite crystalline particles were prepared by coprecipitation of nitrates with NaOH or ammonia followed by calcination,or by hydrothermal synthesis without calcination step.The textural and structural properties were determined by a number of analysis methods,including X-ray diffraction （XRD）,Raman spectroscopy and X-ray photoelectron spectroscopy （XPS）,among which X-ray diffraction （XRD） was at room and variable temperatures.All synthesized oxides showed the presence of micro or nanoparticles of NiFe2O4 inverse spinel,but Fe2O3 （hematite） was also present when ammonia was used for coprecipitation.The reducibility by hydrogen was studied by temperature-programmed reduction （TPR） and in situ XRD,which showed the influence of the preparation method.The surface area （BET）,particle size （Rietveld refinement）,as well as surface Ni/Fe atomic ratio （XPS） and the behavior upon reduction varied according to the synthesis method.The catalytic reactivity was investigated using isopropanol decomposition to determine the acid/base properties.The catalytic performance of methane reforming with CO2 was measured with and without the pre-treatment of catalysts under H2 in 650-800 C range.The catalytic conversions of methane and CO2 were quite low but they increased when the catalysts were pre-reduced.A significant contribution of reverse water gas shift reaction accounted for the low values of H2 /CO ratio.No coking was observed as shown by the reoxidation step performed after the catalytic reactions.The possible formation of nickel-iron alloy observed during the study of reducibility by hydrogen was invoked to account for the catalytic behavior.

Al_2O_3-ZrO_2-Spinel三元纳米复相陶瓷超塑性变形及组织演变

采用真空热压烧结工艺制备了三元纳米复相陶瓷并进行了超塑性压缩试验。结果表明:纳米复相陶瓷中的第二相在烧结和变形过程中有效地阻止了基体Al2O3的晶粒长大。在1650℃材料表现出良好的高应变速率超塑变形能力,变形抗力小于30MPa。微观组织观察表明由于变形过程中存在有益压应力,材料变形后晶界处未出现空洞,经变形量为60%的压缩变形后材料中存在较高密度的位错,位错主要存在于尖晶石和氧化锆第二相中,基体Al2O3的晶粒仍为等轴状,表明位错运动对晶界滑移起到了积极地协调作用。