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.

The metallogenic environment of the Dounan manganese deposit,Southeast Yunnan, China: evidence from geochemistry and Mössbauer spectroscopic

The Dounan manganese deposit is a typical large-scale marine sedimentary manganese deposit of the Middle Triassic in China. The metallogenic environment and change process directly dictate the migration, enrichment, and precipitation of Mn. To better understand its metallogenetic environment, a detailed study was undertaken involving field observation, mineralogical and geochemical and M?ssbauer spectroscopic analyses. The major findings are as follows:(1) Lithofacies paleogeography, sedimentary structural characteristics, and geochemical indexes indicate that the deposits were formed in an epicontinental marine sedimentary basin environment of normal salinity;(2) there were three ore phases including Mn oxides, Mn carbonates, and mixed Mn ores. The ore minerals found were braunite, manganite, Ca-rhodochrosite, manganocalcite, and kutnahorite. Petrographic and mineralogical information indicates that the metallogenic environment was a weakly alkaline and weakly oxidized to weakly reduced environment, and the mineralization occurred near the redox interface;(3) the V/(V + Ni)ratios, δCe and Fe^(2+)/Fe^(3+) found in profiles of Baigu and Gake ore sections show that the redox conditions of the ore-forming environment were continuously changing; and(4) three Fe species, α-Fe_2O_3, para-Fe^(3+), and para-Fe^(2+),were found in hematite and clay mineral samples using M?ssbauer spectrum analysis. The presence and distribution of these Fe species indicate that the deposit was formed in a typical sedimentary environment during the mineralization process. In summary, our study showed that redox was a key factor controlling the mineralization of the Dounan manganese deposit. Our results have led us to the conclusion that transgression and regression caused fluctuations in sea level, which in turn caused the change of the redox environment. M?ssbauer spectroscopy is an effective tool for studying the redox conditions of the paleoenvironment in which sedimentary manganese deposits were formed.

^(57)Fe Mössbauer spectrometry: A powerful technique to analyze the magnetic and phase characteristics in RE–Fe–B permanent magnets

This review summarizes the recent advances on the application of ^(57)Fe Mössbauer spectrometry to study the magnetic and phase characteristics of Nd–Fe–B-based permanent magnets. First of all, the hyperfine structures of the Ce_(2)Fe_(14)B,(Ce,Nd)_(2)Fe_(14)B and MM_(2)Fe_(14)B phases are well-defined by using the model based on the Wigner-Seitz analysis of the crystal structure. The results show that the isomer shift δ and the quadrupole splitting öEQ of those 2:14:1 phases show minor changes with the Nd content, while the hyperfine field Bhfincreases monotonically with increasing Nd content and its value is influenced by the element segregation and phase separation in the 2:14:1 phase. Then, the hyperfine structures of the low fraction secondary phases are determined by the ^(57)Fe Mössbauer spectrometry due to its high sensitivity. On this basis,the content, magnetic behavior, and magnetization of the REFe_(2) phase, the amorphous grain boundary(GB) phase, and the amorphous worm-like phase, as well as their effects on the magnetic properties, are systematically studied.

Investigation of the sodium storage mechanism of iron fluoride hydrate cathodes using X-ray absorption spectroscopy and mossbauer spectroscopy

Elucidation of a reaction mechanism is the most critical aspect for designing electrodes for highperformance secondary batteries.Herein,we investigate the sodium insertion/extraction into an iron fluoride hydrate(FeF_(3)·0.5H_(2)O)electrode for sodium-ion batteries(SIBs).The electrode material is prepared by employing an ionic liquid 1-butyl-3-methylimidazolium-tetrafluoroborate,which serves as a reaction medium and precursor for F^(-)ions.The crystal structure of FeF_(3)·0.5H_(2)O is observed as pyrochlore type with large open 3-D tunnels and a unit cell volume of 1129A^(3).The morphology of FeF_(3)·0.5H_(2)O is spherical shape with a mesoporous structure.The microstructure analysis reveals primary particle size of around 10 nm.The FeF_(3)·0.5H_(2)O cathode exhibits stable discharge capacities of 158,210,and 284 mA h g^(-1) in three different potential ranges of 1.5-4.5,1.2-4.5,and 1.0-4.5 V,respectively at 0.05 C rate.The specific capacities remained stable in over 50 cycles in all three potential ranges,while the rate capability was best in the potential range of 1.5-4.5 V.The electrochemical sodium storage mechanism is studied using X-ray absorption spectroscopy,indicating higher conversion at a more discharged state.Ex-situ M?ssbauer spectroscopy strengthens the results for reversible reduction/oxidation of Fe.These results will be favorable to establish high-performance cathode materials with selective voltage window for SIBs.

Mössbauer Spectroscopic Characterization of Fe Occupation of Columns in the Nb28O70 Structure

In search of an experimental route to produce linear arrays of spins without the use of nanotechnological tools, we have doped Nb28O70 with small amounts of transition metal oxides (TM;in this case Fe2O3) or rare-earth oxides3, and investigated the location of the alien metal (Fe in this case) in the structure. Previous AC magnetic susceptibility measurements at low temperatures have been consistent with the formation of arrays of TM magnetic moments along the widely spaced columns parallel to the crystallographic b-axis in the Nb28O70 structure. To obtain further details about the TM distribution, the previous investigation has been extended now to include a room-temperature Mössbauer spectroscopic analysis of the Fe-doped material. The data are consistent with the presence of low-spin Fe3+ ions in both octahedral and tetrahedral coordinations of oxygens, and confirm (as suggested in the previous work) that Fe also interchanges positions with Nb ions located at tetrahedrally coordinated sites in the columns of the structure.

Mössbauer Spectroscopic Characterization of Fe Occupation of Columns in the Nb28O70 Structure

In search of an experimental route to produce linear arrays of spins without the use of nanotechnological tools, we have doped Nb28O70 with small amounts of transition metal oxides (TM;in this case Fe2O3) or rare-earth oxides3, and investigated the location of the alien metal (Fe in this case) in the structure. Previous AC magnetic susceptibility measurements at low temperatures have been consistent with the formation of arrays of TM magnetic moments along the widely spaced columns parallel to the crystallographic b-axis in the Nb28O70 structure. To obtain further details about the TM distribution, the previous investigation has been extended now to include a room-temperature Mössbauer spectroscopic analysis of the Fe-doped material. The data are consistent with the presence of low-spin Fe3+ ions in both octahedral and tetrahedral coordinations of oxygens, and confirm (as suggested in the previous work) that Fe also interchanges positions with Nb ions located at tetrahedrally coordinated sites in the columns of the structure.

Comment on “Analyses of Mössbauer Experiments in a Rotating System: Proper and Improper Approaches” [Annals of Physics Volume 418, July 2020, 168191]

The notion of classical well localized trajectories of a single photon in Minkowski spacetime does not make any rigorous sense by the well-known existence of a proof that single photons cannot be well localized. This leads to principal difficultness when photodetection probability on relativistic non inertial frame of reference is considered. In order to resolve this tension, we extend canonical Minkowski geometry up to relevant point-free Minkowski geometry [Ann. Physics 423 (2020) 168329]. The photodetection probability density on uniformly rotating frame endrowed with point-free Lorentzian geometry is obtained. The result of S. A. Podosenov et al. [Ann. Physics 413 (2020) 168047] is obtained without any reference to unphysical notion of the classical trajectories of photon. The paper again shows the correctness of the remarkable result of Prof. C. Corda concerning the Mössbauer rotor experiment as new proof of general relativity, which has been awarded by the Gravity Research Foundation. In addition, the paper also shows various very elementary mistakes, misunderstandings and flaws by the self-called “YARK group”, which is a group of fringe researchers who attempts to promote wrong science, in particular, against the relativity theory.

X-Ray and Mössbauer Study of Magnetic Black Sand from Mayotte Island

Natural magnetic black sands are known from several sites often located in areas of volcanic origin. Their elemental and mineral composition provides information on the geology of their territory and depends on several factors occurred during their formation. A sample of black sand was collected on the seashore of the island of Mayotte in the Indian Ocean and its magnetic part was investigated by means of energy dispersive X-ray spectroscopy (EDS), powder X-ray diffraction (XRD), and MÖssbauer spectroscopy at room temperature. The mineral composition is dominantly magnetite, in good agreement with samples collected in other sites of volcanic origin. Contrary to pure magnetite, a relevant fraction of Ti was detected by EDS. The 16% Ti and 1% Mn content increase the magnetite lattice parameter to 8.4312 (25) Å. The broadening of XRD lines pointed towards a significant degree of disorder. This was confirmed by MÖssbauer spectroscopy and is attributed to the presence of Ti replacing Fe in the magnetite lattice. The presence of Ti modifies the local magnetic field on the Fe sites, leading to a broader and more complex MÖssbauer transmission spectrum with respect to the one of pure magnetite. To study the effect of temperature, samples were heated for 12 hours to 600°C and 800°C in argon and to 1000°C in air. Annealing in argon did not improve the crystallinity while annealing in air caused a complete decomposition of magnetite into hematite and pseudobrookite.

Mechanism and kinetics of iron extraction from high silica boehmite−kaolinite bauxite by hydrochloric acid leaching

The chemical and mineral compositions of bauxite recovered from the Severoonezhsk Bauxite Mine(Arkhangelsk region,Russia)were studied by XRD,ICP-OES,TG/DSC,SEM,TEM,and Mössbauer spectroscopy.The iron-containing minerals of the bauxites were found to comprise alumogoethite(α-Fe_(1−x)Al_(x)OOH),alumohematite(α-(Fe_(1−x)Al_(x))_(2)O_(3)),alumoakaganeite(β-Fe_(1−x)Al_(x)O(OH,Cl)),and chromite(FeCr_(2)O_(4)).The efficiency of Fe extraction from the bauxite by HCl leaching was 82.5%at 100℃,HCl concentration of 10%,solid/liquid ratio of 1:10,and the process duration of 60 min,with aluminum loss from the bauxites below 4.5%of the total Al contents in the bauxite.Analysis of the kinetics of the iron leaching process proved diffusion to be the limiting stage of the process at 90−100℃.Bauxite residue after leaching presented traces of α-Fe_(1−x)Al_(x)OOH and β-Fe_(1−x)Al_(x)O(OH,Cl),and most of the iron content was in the FeCr_(2)O_(4).In bauxite residue after HCl leaching,in addition to iron oxide,the contents of chromium and calcium oxides significantly decreased.The iron chloride liquor after leaching contained the rare earth elements(REE)of 6.8 mg/L Sc,4.1 mg/L Ce and 2.3 mg/L Ga.

Determination of Fe^(2+)/Fe^(3+)Ratios of Magnetite using Different Methods:A Case Study from the Qimantag Metallogenic Belt

Determination of Fe^(2+)/Fe^(3+) ratios from metallogenic belts to explore controlling physical and chemical conditions of rock formation is of great significance.In order to explore magnetite Fe^(2+)/Fe^(3+) ratios of the Qimantag metallogenic belt,part of the Eastern Kunlun orogenic belt in the northeastern margin of the Qinghai–Tibetan plateau,western Central Orogenic Belt of China,and overcome the limitation of the traditional electronic probe,five different measurement methods are proposed and their respective advantages and disadvantages evaluated,with the composition data of the magnetite obtained using electron probe microanalysis(EPMA).The direct oxygen measurement method has a significant impact on the determination results of FeO and Fe2O3,but the accuracy and uniformity of the results are low.The valence method(Flank method)based on the spectral intensity ratio of Lαto Lβfor iron is also unreliable for FeO and Fe_(2)O^(3) measurements because it is difficult to establish a relationship between Lβ/Lα,the spectral intensity ratio,and the Fe^(2+)/Fe^(3+) content ratio.In comparison,the charge difference method,the surplus-oxygen method and the Mössbauer spectrum method are still the most favorable.Mössbauer spectroscopy,with its isomer movement particularly sensitive to the oxidation state of iron,yields results closer to 0.5,which is relatively reliable.Earlier magnetite deposits are located in intrusions or contact zones and formed by magmatic fluids with high Fe2+/Fe3+ratios,whereas later magnetite deposits are farther away from intrusions and have low Fe^(2+)/Fe^(3+) ratios.The transformation mechanism of hematite and magnetite in the Qimantage metallogenic belt is also studied.No large volume changes,such as pore filling and shrinkage fracture,were detected in the metallogenic belt,and the transformation mechanism is more similar to a reoxidation and reduction mechanism.

Structural and Magnetic Studies of Ga-doped Yttrium Iron Garnet

Ga-doped Yttrium Iron Garnet (Y_(3)Ga_(x)Fe_(5-x)O_(12),Ga:YIG) was prepared by solid state reaction method and sintering at 1 300 ℃.Rietveld analysis of X-ray diffraction patterns indicated that all samples crystallized in a single cubic structure (space group Ia-3d) with decreasing lattice constant as Ga concentration increased.SEM surface micrograph images of YIG samples showed highly compacted grains with small reduction in the grain size with increasing Ga concentration.Raman spectroscopy measurements confirmed the replacement of Fe^(3+) ions by Ga^(3+) ions in the garnet structure was revealed by the observed blue shifts in Raman spectra.The saturation magnetization decreased from 28.2 to 4.98 emu g^(-1) with increasing x from 0.0 to 1.0 due to the preferential substitution of Ga^(3+) ions for Fe^(3+) ions at tetrahedral sites.Room temperature Mössbauer spectra for the samples revealed a reduction of the hyperfine field values for octahedral and tetrahedral sites,and the development of additional components with increasing Ga concentration.Analysis of the magnetic data and Mössbauer spectra confirmed that spin canting in the substituted garnets plays an important role in explaining the observed reduction of the saturation magnetization as x increased.

Structural reconstruction of Sn-based metal-organic frameworks for efficient electrochemical CO_(2) reduction to formate

MOF-based materials have been widely explored in electrochemical CO_(2)reduction reactions for the production of valuable chemicals.Understanding the reconstruction of those catalysts under working conditions is crucial for the identification of active sites and clarification of reaction mechanism.Herein,a series of six N coordinated Sn-based metal-organic frameworks(Sn-N6-MOFs)are newly developed for electrochemical CO_(2)reduction(CO_(2)RR).2%Sn-N6-MOF achieves the optimal catalytic performance with a formate Faradaic efficiency of~85%and a current density of 23 mA·cm^(-2) at-1.23 V vs.RHE.In-situ Raman results combined with ex-situ ^(119)Sn Mössbauer measurements reveal the structural reconstruction of Sn-N6-MOFs during CO_(2)RR,generating tin nanoclusters as the real active sites for CO_(2)electroreduction to HCOOH.

Recycling of Mud Derived from Backwash Wastewater Coagulation as Magnetic Sodalite Sphere for Zn^(2+) Adsorption

Herein,we reported a method to prepare magnetic sodalite sphere by using the mud from backwash wastewater after polyaluminum chloride(PAC)coagulation.The results showed that approximately 100%of Fe in the wastewater was precipitated as flocculent iron mud(FM)by adding PAC.FM was converted to spherical magnetic sodalite(FMP)with a diameter of 3μm via a facile alkali hydrothermal method without adding Al/Si resources or reductant.The product FMP had the saturated magnetization of 10.9 emu g^(-1) and high Zn^(2+)adsorption capacity of 50.6 mg g^(-1).Without coagulation with PAC,the removal rate of Fe from the wastewater was only 92.7%,and the precipitated mud(RM)was converted to irregular particles(RMP),which had weak magnetic response and low capacity of Zn^(2+)adsorption comparing with FMP.With the method,the Fe in backwash wastewater was effectively recycled,and the generated sludge was converted to well-formed sodalite sphere without generating any secondary waste.

Effect of hydrogen plasma implantation on the micro-structure and magnetic properties of hcp-Co_(80)^(57)Fe_(4)Ir_(16)thin films

We present detailed investigations of structural and static/dynamic magnetic properties of hydrogenated hcp-Co_(80)^(57)Fe_(4)Ir_(16) soft magnetic thin films.Two different kinds of defects,i.e.,destructive and non-destructive,were demonstrated by controlling the negative bias voltage of the hydrogenation process.Our results show that the structure and magnetic properties of our sample can be tuned by the density of the induced defects.These results provide better understanding of the hydrogenation effect and thus can be used in the future for materials processing to meet the requirements of different devices.

基于穆斯堡尔谱的煤气化渣中铁的析出机理

气化条件下,煤中含铁矿物被还原,气化渣中析出单质铁,影响熔渣的黏度。以铁含量较高的煤样为研究对象,借助XRD和穆斯堡尔谱分析煤中矿物尤其是含铁矿物的组成。利用高温管式炉模拟气化条件,制备不同温度不同气氛下的熔渣,采用穆斯堡尔谱定性和定量分析熔渣中的含铁物相,研究熔渣中含铁物相的生成与温度和气氛的关系,探讨单质铁的析出机理。结果表明:气氛对含铁物相的种类和含量均有显著影响;气氛中CO体积分数为60%时,熔渣中含铁物相的组成显现“拐点”特征;在φ(CO)∶φ(N2)=3∶2气氛中,温度升高,含铁物相种类减少,其质量分数变化较复杂;还原性气氛中,煤中含铁矿物以不同途径转化成单质铁;铝硅酸盐矿物中掺杂的Fe3+直接或间接地被还原,黄铁矿转化成一系列铁硫化物,断键、熔化、分解,产生单质铁;综合实验结果,建立了高温熔渣中单质铁的析出模式。

Magnetic glass-ceramics

We present the magnetic properties of magnetic glass ceramics obtained by crystallization of Fe containing borosilicate glass.Two types of nucleators have been used:Cr2O3 and P2O5.The role of the nucleators proved to be crucial in the size and morphology of the crystallites developed within glassy matrix as well in the magnetic response.The former stimulates the growth of regular single crystals uniformly dispersed within the matrix whereas the latter leads to the formation of grains made of tiny(30 nm),nanocrystals.The magnetic response depends on the amount of Fe ions left dispersed within glassy matrix as paramagnetic ions.Although P2O5 leads to the best structural magnetite,almost 42%of Fe ions are left dispersed in the matrix without magnetic interaction.In the case of Cr2O3,the paramagnetic Fe is decreased to 12%but structural deficiency in the occupancy of the Fe sites of magnetite is revealed by Mössbauer spectroscopy.

Magnetic and structural properties of pure and Cr-doped haematite:α-Fe_(2-x)Cr_(x)O_(3)(0≤x≤1)

Solid-state ceramic technique route is used for synthesizing Cr-doped haematiteaα-Fe_(2-x)Cr_(x)O_(3)(x=0,0.125,0.50 and 1)samples.Single phase and corundum(Al2O_(3))type structure is revealed from the X-ray diffraction(XRD)patterns.The Raman spectra ofαa-Fe_(2-x)Cr_(x)O_(3)illustrate seven phonon modes.On substitution of Cr(x=0,0.125,0.50 and 1)at Fe site,all Raman active modes are shifted to higher wave numbers.The coercivity and remanence of Cr-doped haematites increase as x increases.The increased coercivity and remanence for Cr-doped samples can be attributed to their enhanced shape and magneto-crystalline anisotropy.The observed isomer shiftδdvalues from room-temperature Mössbauer data clearly show the presence of ferric(Fe^(3+))and Cr^(3+)ions illustrating strong ferromagnetic ordering up to x=0.125 inaα-Fe_(2-x)Cr_(x)O_(3)haematite and weak ferromagnetic ordering foraα-Fe2-xCrxO_(3)(x>0.125)haematites.

Structural,vibrational and magnetic properties of Ti substituted bulk hematite:-Fe_(2-x)Ti_(x)O_(3)

Ti doped hematitea-Fe_(2-x)Ti_(x)O_(3)(x=0.0,0.0206 and 0.0344)samples are synthesized using solid-state ceramic route technique.Single phase and corundum(Al_(2)O_(3))type structure is revealed from the X-ray diffraction(XRD)pattern.On substitution of Ti at Fe site,all Raman active modes are shifted to higher wave numbers.An additional feature of Eu(LO)mode at about 660 cm^(-1)is observed.The E_(u) mode frequency is decreased and pronounced systematically as a function of Ti doping,and it reaches a value of 658 cm^(-1)for x=0.0344.The coercivity Hc(remanence M_(r))for x=0.0,0.0206 and 0.0344 are determined to be 995 Oe(0.44 emu/mg),1404 Oe(0.00019 emu/mg)and 2023 Oe(0.00016 emu/mg),respectively.The larger coercivity for Ti doped samples can be attributed to their enhanced shape and magneto-crystalline anisotropy.The observed isomer shift(d)from room temperature Mössbauer data clearly shows the presence of ferric(Fe^(3+))and Ti^(4+)ordering ofa-Fe_(2-x)Ti_(x)O_(3)for x=0.0344.

穆斯堡尔光谱仪在揭示地幔氧逸度研究中的应用

利用地幔橄榄岩包体中平衡矿物对的氧逸度计可以有效限定岩石圈地幔的氧化-还原状态.本文使用中国地质大学(武汉)新购置的WSS-10型常温穆斯堡尔光谱仪对华北地块西北部狼山地区橄榄岩包体的四相矿物开展了铁价态的直接测定.结果显示,斜方辉石Fe^(3+)/∑Fe为0.05~0.11,单斜辉石的为0.16~0.25,尖晶石的为0.16~0.22,橄榄石为0.利用橄榄石-斜方辉石-尖晶石氧逸度计,获得狼山地区岩石圈地幔氧逸度为FMQ-0.82至FMQ-0.39(均值为FMQ-0.65).该值略高于依据电子探针测试数据计算获得的氧逸度值(FMQ-1.49至FMQ-0.8,均值为FMQ-1.25),造成这一差异的原因可能是后者忽略了尖晶石晶格中Fe^(3+)过剩和阳离子空位导致的非化学计量比.与全球克拉通岩石圈地幔氧逸度值(均值为FMQ-0.35)相比,华北地块西北缘狼山地区岩石圈地幔整体表现为较还原状态,推测与深部地幔低fO_(2)熔体上升交代有关.

Relation between half-cell and fuel cell activity and stability of FeNC catalysts for the oxygen reduction reaction

FeNC catalysts are promising substitutes of platinum-type catalysts for the oxygen reduction reaction(ORR).While previous research disclosed that high pyrolysis temperatures are required to achieve good stability,it was identified that a trade-off needs to be made regarding the active site density.The central question is,if a good stability can also be reached at milder pyrolysis conditions but longer duration retaining more active sites,while enabling the defect-rich carbon to heal during a long residence time?To address this,a variation of pyrolysis temperatures and durations is used in FeNC fabrication.Carbon morphology and iron species are characterized by Raman spectroscopy and Mössbauer spectroscopy,respectively.Fuel cell(FC)activity and stability data are acquired.The results are compared to ORR activity and selectivity data from rotating ring disc electrode experiments and resulting durability in accelerated stress tests mimicking the load cycle and start-up and shut-down cycle conditions.It is discussed how pyrolysis temperature and duration affect FC activity and stability.But,more important,the results connect the pyrolysis conditions to the required accelerated stress test protocol combination to enable a prediction of the catalyst stability in fuel cells.