Hematite Crystals Research Articles

Kinetics of Fe3+mineral crystallization from ferrihydrite in the presence of Si at alkaline conditions and implications for nuclear waste disposal

Fe 3+ minerals are ubiquitous in diverse near-surface environments, where they exert important controls on trace species transport. In alkaline environments such as the glass-steel interface in geological high-level radioactive waste disposal sites that use cement for plugging and grouting, Fe minerals are closely associated with Si that may affect their crystallization behavior as well as their capacities to regulate hazardous element cycling. While it is well known that Si retards Fe mineral crystallization, there is currently an overall lack of quantitative information on the rates of crystallization of stable Fe minerals in the presence of Si at alkaline conditions. Crystallization of Fe 3+ minerals goethite and hematite from ferrihydrite co-precipitated with different amounts of Si was studied at pH 10 and at temperatures ranging from 50 to 80 °C using powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). Mineral abundances evaluated from Rietveld refinement of XRD data show that the proportion of goethite in the final assemblage decreases relative to hematite with increasing Si. TEM observation of goethite and hematite crystals formed in the presence of Si show significant morphological differences compared to those formed in the absence of Si. Rate constants for crystallization derived from fitting of time-dependent changes in mineral abundances with the Avrami equation show a decreasing trend with increasing Si for both goethite and hematite. Apparent activation energies for crystallization for both minerals increase with increasing Si, with that of goethite increasing more drastically compared to hematite, indicating the inhibitive effect of Si on the crystallization of both minerals. The overall inhibition of crystallization may be explained in terms of the effects of Si on the surface properties of the ferrihydrite precursor. The rate constants and apparent activation energies reported in this study may be useful in estimating the crystallization behavior and timescales of Fe minerals in both natural and engineered environments. This information may eventually be helpful in predicting the fate of hazardous elements in such environments.

Study on preparation of thermal storage ceramic by using clay shale

Shale was used as main raw material for developing thermal storage ceramics. The samples were fabricated via semi-dry pressing followed by pressureless sintering. The result showed that the sample (75% shale, 10% kaolin, 10% potash feldspar and 5% soda feldspar) fired at 1080°C exhibited the best comprehensive performance. Ocular examination reveals that no cracks were observed after 30 cycle times thermal shock tests (wind cooling from 600°C to room temperature). The results presented that the high bending strength remained after 20 cycle times thermal shock tests but plummeted at the thirtieth time. Other properties were given as follows: bulk density: 2.60g/cm3; thermal conductivity: 2.33W/(m°C); and heat storage density: 578.50mJ/m3. XRD analysis indicated that the quartz and hematite were the main solid phases in the sample. Some isolated pores, quartz crystals, granular hematite crystals and needle-like mullite crystals were observed in the matrix according to the SEM (Scanning Electron Microscope) analysis. More pores were found with temperature rizing according to SEM analysis. The relatively high content of Fe2O3 contributed to the formation of the vitreous phase and favored the densification. Overall, the introduction of shale effectively reduced the firing temperature and performed the better thermal storage properties.

Imitation of ancient black-glazed Jian bowls (Yohen Tenmoku): Fabrication and characterization

Yohen Tenmoku is a kind of famous black glazed Jian bowls made in ancient China. Here, imitations of Oil Spot Yohen Tenmoku were sintered at about 1280°C in a shuttle kiln with oxygen flow. Microstructure characteristics and chemical compositions were investigated by a combination of X-ray based and photon based characterization methods. The results showed that quartz and mullite were the main crystalline phases in the bowl bodies. At the glaze surface of the bowl, the highly reflective red iridescence and the silvery appearance of Oil Spot patterns were resulted from the precipitation of hematite (α-Fe2O3) crystals. A detailed study has revealed the partially ordered microstructure within one Oil Spot which produced the striking optical effects.

Modulated magnetic phase of structurally heterogeneous easy-plane weak ferromagnets

The modulated magnetic phase of a structurally heterogeneous easy-plane weak ferromagnet is considered in terms of the thermodynamic Landau theory of phase transitions. The temperature and field dependences of the main magnetic order modulation parameters are determined. The results obtained are compared with the experimental data obtained for the orientational phase transition into a modulated magnetic state that occurs in hematite and iron borate crystals doped with diamagnetic ions to create structural heterogeneity. The proposed theoretical model is shown to describe the entire set of experimental results consistently with some exceptions.

Orientation modulated charge transport in hematite for photoelectrochemical water splitting

Hematite is currently considered one of the most promising photoanode materials for light-driven water splitting. The photoelectrochemical performance of hematite is limited by its low conductivity. In this work, we demonstrate that the conductivity of hematite films can be tuned by controlling the orientation of hematite crystals. By applying a high magnetic field (up to 10 T) during the drop-casting preparation, hematite films composed of single crystal particles show featured texture by promoting those particles alignment with (001) normal to the substrate. By enhancing the photocurrent densities with tuned hematite orientation, the current method provides an effective way for increasing the number of carriers that can reach the surface.

Recycling of Iron Sintered Wastes Into Nanoparticles Barium Hexaferrite and Zinc-Ferrite Glass-Ceramics

About 25 % of iron oxides in the sintering process are wastes. In this paper, sintered waste (SW) was used as a source of iron oxides to prepare both hard and soft magnetic glass-ceramics via a melting-quenching technique. About 71 % by wt. of sintered waste was used for preparing soft magnetic glass-ceramics, while ∼46 % was used for preparing hard magnetic glass-ceramics. The comparison between ferrimagnetic glass-ceramics prepared from pure chemicals and that from sintered waste before and after heat treatment was studied. X-ray diffraction shows crystallization of both hematite and Zn-ferrite phases in sintered waste while pure Zn-ferrite or Ba-hexaferrite phases were crystallized in soft magnetic and hard magnetic glass-ceramics, prepared from sintered waste, respectively. Transmission electron microscopy determined the crystalliza- tion of nano-particles ∼20 nm and <15 nm for soft and hard magnetic glass-ceramics respectively. Vibrating scanning magnetometry revealed a significant increase in saturation magnetization from ∼26 emu/g for sintered waste to ∼44 emu/g in soft magnetic glass ceramics while it decreased to ∼12 emu/g for hard magnetic glass-ceramics.

Mineralogy and origin of coarse-grained segregations in the pyrometallurgical Zn-Pb slags from Katowice-Wełnowiec (Poland)

The unique among pyrometallurgical slags, coarse-grained (up to 2.5 cm) segregations (up to 40 cm long) rimmed by “aplitic” border zones occur within holocrystalline historical Zn-smelting slag in Katowice, S Poland. Slag surrounding the segregations consists of olivine, spinel series, melilite, clinopyroxene, leucite, nepheline and sulphides. Ca-olivines, kalsilite and mica compositionally similar to oxykinoshitalite occur in border zones in addition to olivine, spinel series and melilite. Miarolitic and massive pegmatite-like segregations are built of subhedral crystals of melilite, leucite, spinel series, clinopyroxene and hematite. Melilite, clinopyroxenes and spinels in the segregations are enriched in Zn relatively to original slag and to fine-grained border zones. The segregations originated as a result of crystallization from residual melt rich in volatiles (presumably CO2). The volatile-rich melt was separated during fractional crystallization of molten slag under the cover of the overlying hot (ca. 1250 °C) vesicular slag, preventing the escape of volatiles. That unique slag system is analogous to natural magmatic systems.

Controls on the Fate and Speciation of Np(V) During Iron (Oxyhydr)oxide Crystallization.

The speciation and fate of neptunium as Np(V)O2(+) during the crystallization of ferrihydrite to hematite and goethite was explored in a range of systems. Adsorption of NpO2(+) to iron(III) (oxyhydr)oxide phases was reversible and, for ferrihydrite, occurred through the formation of mononuclear bidentate surface complexes. By contrast, chemical extractions and X-ray absorption spectroscopy (XAS) analyses showed the incorporation of Np(V) into the structure of hematite during its crystallization from ferrihydrite (pH 10.5). This occurred through direct replacement of octahedrally coordinated Fe(III) by Np(V) in neptunate-like coordination. Subsequent analyses on mixed goethite and hematite crystallization products (pH 9.5 and 11) showed that Np(V) was incorporated during crystallization. Conversely, there was limited evidence for Np(V) incorporation during goethite crystallization at the extreme pH of 13.3. This is likely due to the formation of a Np(V) hydroxide precipitate preventing incorporation into the goethite particles. Overall these data highlight the complex behavior of Np(V) during the crystallization of iron(III) (oxyhydr)oxides, and demonstrate clear evidence for neptunium incorporation into environmentally important mineral phases. This extends our knowledge of the range of geochemical conditions under which there is potential for long-term immobilization of radiotoxic Np in natural and engineered environments.

Iron and silica enrichments in the middle Albian neptunian dykes from the High-Tatric Unit, Central Western Carpathians: an indication of hydrothermal activity for an extensional tectonic regime

AbstractStudies dealing with the response of subaqueous volcanic and hydrothermal activities to carbonate sedimentation in hemipelagic environments affected by tectonic processes are comparatively rare. Here, a microfacies record with combined chemical data from the neptunian dykes found at an intrabasinal ridge (Tatric Ridge; Carpathian domain of the Western Tethys), close to a source of alkaline volcanism with possible hydrothermal vents (Zliechov Basin), is presented. The characteristic features of the neptunian dykes, up to 20 cm thick, in the middle Albian echinoderm-foraminiferal limestones (Tatra Mountains, Inner Carpathians) are their red fillings. Microprobe and x-ray diffraction analyses show that this reddish material, partly mixed with sparitic clasts coming from the host limestone, consists mainly of hematite crystals which are associated with low crystalline silica and quartz. The microfacies data suggest that the reddish infillings of the dykes is partly related to dissolution processes inside the fissures that could have taken place during the transport of FeCl3 fluids together with silica gel. The fluids could have been derived from hydrothermal vents occurring along the extensional faults in the neighbouring Zliechov Basin. Rare Earth element (REE) signatures of the reddish infill (i.e. low values of total REE content, chondrite- and Post-Archean Australian Shale-normalized REE + Y patterns with negative Ce anomaly) and a high Y/Ho ratio suggest authigenic removal of REEs from the water column. This suggests that the fissures were open to the sea bottom and were in contact with sea water during their filling.

Clay mineralogy of the Boda Claystone Formation (Mecsek Mts., SW Hungary)

AbstractBoda Claystone Formation (BCF) is the host rock of the planned site for high level nuclear waste repository inHungary. Samples representing the dominant rock types of BCF were studied: albitic claystone, claystone with high illite content, and analcime bearing claystone. Clay minerals in these three rock types were characterized by Xray powder diffraction (XRD), transmission electron microscopy (TEM) and thermal analysis (DTA-TG), and the results were discussed from the point of view of the radionuclide sorption properties being studied in the future. Mineral compositions of bulk BCF samples vary in wide ranges. In the albitic sample, besides the dominant illite, few percent of chlorite represents the layer silicates in the clay fraction. Illite is the dominating phase in the illitic sample, with a few percent of chlorite. HRTEM study revealed that the thickness of illite particles rarely reaches 10 layers, usually are of 5-6 TOT layer thick. Illite crystals are generally thicker in the albitic sample than in the illitic one. The significant difference between the clay mineral characterisitics of the analcimous and the other two samples is that the former contains regularly interstratified chlorite/smectite beside the dominant illite.Based on the structural and chemical data two illite type minerals are present in the BCF samples: 1M polytype containing octahedral Fe and Mg besides Al, 2M polytype illite generally is free of Fe andMg. Close association of very thin illite plates and nanosized hematite crystals is typical textural feature for BCF.The goal of this study is to provide solid mineralogical basis for further studies focusing on radionuclide sorption properties.

Facet-Controlling Agents Free Synthesis of Hematite Crystals with High-Index Planes: Excellent Photodegradation Performance and Mechanism Insight.

Hematite (α-Fe2O3) crystals with uniform size and structure are synthesized through very facile one-pot hydrothermal methods without any additive. The as-synthesized sub-micrometer-sized α-Fe2O3 crystals with small surface areas perform superb visible light photodegradation activities, even much better than most other α-Fe2O3 nanostructures with large surface areas. Profound mechanism analyses reveal that the microwave-assisted hydrothermal (Mic-H) synthesized α-Fe2O3 is enclosed by 12 high-index {2-15} facets. The structure and the low unoccupied molecular orbital (LUMO) of the high-index planes result in the excellent photocatalytic activity. This is the first report on the formation of {2-15} plane group of hematite, and the synthesis of the hematite particles with the {2-15} planes is very simple and no any facet-controlling agent is used. This study may pave the way to further performance enhancement and practical applications of the cheap hematite materials.

Effective hexagonal magnetic anisotropy of hematite: Accounting for higher-order invariants

The contribution caused by hydrostatic pressure to the basal magnetic anisotropy of a rhombohedral easy-plane weak ferromagnet has been calculated based on the thermodynamic potential including new magnetoelastic invariants. It has been shown that, taking into account the magnetoelastic terms of a higher order with respect to the magnetic variables, it is possible to simulate the observed substantial increase in the effective hexagonal anisotropy constant in a strained hematite crystal by the action of a relatively weak hydrostatic pressure. This approach enables one to obtain additional terms proportional to the pressure in the cubic and hexagonal anisotropies. The contribution of new terms into the effective hexagonal anisotropy is substantially greater than the contribution from the previously considered addition to the uniaxial anisotropy constant. Estimates of higher-order magnetoelastic constants for hematite are presented.

Facile synthesis of ellipsoidal hematite nanostructures via an EDA-assisted solvothermal method

Novel ellipsoidal hematite nanostructures were successfully prepared by an ethylenediamine (EDA)-assisted solvothermal method. The EDA served as ligand and alkaline source, and facilitated the growth of α-Fe2O3 ellipsoids. The products were characterized by XRD, SEM, and TEM techniques. These ellipsoidal α-Fe2O3 crystals possess smooth surface, and have an average length of 360 nm and width of 170 nm in the middle part. It was found that the types of alkaline have a distinct influence on the shape of final hematite crystals. Magnetic measurement showed that the hematite ellipsoids possessed ferromagnetic nature with magnetization value of 0.64 emu/g at the maximum magnetic field and a coercivity of 178.9 Oe, respectively.

Redox state of iron during high-pressure serpentinite dehydration

The Cerro del Almirez massif (Spain) represents a unique fragment of serpentinized oceanic lithosphere that has been first equilibrated in the antigorite stability field (Atg-serpentinites) and then dehydrated into chlorite–olivine–orthopyroxene (Chl-harzburgites) at eclogite facies conditions during subduction. The massif preserves a dehydration front between Atg-serpentinites and Chl-harzburgites. It constitutes a suitable place to study redox changes in serpentinites and the nature of the released fluids during their dehydration. Relative to abyssal serpentinites, Atg-serpentinites display a low Fe3+/FeTotal(BR) (=0.55) and magnetite modal content (=2.8–4.3 wt%). Micro-X-ray absorption near-edge structure (μ-XANES) spectroscopy measurements of serpentines at the Fe–K edge show that antigorite has a lower Fe3+/FeTotal ratio (=0.48) than oceanic lizardite/chrysotile assemblages. The onset of Atg-serpentinites dehydration is marked by the crystallization of a Fe3+-rich antigorite (Fe3+/FeTotal = 0.6–0.75) in equilibrium with secondary olivine and by a decrease in magnetite amount (=1.6–2.2 wt%). This suggests a preferential partitioning of Fe3+ into serpentine rather than into olivine. The Atg-breakdown is marked by a decrease in Fe3+/FeTotal(BR) (=0.34–0.41), the crystallization of Fe2+-rich phases and the quasi-disappearance of magnetite (=0.6–1.4 wt.%). The observation of Fe3+-rich hematite and ilmenite intergrowths suggests that the O2 released by the crystallization of Fe2+-rich phases could promote hematite crystallization and a subsequent increase in fo2 inside the portion of the subducted mantle. Serpentinite dehydration could thus produce highly oxidized fluids in subduction zones and contribute to the oxidization of the sub-arc mantle wedge.

Electrochemical Signatures of Crystallographic Orientation and Counterion Binding at the Hematite/Water Interface

The interfacial electrochemistry of hematite (α-Fe2O3) is a key aspect for understanding the behavior of this important mineral phase in photocatalytic water-splitting devices as well as in terrestrial and atmospheric systems. Nano- to microsized particles are often multifaceted and exhibit terminations of varied crystallographic orientations and structures. As structure often controls reactivity, this study was devised to identify the impact of crystallographic orientation on the electrochemical response of hematite electrode surfaces contacted with technologically, geochemically, and environmentally important solutions of inorganic ions (NaCl, NaHCO3, and NH4Cl). Electrochemical impedance spectroscopy (EIS) measurements of single hematite crystals oriented along the (001) and (012) faces were used for this purpose. The EIS responses of the electrodes were described in terms of an equivalent electrical circuit that accounts for fast bulk and slower interfacial processes. Capacitance and resistance values...

The Magdalenian human burial of El Mirón Cave (Ramales de la Victoria, Cantabria, Spain): introduction, background, discovery and context

During the course of long-term excavations of El Mirón Cave in Cantabrian Spain, remains of an adult human woman were found in deposits dating to the Lower Magdalenian (18.9–18.7 cal. kya). Interred with abundant red ochre (including specular hematite crystals) in culturally rich sediments characterized by abundant lithic and osseous artifact assemblages, faunal remains dominated by red deer and ibex, with some marine shells from an Oldest Dryas shore ca. 25 km distant, the “Red Lady of El Mirón” was buried between the rear cave vestibule wall and a large block, both of which (but especially the latter-also stained with red ochre in proximity to the corpse) bear engravings, possibly symbolically related to the burial. The papers of this special issue of Journal of Archaeological Science present the stratigraphic and archeological contexts, environmental background, dating, taphonomy, spatial distribution, human osteology, dietary information of the skeleton, and the rock art, ochre, artifacts and faunas associated with this burial, the first major human interment of Magdalenian age to be discovered on the Iberian Peninsula.

Topotaxial reactions during the genesis of oriented rutile/hematite intergrowths from Mwinilunga (Zambia)

Oriented rutile/hematite intergrowths from Mwinilunga in Zambia were investigated by electron microscopy methods in order to resolve the complex sequence of topotaxial reactions. The specimens are composed of up to several-centimeter-large euhedral hematite crystals covered by epitaxially grown reticulated rutile networks. Following a top-down analytical approach, the samples were studied from their macroscopic crystallographic features down to subnanometer-scale analysis of phase compositions and occurring interfaces. Already, a simple morphological analysis indicates that rutile and hematite are met near the \(\left\langle {0 10} \right\rangle_{R} \left\{ { 10 1} \right\}_{R} ||\left\langle {00 1} \right\rangle_{H} \left\{ { 1 10} \right\}_{H}\) orientation relationship. However, a more detailed structural analysis of rutile/hematite interfaces using electron diffraction and high-resolution transmission electron microscopy (HRTEM) has shown that the actual relationship between the rutile and hosting hematite is in fact \(\left\langle {0 10} \right\rangle_{R} \left\{ { 40 1} \right\}_{R} ||\left\langle {00 1} \right\rangle_{H} \left\{ { 1 70} \right\}_{H}\). The intergrowth is dictated by the formation of \(\left\{ { 1 70} \right\}_{H} |\left\{ { 40 1} \right\}_{R}\) equilibrium interfaces leading to 12 possible directions of rutile exsolution within a hematite matrix and 144 different incidences between the intergrown rutile crystals. Analyzing the potential rutile–rutile interfaces, these could be classified into four classes: (1) non-crystallographic contacts at 60° and 120°, (2) {101} twins with incidence angles of 114.44° and their complementaries at 65.56°, (3) {301} twins at 54.44° with complementaries at 125.56° and (4) low-angle tilt boundaries at 174.44° and 5.56°. Except for non-crystallographic contacts, all other rutile–rutile interfaces were confirmed in Mwinilunga samples. Using a HRTEM and high-angle annular dark-field scanning TEM methods combined with energy-dispersive X-ray spectroscopy, we identified remnants of ilmenite lamellae in the vicinity of rutile exsolutions, which were an important indication of the high-T formation of the primary ferrian–ilmenite crystals. Another type of exsolution process was observed in rutile crystals, where hematite precipitates topotaxially exsolved from Fe-rich parts of rutile through intermediate Guinier–Preston zones, characterized by tripling the {101} rutile reflections. Unlike rutile exsolutions in hematite, hematite exsolutions in rutile form \(\left\{ { 30 1} \right\}_{R} |\left\{ {0 30} \right\}_{H}\) equilibrium interfaces. The overall composition of our samples indicates that the ratio between ilmenite and hematite in parent ferrian–ilmenite crystals was close to Ilm67Hem33, typical for Fe–Ti-rich differentiates of mafic magma. The presence of ilmenite lamellae indicates that the primary solid solution passed the miscibility gap at ~900 °C. Subsequent exsolution processes were triggered by surface oxidation of ferrous iron and remobilization of cations within the common oxygen sublattice. Based on nanostructural analysis of the samples, we identified three successive exsolution processes: (1) exsolution of ilmenite lamellae from the primary ferrian–ilmenite crystals, (2) exsolution of rutile lamellae from ilmenite and (3) exsolution of hematite precipitates from Fe-rich rutile lamellae. All observed topotaxial reactions appear to be a combined function of temperature and oxygen fugacity, fO2.

EBSD analysis of rhombohedral twinning in hematite crystals of naturally deformed iron formations

The rhombohedral twinning in hematite has an important role in the accommodation of the deformation of hematite single crystals and hematite aggregates. It is a contact twinning and occurs as lamellae parallel to the \{10{\overline 1}2\} planes of hematite as a result of twin gliding on such planes. On account of the recent applications of electron backscatter diffraction (EBSD) techniques in a wide range of microstructural studies, the determination of symmetry operations that relate crystals in a deformed crystalline aggregate is crucial for the full textural characterization. This study presents an EBSD-based crystallographic analysis of the rhombohedral twinning on hematite crystals of a naturally deformed banded iron formation. Manipulations of theoretical pole figures depicting the symmetry relation of the rhombohedral twinning and misorientation and crystallographic data obtained by EBSD are used to establish the rotational relationship between twin and parent crystals. A method for determining pairs of axes and angles of rotation was developed which can be extended to any other twin laws or misorientation patterns in any other crystal system. It was found that the hematite rhombohedral twins are related to the parent crystal by an approximately 85° rotation about the 〈02{\overline 2}1〉 directions. Hence it could be determined that this consists of a macroscopic twinning element which is an alternative to the conventional ones used to describe the symmetry of the twin. It also matches microscopic twinning elements for the rhomb twinning law. Additionally, this method allows the determination of the crystallographic orientation of the twin lamellae and which particular 〈02{\overline 2}1〉 axis satisfies the 85°〈02{\overline 2}1〉 pair of rotation. The use of an unambiguous angle–axis pair of rotation allows the identification of twin boundaries in complex and finely grained aggregates and the distinction of twinning laws in a particular crystal.

Morphology evolution of α-Fe2O3controlled via incorporation of alkaline earth metal ions

Hematite (α-Fe2O3) crystals with different morphologies were successfully fabricated via an environmental friendly hydrothermal route by applying alkaline earth metal ions along the row from Mg2+ to Ba2+ ions as structure-directing agents without employing any surfactants or templates. It was found that the ionic radii mismatch degree between the alkaline earth metal ions and Fe3+ ions played a vital role in determining the crystalline phase and morphology of the iron oxide. Pure α-Fe2O3 crystals were created with Mg2+, Ca2+ and Sr2+ ions (30.9%, 81.8% and 114.5% ionic radii mismatch degree with that of Fe3+) as additives while goethite iron oxide nanoparticles were obtained with Ba2+ ions (145.5% ionic radius mismatch degree with that of Fe3+) as additives. Mg2+ ion-induced α-Fe2O3 crystals had a quasi-cube structure with a rough surface while Ca2+-induced α-Fe2O3 crystals had a quasi-cube structure with a very smooth surface, and the edge length of which is much smaller than that of the Mg2+ ion-controlled α-Fe2O3 crystals. However, when Sr2+ ions were introduced into the reaction system, the product tended to have plate-like structures. The effects of alkaline earth metal ions on the crystal growth rate and final morphology through anisotropic incorporation were proposed in this paper. Moreover, the effects of incorporation of alkaline earth metal ions on the magnetic properties of α-Fe2O3 crystals were investigated.

Shape-controlled Synthesis of Hematite for Microwave Gas Sensing

Hematite crystals of different shapes (dendrites, cubes, spindles and rhombohedra) were obtained via a low cost and environment-friendly microwave route. The structure and morphology were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). At last, a comparative microwave gas sensing study was performed to assess the influence of morphology on sensor response.