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At least 73 records · Page 4

Effect of aluminum substitution on the reflectance spectra of hematite

Hematite and aluminous hematite were synthesized and the diffuse reflectance spectra were recorded for the region between 0.35 and 1.20 microns. Results show that the near-IR based minimum for the aluminous hematite is shifted longward by about 0.02 microns and is much more shallow. Also, the aluminous specimen is considerably more reflective shortward of approximately 0.55 microns where the ferritic specimen is strongly absorbing. This is noteworthy since the visible slope and the red shoulder are often used in the construction of false color and band ratio images.

Morris, R. V.↗

Synthesis and properties of Ti-substituted goethites and hematites

The objective was to synthesize Ti-substituted goethites and hematites and to characterize them using x-ray diffraction, thermogravimetric analysis, coulimetry, optical and Mossbauer spectroscopies, and magnetic data in order to determine the evidence of Ti substitution for Martian spectral data. Evidence is provided that up to 4 mole percent can be incorporated into the goethite structure during the low temperature synthesis. Because the spectral data in the visible and near-IR are not sensitive to the degree of Ti-substitution in goethites and hematites, such data cannot be used to infer the presence or absence of Ti substitution in Martian hematites and goethites.

Vempati, R. K.↗

Meridiani Planum Hematite Deposit: Potential for Preservation of Microfossils

Christensen et al., using data from the Mars Global Surveyor Thermal Emission Spectrometer (TES), have identified gray crystalline hematite in a 350 km by 750 km region near Meridiani Planum. The deposit corresponds closely to the low-albedo highlands unit sm, mapped as a wind-eroded, ancient, subaqueous sedimentary deposit. Christensen et al. interpreted the Meridiani Planum deposit to be an in-place, rock-stratigraphic sedimentary unit characterized by smooth, friable layers composed primarily of basaltic sediments with approximately 10 to 15% crystalline gray hematite. The Meridiani Planum hematite deposit has recently been designated as the prime landing site for one of the two Mars Exploration Rover (MER) spacecraft. The MER landings are scheduled for January, 2004. Christensen et al. discussed five possible mechanisms for the formation of this deposit: direct precipitation from standing, oxygenated, Fe-rich water; precipitation from Fe-rich hydrothermal fluids; low-temperature dissolution and precipitation through mobile groundwater leaching; surface weathering and coatings; thermal oxidation of magnetite-rich lavas. Four of these mechanisms involve the interactions of rock with water, and thus have implications in the search for evidence of microbial life.

C C Allen↗

Hematite at Meridiani Planum, Mars, Investigated by Simultaneous Fitting of MER Mossbauer Spectra

The Mars Exploration Rover Opportunity encountered sedimentary outcrop rocks at its landing site. Spherules with diameters in the millimeter range were found to weather from the outcrop rocks. With Opportunity s miniaturised M ssbauer spectrometer MIMOS II, hematite was detected in spherules and in the outcrop matrix [1,2]. Figure 1 shows the target Berry Bowl, where brushed outcrop and an accumulation of spherules could be investigated on sols 46 and 48 of Opportunity s mission. Hematite undergoes a transition from a weakly ferromagnetic above to an antiferromagnetic state below the Morin temperature (T(sub M) approx.265 K for chemically pure, crystalline hematite). The magnetic hyperfine splitting (B(sub hf)) shows a general decrease with increasing temperature and a drop of approx.0.8 T at T(sub M). The quadrupole splitting ((Delta)EQ) changes its sign at T(sub M), with negative values above and positive values below the transition. Crystallinity and particle size influence the magnitude and temperature dependence of the magnetic splitting and the quadrupole splitting [3].

Fleischer, I.↗

Hematite-Rich Fracture Fill at Meridiani Planum, Mars: Implications for Fluid Chemistry

The Mars Exploration Rover Opportunity has been operating at the surface of Mars for over 2100 sols and has driven a distance of approximately 20 km. Throughout the traverse, outcrop rocks with margins and fracture fill resistant to erosion have been imaged and analyzed in detail by the Moessbauer (MB) spectrometer and the Alpha Particle X-ray Spectrometer (APXS). A recent APXS analysis of an outcrop block excavated by a young impact crater shows a coating with the highest concentration of iron measured by either rover, not including the iron-nickel meteorites. Texturally, this sample (referred to as "Chocolate Hills -Aloya") appears as a cemented collection of partially fragmented \blueberries." With the exception of an elevated sulfur content, the elemental chemistry of this particular sample is entirely consistent with other analyses of hematite spherules at Merdiani Planum. As a result, it is difficult to determine whether this coating, which may have been filling a fracture in outcrop rocks prior to disruption by the impact, was simply an agglomeration of spherules or a result of a more complicated aqueous process. In contrast, a number of other fracture-filling exposures and erosion-resistant rinds have been analyzed by the APXS and MB instruments showing significant concentrations of iron in the form of hematite without the texture of spherule fragments. In one of these samples, a broken piece of fracture fill within Victoria crater referred to as "Dorsal," showed over 50% of the iron in hematite, the highest Mn concentration of any sample measured by the rovers, and elevated levels of Cl and Br. While the Fe:Mn ratio of the Dorsal analyses are comparable to that of Gusev and Meridiani basalts, it is clear that chemistry of this sample cannot be completely explained by a simple mixing of outcrop and blueberry compositions

Yen, Albert↗

Experimental Acid Weathering of Fe-Bearing Mars Analog Minerals and Rocks: Implications for Aqueous Origin of Hematite-Bearing Sediments in Meridiani Planum, Mars

A working hypothesis for Meridiani evaporite formation involves the evaporation of fluids derived from acid weathering of Martian basalts and subsequent diagenesis [1, 2]. However, there are no reported experimental studies for the formation of jarosite and gray hematite (spherules), which are characteristic of Meridiani rocks from Mars analog precursor minerals. A terrestrial analog for hematite spherule formation from basaltic rocks under acidic hydrothermal conditions has been reported [3], and we have previously shown that the hematite spherules and jarosite can be synthetically produced in the laboratory using Fe3+ -bearing sulfate brines under hydrothermal conditions [4]. Here we expand and extend these studies by reacting Mars analog minerals with sulfuric acid to form Meridiani-like rock-mineral compositions. The objective of this study is to provide environmental constraints on past aqueous weathering of basaltic materials on Mars.

Golden, D. C.↗

Pu'u Poli'ahu, Mauna Kea: A Possible Analog for the Hematite Bearing Layer Located in Gale Crater, Mars.

Hyperspectral data detected by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) on board Mars Reconnaissance Orbiter (MRO) indicated the presence of a hematite bearing ridge on Mount Sharp situated in the Gale Crater, Mars. [Fraeman]. The presence of this mineral in high concentrations is indicative of possible aqueous origins. [Fraeman] In 2012, Curiosity Rover landed in Gale Crater on Mars. Curiosity's mission is to determine Mars' habitability and is equipped with an advanced suite of scientific instruments that are capable of conducting analyses on rocks and soil. The hematite bearing ridge on Mount Sharp is thought to be a good candidate of study for Curiosity. To better understand this type of terrain, the study of analog sites similar in geologic setting is of great importance. One site thought to be a comparable analog is a cinder cone called Pu'u Poli'ahu located on the summit of Mauna Kea, Hawaiʻi. Poli'ahu is unique among the tephra cones of Mauna Kea because it is thought to have formed in subaqueous conditions approximately 170,000 to 175,000 years ago. [Porter] Consequently located on the inner flanks of Poli'ahu is a rock outcrop that contains hematite. Samples were collected from the outcrop and characterized using the following instruments: Digital Microscope, Panalytical X‐ray diffraction (XRD), and scanning electron microscope (SEM). The initial preparation of the rocks involved documenting each sample by creating powdered samples, thick sections, and photo documentation.

Adams, M. E.↗

Hematite Is a Mineralogical Marker of Ancient Climate Change on Mars

The ancient climate of Mars changed from warm to cold surface conditions. This climate transition is demonstrated by geomorphological evidence, but lacks suitable mineralogical indicators. We investigate the crystallographic properties of hematite (iron oxide) in Gale crater, measured by the Curiosity rover, and compare them to laboratory experiments. Hematite crystallite sizes are ~5 to ~65 nm in the oldest sedimentary rocks investigated by the rover (the Murray formation) and <10 nm in the younger overlying strata (Mirador and Carolyn Shoemaker formations). We attribute the larger crystallites in the Murray formation to post-depositional coarsening by groundwater in warm and wet conditions, which persisted for several million years. Hematite with small crystallites co-occurs with goethite (iron oxyhydroxide) in the overlying layers, consistent with colder and water- limited conditions.

Marek Szczerba↗

Microstructural Changes and Kinetics of Reduction of Hematite to Magnetite in CO/CO{sub 2} Gas Atmospheres

The microstructures of porous magnetite formed on gaseous reduction of dense hematite have been examined using high-resolution scanning electron microscopy. It has been shown that cellular pores are formed on reduction in the temperature range 573 K to 973 K (300 °C to 700 °C). Dendritic shaped gas pores are formed on reduction at temperatures between 1073 K and 1273 K (800 °C and 1000 °C). The apparent chemical reaction rate constant for the reduction of hematite to magnetite in CO/CO{sub 2} gas mixtures has been derived from measurements of product thickness against reaction time; the rate constant is described by the relation φ{sub CO} = 0.232exp(76,000/RT) µm s{sup −1} atm{sup −1}.

36 MATERIALS SCIENCE↗

Analysis of hematite attrition in a grid jet apparatus

Particulate attrition is of interest for novel carbon-capture processes such as chemical looping combustion because the makeup cost of oxygen carrier is a significant portion of operating cost. As such, models to study and predict attrition of various oxygen carriers in fluidized bed systems are being developed. One of the regions of concern in fluidized bed systems is the high-velocity jet region near gas distributors in a fluid bed. This work studies the attrition of hematite particles using a modified ASTM apparatus to measure the particle size distribution throughout the experiment. Bed weight and gas velocity were varied. Hematite particles above the corresponding threshold value had a severe variation of particle size distributions which decreased with time. Weight fractions of the sieves over time were fit to a linear, time-variant population balance model to offer insight into particle attrition. The first-order rate constant was modified as a decaying exponential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sound Velocity of Hematite up to 13 GPa

We performed acoustic measurements on polycrystalline hematite using ultrasonic interferometric techniques in a Kawai-type multi-anvil apparatus. The elastic moduli and their pressure derivatives were determined by fitting the experimental data to third-order finite strain equations, yielding: 𝐾 𝑆,0 = 214.8 (20) GPa, 𝐺 0 = 92.0 (2) GPa, 𝐾$^{′}_{S,0}$ = 5.70 (1), and 𝐺$^{′}_{0}$ = 0.88 (4). Modeling of the velocity profiles of hematite along hot and cold slab geotherms shows that compressional (V P ) and shear (V S ) wave velocities are 22%–24% and 53%–55% lower, respectively, compared to the Preliminary Reference Earth Model at the top of the lower mantle. Furthermore, these findings likely offer a potential explanation for the low-velocity anomalies associated with slab graveyards at the base of the lower mantle.

36 MATERIALS SCIENCE↗

Particle-based hematite crystallization is invariant to initial particle morphology

Significance Many crystallization processes occurring in nature produce highly ordered hierarchical architectures. Their formation cannot be explained using classical models of monomer-by-monomer growth. One of the possible pathways involves crystallization through the attachment of oriented nanocrystals. Thus, it requires detailed understanding of the mechanism of particle dynamics that leads to their precise crystallographic alignment along specific faces. In this study, we discover a particle-morphology–independent oriented attachment mechanism for hematite nanocrystals. Independent of crystal morphology, particles always align along the [001] direction driven by aligning interactions between (001) faces and repulsive interactions between other pairs of hematite faces. These results highlight that strong face specificity along one crystallographic direction can render oriented attachment to be independent of initial particle morphology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modulating Charge Transfer Efficiency of Hematite Photoanode with Hybrid Dual‐Metal–Organic Frameworks for Boosting Photoelectrochemical Water Oxidation

Abstract The glorious charge transfer efficiency of photoanode is an important factor for efficient photoelectrochemical (PEC) water oxidation. However, it is often limited by slow kinetics of oxygen evolution reaction. Herein, a dual transition metal‐based metal–organic frameworks (MOF) cocatalyst, Fe@Ni–MOF, is introduced into a titanium‐doped hematite (Fe 2 O 3 :Ti) photoanode. The combination of Ni and Fe can optimize the filling of 3d orbitals. Moreover, the introduction of Fe donates electrons to Ni in the MOF structure, thus, suppressing the irreversible (long‐life‐time) oxidation of Ni 2+ into Ni 3+ . The resulting Fe@Ni–MOF/Fe 2 O 3 :Ti photoanode exhibits ∼threefold enhancement in the photocurrent density at 1.23 V versus the reversible hydrogen electrode. Kinetic analysis of the PEC water oxidation processes indicates that this performance improvement is primarily due to modulating the charge transfer efficiency of hematite photoanode. Further results show that a single transition metal‐based MOF cocatalyst, Ni–MOF, exhibits slow charge transfer in spite of a reduction in surface charge recombination, resulting in a smaller charge transfer efficiency. These findings provide new insights for the development of photoelectrodes decorated with MOFs.

36 MATERIALS SCIENCE↗

A kinetic model for simulating non-equilibrium mass transport in oxides applied to hematite growth under irradiation

We propose an approach to simulating the dynamic evolution and transport of charged point defects within and through the oxide scales that form during corrosion. The method follows the cluster dynamics formalism widely adopted for radiation damage in solids, which can apply in both quasi-static and far from equilibrium conditions, such as in radiation environments. By treating each charged defect as a cluster of an atomic defect and associated unit charges, the proposed model flexibly allows charge state transitions and shifts in the Fermi level by absorption and emission of charge carriers from point defects in a reaction network with rates constrained by local equilibrium. Applying this model to hematite predicts changes in self-diffusion and oxidation kinetics in irradiation environments, surprisingly showing reduced oxidation rates in many conditions, despite enhanced self-diffusion. In conclusion, the origin of this effect lies in a change in Fermi level induced by excess vacancies formed under irradiation, which in turn suppresses the transport of cation interstitials which facilitate hematite growth.

36 MATERIALS SCIENCE↗

Mechanism of H 2 plasma-enabled reduction of hematite thin films

Hydrogen plasma is gaining significant interest as a promising pathway for direct iron ore reduction and for lowering process temperatures but the reduction mechanism remains poorly understood. In this work we analyzed the plasma and thermal reduction of thin-film hematite (Fe 2 O 3 ) at temperatures below 340 °C using X-ray diffraction and scanning electron microscopy with energy-dispersive X-ray spectroscopy. Plasma reduced the incubation period by an order of magnitude and increased the reduction rate by a factor of 2.6 compared to thermal reduction. Plasma-produced H-atoms facilitate the formation of numerous iron nucleation sites, bypassing the energetically unfavorable dissociative adsorption of H 2 on iron oxide. These iron nuclei can autocatalyze the reduction of the surrounding hematite via a hydrogen spillover mechanism. Our results demonstrate that plasma-derived H-atoms primarily impact the initial nucleation-limited stage. These new insights provide a mechanistic framework that can aid the implementation and optimization of hydrogen plasma-assisted iron oxide reduction at reduced temperatures.

08 HYDROGEN↗

Reduction kinetics of hematite powder using argon/hydrogen plasma with prospects for near net shaping of sustainable iron

Direct reduction of iron ore using hydrogen plasma is being explored as a potential solution to decarbonize the iron and steel sector. The current state-of-the-art demonstrated reduction of hematite pellets via hydrogen plasma using Ar + 10% H 2 but had slow reduction kinetics, requiring 30 minutes of plasma exposure for complete reduction. Here we show that using hematite in a powder form, easily obtainable from beneficiated ore, results in 10× faster kinetics using plasma generated from Ar + 2% H 2 shielding gas compared to the current state-of-the art. Additionally, the increased kinetics using powders and a dilute hydrogen concentration can enable the use of advanced manufacturing techniques like blown powder directed energy deposition using a plasma tungsten arc welding torch to manufacture near net shape components directly from the ore concentrates. This ore to part approach will also reduce the emissions associated with downstream processes like rolling, forging, and machining, thereby further aiding in the sectorial decarbonization efforts.

36 MATERIALS SCIENCE↗

Doping Bottleneck in Hematite: Multipole Clustering by Small Polarons

We report highly effective doping in transition metal oxides is critical to fundamentally overcome low carrier conductivity due to small polaron formation and reach their ideal efficiency for energy conversion applications. However, the optimal doping concentration in polaronic oxides such as hematite has been extremely low, for example, less than a percent, which hinders the benefits of doping for practical applications. In this work, we investigate the underlying mechanism of low optimal doping concentration with group IV (Ti, Zr, and Hf) and XIV (Si, Ge, Sn, and Pb) dopants from first-principles calculations. We find that novel dopant-polaron clustering occurs even at very low dopant concentrations and resembles electric multipoles. These multipoles can be very stable at room temperature and are difficult to fully ionize compared to separate dopants, and thus they are detrimental to carrier concentration improvement. This allows us to uncover mysteries of the doping bottleneck in hematite and provide guidance for optimizing doping and carrier conductivity in polaronic oxides toward highly efficient energy conversion applications.

36 MATERIALS SCIENCE↗