The straightforward creation of an unreported glutathione-stabilised iron(iii) complex that enhances L929 fibroblast cell viability, and inhibits matrix metalloproteinase-13 activity is described.
We have developed a conceptual model describing the formation and mineralisation processes of hydroxyapatite during biogenic and abiotic treatment on cement surfaces.
Sr2Fe3Se2O3 is a localized-moment iron oxide selenide in which two unusual coordinations for Fe2+ ions form two sublattices in a 2:1 ratio. In the paramagnetic region at room temperature, the compound adopts the crystal structure first reported for Sr2Co3S2O3, crystallizing in space group Pbam with a = 7.8121 Å, b = 10.2375 Å, c = 3.9939 Å, and Z = 2. The sublattice occupied by two-thirds of the iron ions (Fe2 site) is formed by a network of distorted mer-[FeSe3O3] octahedra linked via shared Se2 edges and O vertices forming layers, which connect to other layers by shared Se vertices. As shown by magnetometry, neutron powder diffraction, and Mössbauer spectroscopy measurements, these moments undergo long-range magnetic ordering below TN1 = 118 K, initially adopting a magnetic structure with a propagation vector (1/2 - δ, 0, 1/2) (0 ≤ δ ≤ 0.1) which is incommensurate with the nuclear structure and described in the Pbam1 '( a01/2)000 s magnetic superspace group, until at 92 K ( TINC) there is a first order lock-in transition to a structure in which these Fe2 moments form a magnetic structure with a propagation vector (1/2, 0, 1/2) which may be modeled using a 2 a × b × 2 c expansion of the nuclear cell in space group 36.178 B a b21 m (BNS notation). Below TN2 = 52 K the remaining third of the Fe2+ moments (Fe1 site) which are in a compressed trans-[FeSe4O2] octahedral environment undergo long-range ordering, as is evident from the magnetometry, the Mössbauer spectra, and the appearance of new magnetic Bragg peaks in the neutron diffractograms. The ordering of the second set of moments on the Fe1 sites results in a slight reorientation of the majority moments on the Fe2 sites. The magnetic structure at 1.5 K is described by a 2 a × 2 b × 2 c expansion of the nuclear cell in space group 9.40 I a b (BNS notation).
The phase Na 5 FeSi 4 O 12 [pentasodium iron(III) silicate] crystallizes readily from the Na 2 O–Fe 2 O 3 –SiO 2 glass system in a relatively large compositional range. However, its crystal structure and properties have not been studied in detail since its discovery in 1930. In this work, the Na 5 FeSi 4 O 12 phase was crystallized from a host glass with 5Na 2 O·Fe 2 O 3 ·8SiO 2 stoichiometry, and both the glass and the crystal were studied. It was found that the Na 5 FeSi 4 O 12 phase crystallizes at ∼720 °C from the glass and melts at ∼830 °C when heated at a rate of 10 °C min −1 . The crystal structure was solved using single-crystal X-ray diffraction and the refined data are reported for the first time for the Na 5 FeSi 4 O 12 phase. It exhibits trigonal symmetry, space group R \overline{3} c , with a = 21.418 and c = 12.2911 Å. The Na atoms located between adjacent structural channels exhibit positional disorder and splitting which was only refined by using low-temperature data collection (150 K). While ∼7% of the total Fe cations occur as Fe 2+ in the glass, four-coordinated Fe 3+ constitutes ∼93% of the total Fe cations. However, iron in the crystal, which exhibits a paramagnetic behavior, is solely present as six-coordinated Fe 3+ . The magnetic and vibrational properties of the glass and crystal are discussed to provide additional insight into the structure.
Cation migration on electrochemical cycling can significantly influence the performance of li-ion cathode materials. Phases of composition LiFe2–xInxSbO6 (0 < x <1) adopt crystal structures described in space group Pnnm, consisting of a hexagonally close-packed array of oxide ions, with Fe/In and Sb cations ordered on octahedral sites, and lithium cations located within partially occupied tetrahedral sites. NPD, SXRD, and 57Fe Mössbauer data indicate that on reductive lithium insertion (either chemically or electrochemically), LiFe2SbO6 is converted to Li2Fe2SbO6 accompanied by large-scale cation migration, to form a partially Fe/Li cation-ordered and Fe2+/Fe3+ charge-ordered phase from which lithium cations cannot be easily removed, either chemically or electrochemically. Partial substitution of Fe with In suppresses the degree of cation migration that occurs on lithium insertion such that no structural change is observed when LiFeInSbO6 is converted into Li1.5FeInSbO6, allowing the system to be repeatedly electrochemically cycled between these two compositions. Phases with intermediate levels of In substitution exhibit low levels of Fe migration on Li insertion and electrochemical capacities which evolve on cycling. The mechanism by which the In3+ cations suppress the migration of Fe cations is discussed along with the cycling behavior of the LiFe1.5In0.5SbO6–Li1.75Fe1.5In0.5SbO6.
The energy intensive and CO2-generating nature of commercial mineral wool and glass production necessitates advances and changes in materials and processes. The derivation of raw materials from waste products arising from biomass energy generation offers the possibility of a two-fold environmental benefit: partial replacement of carbonate raw minerals in production, leading to lower CO2 release during melting; and the utilisation and valorisation of byproducts which may otherwise be sent to landfill. Glass samples with a basaltic mineral wool composition were produced with additions to the raw materials of 0, 1, 5 and 10 wt% of a fly ash and a bottom ash arising from biomass combustion. The resulting glasses were analysed by x-ray fluorescence, x-ray diffraction, dilatometry, 57Fe Mössbauer and Raman spectroscopies, and their densities, molar volumes and viscosity–temperature profiles were calculated and compared against benchmark glass samples. All biomass ash-containing glasses were closely similar in both composition and properties to the benchmark glass, with up to 10 wt% ash additions to the raw materials. In addition, the use of the biomass fly ash led to a reduction in batch CO2 content estimated to be 1·5 kg CO2 per tonne of batch for each 1 wt% addition. These initial results provide evidence supporting the further development of these ash materials as potential value-added raw materials for mineral wool manufacture.
Abstract Pure (BNT) and iron-doped bismuth sodium titanate (Fe-BNT) ceramics were produced according to the formula Bi 0.5 Na 0.5 Ti 1− x Fe x O 3−0.5 x , where x = 0 to 0.1. The addition of Fe 2 O 3 enables decreasing the sintering temperature to 900 °C in comparison with 1075 °C for pure BNT, whilst also achieving lower porosities and greater densities. This is attributed to oxygen vacancy generation arising from substitution of Fe 3+ onto the Ti 4+ site of the BNT perovskite structure, and the resulting increase in mass transport that this enables during sintering. X-ray diffraction (XRD) analysis of Fe-BNT samples shows single-phase BNT with no secondary phases for all studied Fe contents, confirming complete solid solution of Fe. Rietveld refinement of XRD data revealed a pseudocubic perovskite symmetry (Pm-3m), and unit cell lengths increased with increasing Fe content. Scanning electron microscopy (SEM) showed that average grain size increases with increasing Fe content from an average grain size of ~ 0.5 μm in ( x = 0) pure BNT to ~ 5 μm in ( x = 0.1) Fe-doped BNT. Increasing Fe content also led to decreasing porosity, with relative density increasing to a maximum > 97% of its theoretical value at x = 0.07 to 0.1. The addition of Fe to BNT ceramics significantly affects electrical properties, reducing the remnant polarization, coercive field, strain and desirable ferroelectric properties compared with those of pure densified BNT. At room temperature, a high relative permittivity (ɛ′) of 1050 ( x = 0.07) at an applied frequency of 1 kHz and a lower loss factor (tanδ) of 0.006 ( x = 0.1) at an applied frequency of 300 kHz were observed by comparison with pure BNT ceramics.
Foaming during vitrification of radioactive waste in Joule-Heated Ceramic Melters (JHCM) is exacerbated by trapping of evolving gases, such as CO2, NOx and O2, beneath a viscous reaction layer. Foaming restricts heat transfer during melting. Sucrose is employed as the baseline additive at the Hanford site in Washington State, USA to reduce foaming. Alternative carbon-based reductant additives were explored in simulated, inactive Hanford high-iron HLW-NG-Fe2 feeds, for both their effect on foaming and to give insight to the behaviour of multivalent species in glass melts under different redox conditions. Graphite, coke (93% C), formic acid and HEDTA additives were compared with sucrose, and a feed with no additive. Graphite and coke additions proved most effective in reducing the maximum foam volume by 51 ± 3% and 54 ± 2%, respectively, compared with 24 ± 5% for sucrose. Lower foaming could result in more efficient vitrification in JHCMs. Reductants also affected redox ratios in the multivalent species present in the feed. The order of reduction, Mn3+/Mn2+ > Cr6+/Cr3+ > Ce3+/Ce4+ > Fe3+/Fe2+ was as predicted on the basis of their redox potentials. There is less reduction overall, particularly in the Fe3+ → Fe2+, than predicted by the calculations, attributed to the oxygenated atmosphere of the experiments.
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