Mössbauer Study of the Influence of Fe-Si-N Liquid in the Synthesis of β-Si3N4 from Silica

Mössbauer spectra of the products obtained by carbothermal reduction and distribution of silica in the presence of iron in the temperatures range 1200^o to 1540^o were studied. The preponderance of β- Si₃N₄ over the α form at a higher reaction temperature were assumed to be related to the formation of an Fe-Si-N liquid. The liquid did not alter its composition with the variation of reduction-temprature, Iron had no effect on the reaction mechanism below 1300^oC.     

从高锌硫铁矿中提取碱式碳酸锌的研究

探讨用硫酸分解经焙烧的高锌硫铁矿、从硫酸锌溶液中净化除去杂质、制备碱式碳酸锌的工艺条件,同时,还可以综合提取矿物中的其它有价金属。     

A Novel Mixed-Valence Tetranuclear Iron-Oxygen Clusters in the Organically Templated Iron Phosphate [H3N(CH2)2NH3]2 Fe4O(PO4)4 ċH2O

A novel iron phosphate templated with ethylenediammonium cation, [H₃N(CH₂)₂NH₃]₂ Fe₄ O(PO₄)₄H₂O, has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction, thermo-gravimetric analysis, magnetic susceptibility and Mossbauer spectroscopy. The compound crystallizes in the mono-clinic space group C2 with a= 30.3801(5),b= 10.1204(5),c= 10.0977(5) Å, = 107.712(1)°, V = 2957.5(4) ų and Z = 6. The structure contains 5 and 6-coordinated Fe atoms bridged by ₄-oxygen and PO₄ groups to form two types of mixed-valence Fe₄P₄ cubane-like clusters, which are connected via Fe- O- P bonds to give rise to intersecting channels that house the ethylenediammonium cations and water molecules. Room-temperature Mossbauer data confirm the presence of Fe^II and Fe^III.     

Acid-activated organoclays: preparation, characterisation and catalytic activity of polycation-treated bentonites

Samples of SWy-2 and SAz-1 loaded with increasing amounts of the polycation magnafloc 206, [(Me₂NCH₂CHOHCH₂)_n]ⁿ⁺Cl_n, were acid-treated using 6 M HCl at 95°C for 30, 90 and 180 min. The activity of these acid-activated polycation-exchanged clays for the conversion of α-pinene to camphene and limonene was determined and compared with that from clay samples (without polycation) acid-treated in the same manner. Acid treatment of polycation-exchanged bentonites produced hybrid catalysts which enhanced the activity of the clays for the isomerisation of α-pinene to camphene and limonene. The presence of the polycation had a more marked influence on the activity of samples derived from SAz-1 increasing the yield from 25% for acid-activated SAz-1 with no added polycation to 50% camphene for acid-activated polycation-exchanged SAz-1. The increase in yield for corresponding samples derived from SWy-2 was only from 42 to 52%. This enhancement in yield for samples derived from SAz-1 was attributed to the increased hydrophobicity of the polycation loaded clay whilst the comparable yields for SWy-2 in the absence and presence of polycation may suggest that SWy-2 disperses well in the non-polar α-pinene. The total yields (based on α-pinene) for the most active catalysts was between 80 and 90%. These yields are directly comparable with those obtained by others using zeolites and pillared clays although the acid-activated polycation-treated clays were marginally less selective towards camphene.     

Synthesis, structure and catalytic properties of Fe-substituted barium hexaaluminates

A sol–gel method using Ba and Al isopropylates and iron nitrate has been used to synthesise barium hexaaluminate partially substituted with iron. After calcination under oxygen at 1200°C the -alumina structure was obtained. Formation of the mixed BaFe_xAl_12-xO₁₉ phase occurred for x=1–4. XRD measurements showed a good crystallinity of the structure and expansion of unit cell parameters due to the presence of larger Fe³⁺ ions substituting Al³⁺ ones in octahedral sites only. Mössbauer spectroscopy revealed that Fe³⁺ ions are present in four different octahedral sites slightly distorted. Catalytic activity in methane combustion showed that an optimum was obtained for solid containing 2 Fe ions per unit cell: the increase of the amount of introduced iron was counterbalanced by the decrease of specific surface area. Intrinsic activities have been calculated for the four solids in both the fresh and aged states. It is observed that increasing iron content increases relative activities in the same ratio as the populations of iron located in two sites as deduced from Mössbauer spectroscopy. It is then tentatively assumed that activity is attributed to octahedrally coordinated Fe³⁺ ions in some specific sites.     

Piezoresistivity in Polymer-Ceramic Composites

Composite materials composed of randomly dispersed semiconducting ceramic particles in an insulating polymer matrix show a pronounced change in resistivity with pressure. Different amounts of iron oxide (Fe₃O₄) powder and antimony-doped tin oxide (SnO₂:Sb) powder were dispersed in an epoxy polymer matrix to form pressure-sensitive composites. In each family of materials, an insulator-to-semiconductor transition is observed in agreement with percolation theory. Composites within a certain range of filler content showed substantial piezoresistive effect under both uniaxial and hydrostatic pressure in which sensitivity is controlled by the choice of filler material and the volume fraction. The effect of temperature on the piezoresistance effect was also examined. Piezoresistors made from Fe₃O₄ composites showed larger temperature changes than those filled with Sb-doped SnO₂.     

Determination of the Fe2+/Fe3+ Ratio in Nuclear Waste Glasses

The Fe²⁺/Fe³⁺ ratios of 47 simulated nuclear waste glass samples with ratios varying from 0.01 (oxidized) to 1.6 (reduced) were determined by wet-chemical and Mössbauer spectral analyses. The wet-chemical method involved the spectrophotometric determination of Fe²⁺ and total iron using remote spectroscopy with fiber optic chemical sensing. Interferences from other species present in these glasses were examined and alternative analytical techniques were investigated. Results of wet-chemical and Mössbauer spectral analysis were comparable; however, the wet-chemical method is probably preferable for the analysis of highly radioactive glasses until such glasses have been shown to have satisfactory Mössbauer spectra.     

Solubility and agronomic effectiveness of partially acidulated phosphate rocks as influenced by their iron and aluminium oxide content

Partially acidulated phosphate rock (PAPR) has been shown to be an effective source of P for plants grown on acid soils. Less information in available, however, regarding the effect of the phosphate rock (PR) source on the solubility and agronomic effectiveness of PAPR.The effect of Fe₂O₃ + Al₂O₃ content in PR on the quality of PAPR produced was investigated in this study. Nine sources of PR from Africa, Latin America, and the United States, representing a range of Fe₂O₃ + Al₂O₃ from 0.7% to 12.4%, were used. In a single-step process, the finely ground PRs were partially acidulated with H₂SO₄ at the 30% or 50% acidulation level and granulated (–3.35 + 1.18 mm or –6 + 14 mesh). It was found that the water-soluble P content in PAPR decreased with increasing Fe₂O₃ + Al₂O content in the PR used. Apparently, the presence of Fe₂O₃ + Al₂O₃ resulted in a reversion of some of the water-soluble P to citrate-soluble P and sometimes even to citrate-insoluble P.A short-term (6 weeks) greenhouse study was conducted to evaluate crop response to PAPRs and single superphosphate (SSP); maize, the test crop, was grown on an acid soil (pH 4.5)—Hartsells silt loam (Typic Hapludults). The agronomic effectiveness of PAPRs with respect to SSP (in terms of dry-matter yield of maize) decreased with increasing Fe₂O₃ + Al₂O₃ content in PRs. Phosphorus uptake by maize from PAPRs was found to correlate well with water solubility but not with citrate solubility. The results obtained in this study show that the detrimental effect of Fe₂O₃ + Al₂O₃ content on the solubility and P availability of PAPR should be considered when selecting a PR for PAPR production.     

Hepcidin-Induced Iron Deficiency Is Related to Transient Anemia and Hypoferremia in Kawasaki Disease Patients

Kawasaki disease (KD) is a type of systemic vasculitis that primarily affects children under the age of five years old. For sufferers of KD, intravenous immunoglobulin (IVIG) has been found to successfully diminish the occurrence of coronary artery lesions. Anemia is commonly found in KD patients, and we have shown that in appropriately elevated hepcidin levels are related to decreased hemoglobin levels in these patients. In this study, we investigated the time period of anemia and iron metabolism during different stages of KD. A total of 100 patients with KD and 20 control subjects were enrolled in this study for red blood cell and hemoglobin analysis. Furthermore, plasma, urine hepcidin, and plasma IL-6 levels were evaluated using enzyme-linked immunosorbent assay in 20 KD patients and controls. Changes in hemoglobin, plasma iron levels, and total iron binding capacity (TIBC) were also measured in patients with KD. Hemoglobin, iron levels, and TIBC were lower (p < 0.001, p = 0.009, and p < 0.001, respectively) while plasma IL-6 and hepcidin levels (both p < 0.001) were higher in patients with KD than in the controls prior to IVIG administration. Moreover, plasma hepcidin levels were positively and significantly correlated with urine hepcidin levels (p < 0.001) prior to IVIG administration. After IVIG treatment, plasma hepcidin and hemoglobin levels significantly decreased (both p < 0.001). Of particular note was a subsequent gradual increase in hemoglobin levels during the three weeks after IVIG treatment; nevertheless, the hemoglobin levels stayed lower in KD patients than in the controls (p = 0.045). These findings provide a longitudinal study of hemoglobin changes and among the first evidence that hepcidin induces transient anemia and hypoferremia during KD’s acute inflammatory phase.     

Accumulation and Toxicity of Superparamagnetic Iron Oxide Nanoparticles in Cells and Experimental Animals

The uptake and distribution of negatively charged superparamagnetic iron oxide (Fe₃O₄) nanoparticles (SPIONs) in mouse embryonic fibroblasts NIH3T3, and magnetic resonance imaging (MRI) signal influenced by SPIONs injected into experimental animals, were visualized and investigated. Cellular uptake and distribution of the SPIONs in NIH3T3 after staining with Prussian Blue were investigated by a bright-field microscope equipped with digital color camera. SPIONs were localized in vesicles, mostly placed near the nucleus. Toxicity of SPION nanoparticles tested with cell viability assay (XTT) was estimated. The viability of NIH3T3 cells remains approximately 95% within 3–24 h of incubation, and only a slight decrease of viability was observed after 48 h of incubation. MRI studies on Wistar rats using a clinical 1.5 T MRI scanner were showing that SPIONs give a negative contrast in the MRI. The dynamic MRI measurements of the SPION clearance from the injection site shows that SPIONs slowly disappear from injection sites and only a low concentration of nanoparticles was completely eliminated within three weeks. No functionalized SPIONs accumulate in cells by endocytic mechanism, none accumulate in the nucleus, and none are toxic at a desirable concentration. Therefore, they could be used as a dual imaging agent: as contrast agents for MRI and for traditional optical biopsy by using Prussian Blue staining.