Low temperature electrical transport properties of carbon matrix containing iron nanoparticles

We present a comparative study of the low temperature electrical transport properties of the carbon matrix containing iron nanoparticles and the films. The conductivity of the nanoparticles located just below the metal-insulator transition exhibits metallic behavior with a logarithmic temperature dependence over a large temperature interval. The zero-field conductivity and the negative magnetoresistance, showing a characteristic upturn at liquid helium temperature, are consistently explained by incorporating the Kondo relation and the two dimensional electron-electron interaction. The films, in contrast, exhibit a crossover of the conductivity from power-law dependence at high temperatures to an activated hopping law dependence in the low temperature region. The transition is attributed to changes in the energy dependence of the density of states near the Fermi level. The observed magnetoresistance is discussed in terms of quantum interference effect on a three-dimensional variable range hopping mechanism.

Investigations of the reduction behavior of Iron-impregnated alumina gels (Fe/AlOOH) and the formation of Fe0-Al2O3 metal-ceramic composites

Fe/AlOOH gels calcined and reduced at different temperatures have been investigated by a combined use of Mossbauer spectroscopy, x-ray diffraction, and electron microscopy in order to obtain information on the nature of the iron species formed as well as the various reduction processes. Calcination at or below 1070 K mainly gives reducible Fe3+ while calcination at higher temperatures gives substitutional Fe3+ in the form of Al2-xFexO3. The Fe3+ species in the calcined samples are, by and large, present in the form of small superparamagnetic particles. Crystallization of Al2O3 from the gels is catalyzed by Fe2O3 as well as FeAl2O4. Fe (20 wt. %)/AlOOH gels calcined at or below 870 K give FeAl2O4 when reduced in hydrogen at 1070 K or lower and a ferromagnetic Fe0-Al2O3 composite (with the metallic Fe particles >100 angstrom) when reduced at 1270 K. Samples calcined at 1220 K or higher give the Fe0-Al2O3 composite when reduced in the 870-12,70 K range, but a substantial proportion of Fe3+ remains unreduced in the form of Al2-xFexO3, showing thereby the extraordinary stability of substitutional Fe3+ to reduction even at high temperatures. Besides the ferromagnetic Fe0-Al2O3 composite, high-temperature reduction of Al2-xFexO3 yields a small proportion of superparamagnetic Fe0-Al2O3 wherein small metallic particles (<100 angstrom) are embedded in the ceramic matrix. In order to preferentially obtain the Fe0-Al2O3 composite on reduction, Fe/AlOOH gels should be calcined at low temperatures (less-than-or-equal-to 1100 K); high-temperature calcination results in Al2-xFexO3. Several modes of formation of FeAl2O4 are found possible during reduction of the gels, but a novel one is that involving the reaction, 2Fe3+ + Fe0 --> 3Fe2+.

Synthesis of pure iron magnetic nanoparticles in large quantity

Free nanoparticles of iron (Fe) and their colloids with high saturation magnetization are in demand for medical and microfluidic applications. However, the oxide layer that forms during processing has made such synthesis a formidable challenge. Lowering the synthesis temperature decreases rate of oxidation and hence provides a new way of producing pure metallic nanoparticles prone to oxidation in bulk amount (large quantity). In this paper we have proposed a methodology that is designed with the knowledge of thermodynamic imperatives of oxidation to obtain almost oxygen-free iron nanoparticles, with or without any organic capping by controlled milling at low temperatures in a specially designed high-energy ball mill with the possibility of bulk production. The particles can be ultrasonicated to produce colloids and can be bio-capped to produce transparent solution. The magnetic properties of these nanoparticles confirm their superiority for possible biomedical and other applications.

A Study on iron-based amorphous alloys : alloy development, thermodynamics and soft magnetism

Metallic glass has since its debut been of great research interest due to its profound scientific significance. Magnetic metallic glasses are of special interest because of their promising technological applications. In this thesis, we introduced a novel series of Fe-based alloys and offer a holistic review of the physics and properties of these alloys. A systematic alloy development and optimization method was introduced, with experimental implementation on transition metal based alloying system. A deep understanding on the influencing factors of glass forming ability was brought up and discussed, based on classical nucleation theory. Experimental data of the new Fe-based amorphous alloys were interpreted to further analyze those influencing factors, including reduced glass transition temperature, fragility, and liquid-crystal interface free energy. Various treatments (fluxing, overheating, etc.) were discussed for their impacts on the alloying systems' thermodynamics and glass forming ability. Multiple experimental characterization methods were discussed to measure the alloys' soft magnetic properties. In addition to theoretical and experimental investigation, we also gave a detailed numerical analysis on the rapid-discharge-heating-and-forming platform. It is a novel experimental system which offers extremely fast heating rate for calorimetric characterization and alloy deformation.

The phase of iron catalyst nanoparticles during carbon nanotube growth

We study the Fe-catalyzed chemical vapor deposition of carbon nanotubes by complementary in situ grazing-incidence X-ray diffraction, in situ X-ray reflectivity, and environmental transmission electron microscopy. We find that typical oxide supported Fe catalyst films form widely varying mixtures of bcc and fcc phased Fe nanoparticles upon reduction, which we ascribe to variations in minor commonly present carbon contamination levels. Depending on the as-formed phase composition, different growth modes occur upon hydrocarbon exposure: For γ-rich Fe nanoparticle distributions, metallic Fe is the active catalyst phase, implying that carbide formation is not a prerequisite for nanotube growth. For α-rich catalyst mixtures, Fe3C formation more readily occurs and constitutes part of the nanotube growth process. We propose that this behavior can be rationalized in terms of kinetically accessible pathways, which we discuss in the context of the bulk iron-carbon phase diagram with the inclusion of phase equilibrium lines for metastable Fe3C. Our results indicate that kinetic effects dominate the complex catalyst phase evolution during realistic CNT growth recipes. © 2012 American Chemical Society.

Density Functional Theory Study of Iron and Cobalt Carbides for Fischer-Tropsch Synthesis

Carbides are important phases in heterogeneous catalysis. However, the understanding of carbide phases is inadequate: Fe and Co are the two commercial catalysts for Fischer-Tropsch (FT) synthesis, and experimental work showed that Fe carbide is the active phase in FT synthesis, whereas the appearance of Co carbide is considered as a possible deactivation cause, TO understand very different catalytic roles of carbides, all the key elementary steps in FT synthesis, that is, CO dissociation, C(1) hydrogenation, and C(1)+C(1) coupling, are extensively investigated on both carbide surfaces using first principles calculations. In particular, the most important issues in FT synthesis, the activity and methane selectivity, on the carbide surfaces are quantitatively determined and analyzed. They are also discussed together with metallic Fe and Co surfaces. It is found that (i) Fe carbide is more active than metallic Fe and has similar methane selectivity to Fe, being consistent with the experiments; and (ii) Co carbide is less active than Co and has higher methane selectivity, providing evidence on the molecular level to support the suggestion that the formation of Co carbide is a cause of relatively high methane selectivity and deactivation on Co catalysts.

Identification of species formed after pyridine adsorption on iron, cobalt, nickel and silver electrodes by SERS and theoretical calculations

The adsorption of pyridine (py) on Fe, Co, Ni and Ag electrodes was studied using surface-enhanced Raman scattering (SERS) to gain insight into the nature of the adsorbed species. The wavenumber values and relative intensities of the SERS bands were compared to the normal Raman spectrum of the chemically prepared transition metal complexes. Raman spectra of model clusters M(4)(py) (four metal atoms bonded to one py moiety) and M(4)(alpha-pyridil) where M = Ag, Fe, Co or Ni were calculated by density functional theory (DFT) and used to interpret the experimental SERS results. The similarity of the calculated M(4)(py) spectra with the experimental SERS spectra confirm the molecular adsorption of py on the surface of the metallic electrodes. All these results exclude the formation of adsorbed alpha-pyridil species, as suggested previously. Copyright (C) 2009 John Wiley & Sons, Ltd.

Evaluation of ionic degradation and slot corrosion of metallic brackets by the action of different dentifrices

OBJETIVO: avaliar in vitro a degradação iônica e corrosão do fundo do slot de braquetes metálicos submetidos à escovação com dentifrícios, realizando análises da composição química por Espectroscopia de Energia Dispersiva (EDS) e qualitativa por Microscopia Eletrônica de Varredura (MEV). MÉTODOS: foram selecionados 38 braquetes divididos aleatoriamente em quatro grupos experimentais (n = 7). Dois grupos (n = 5) funcionaram como controles positivo e negativo. Aparelhos ortodônticos simulados foram confeccionados com fios de aço inoxidável 0,019" x 0,025" e anéis elastoméricos. Os grupos foram divididos de acordo com o tratamento de superfície: G1 (Máxima Proteção Anticáries®); G2 (Total 12®); G3 (Sensitive®); G4 (Branqueador®); Controle Positivo (saliva artificial) e Controle Negativo (sem tratamento). Foram realizados 28 ciclos de escovação e avaliações antes (T0) e após (T1) o experimento. RESULTADOS: o teste de Wilcoxon indicou não existir diferença nas concentrações iônicas de titânio (Ti), cromo (Cr), ferro (Fe) e níquel (Ni) entre os grupos. O grupo G2 apresentou redução significativa (p < 0,05) na concentração do íon alumínio (Al) e os grupos G3 e G4 apresentaram aumento significativo (p < 0,05) nas concentrações do íon alumínio. A análise em MEV mostrou aumento nas características indicativas de corrosão dos grupos G2, G3 e G4. CONCLUSÃO: a análise por EDS revelou que os grupos controle e G1 não sofreram alterações na composição química. O grupo G2 apresentou degradação na quantidade de íons Al, e G3 e G4 sofreram aumento na concentração de Al. A imersão em saliva artificial e o dentifrício Máxima Proteção Anticáries® não alteraram o polimento de superfície. Os dentifrícios Total 12®, Sensitive® e Branqueador® alteraram o polimento de superfície.

Cluster-derived Gold/Iron catalysts for environmental applications

During the last years we assisted to an exponential growth of scientific discoveries for catalysis by gold and many applications have been found for Au-based catalysts. In the literature there are several studies concerning the use of gold-based catalysts for environmental applications and good results are reported for the catalytic combustion of different volatile organic compounds (VOCs). Recently it has also been established that gold-based catalysts are potentially capable of being effectively employed in fuel cells in order to remove CO traces by preferential CO oxidation in H2-rich streams. Bi-metallic catalysts have attracted increasing attention because of their markedly different properties from either of the costituent metals, and above all their enhanced catalytic activity, selectivity and stability. In the literature there are several studies demostrating the beneficial effect due to the addition of an iron component to gold supported catalysts in terms of enhanced activity, selectivity, resistence to deactivation and prolonged lifetime of the catalyst. In this work we tried to develop a methodology for the preparation of iron stabilized gold nanoparticles with controlled size and composition, particularly in terms of obtaining an intimate contact between different phases, since it is well known that the catalytic behaviour of multi-component supported catalysts is strongly influenced by the size of the metal particles and by their reciprocal interaction. Ligand stabilized metal clusters, with nanometric dimensions, are possible precursors for the preparation of catalytically active nanoparticles with controlled dimensions and compositions. Among these, metal carbonyl clusters are quite attractive, since they can be prepared with several different sizes and compositions and, moreover, they are decomposed under very mild conditions. A novel preparation method was developed during this thesis for the preparation of iron and gold/iron supported catalysts using bi-metallic carbonyl clusters as precursors of highly dispersed nanoparticles over TiO2 and CeO2, which are widely considered two of the most suitable supports for gold nanoparticles. Au/FeOx catalysts were prepared by employing the bi-metallic carbonyl cluster salts [NEt4]4[Au4Fe4(CO)16] (Fe/Au=1) and [NEt4][AuFe4(CO)16] (Fe/Au=4), and for comparison FeOx samples were prepared by employing the homometallic [NEt4][HFe3(CO)11] cluster. These clusters were prepared by Prof. Longoni research group (Department of Physical and Inorganic Chemistry- University of Bologna). Particular attention was dedicated to the optimization of a suitable thermal treatment in order to achieve, apart from a good Au and Fe metal dispersion, also the formation of appropriate species with good catalytic properties. A deep IR study was carried out in order to understand the physical interaction between clusters and different supports and detect the occurrence of chemical reactions between them at any stage of the preparation. The characterization by BET, XRD, TEM, H2-TPR, ICP-AES and XPS was performed in order to investigate the catalysts properties, whit particular attention to the interaction between Au and Fe and its influence on the catalytic activity. This novel preparation method resulted in small gold metallic nanoparticles surrounded by highly dispersed iron oxide species, essentially in an amorphous phase, on both TiO2 and CeO2. The results presented in this thesis confirmed that FeOx species can stabilize small Au particles, since keeping costant the gold content but introducing a higher iron amount a higher metal dispersion was achieved. Partial encapsulation of gold atoms by iron species was observed since the Au/Fe surface ratio was found much lower than bulk ratio and a strong interaction between gold and oxide species, both of iron oxide and supports, was achieved. The prepared catalysts were tested in the total oxidation of VOCs, using toluene and methanol as probe molecules for aromatics and alchols, respectively, and in the PROX reaction. Different performances were observed on titania and ceria catalysts, on both toluene and methanol combustion. Toluene combustion on titania catalyst was found to be enhanced increasing iron loading while a moderate effect on FeOx-Ti activity was achieved by Au addition. In this case toluene combustion was improved due to a higher oxygen mobility depending on enhanced oxygen activation by FeOx and Au/FeOx dispersed on titania. On the contrary ceria activity was strongly decreased in the presence of FeOx, while the introduction of gold was found to moderate the detrimental effect of iron species. In fact, excellent ceria performances are due to its ability to adsorb toluene and O2. Since toluene activation is the determining factor for its oxidation, the partial coverage of ceria sites, responsible of toluene adsorption, by FeOx species finely dispersed on the surface resulted in worse efficiency in toluene combustion. Better results were obtained for both ceria and titania catalysts on methanol total oxidation. In this case, the performances achieved on differently supported catalysts indicate that the oxygen mobility is the determining factor in this reaction. The introduction of gold on both TiO2 and CeO2 catalysts, lead to a higher oxygen mobility due to the weakening of both Fe-O and Ce-O bonds and consequently to enhanced methanol combustion. The catalytic activity was found to strongly depend on oxygen mobility and followed the same trend observed for catalysts reducibility. Regarding CO PROX reaction, it was observed that Au/FeOx titania catalysts are less active than ceria ones, due to the lower reducibility of titania compared to ceria. In fact the availability of lattice oxygen involved in PROX reaction is much higher in the latter catalysts. However, the CO PROX performances observed for ceria catalysts are not really high compared to data reported in literature, probably due to the very low Au/Fe surface ratio achieved with this preparation method. CO preferential oxidation was found to strongly depend on Au particle size but also on surface oxygen reducibility, depending on the different oxide species which can be formed using different thermal treatment conditions or varying the iron loading over the support.

Retrofitting boreholes contaminated with iron in rural Uganda

During my Peace Corps service as a community health liaison in rural Uganda I noticed that many improved water wells in our area had been abandoned. The communities described the water in these wells as being reddish in color, having a foul taste and odor, discoloring clothes and food, and not able to produce lather for washing. Personal investigations and an initial literature search suggested that the primary contaminant was iron. The water in these wells had a low pH and a rusty metallic smell. The water produced early in the morning appeared very red but the water became more transparent as pumping continued. The iron components of many of these wells experienced accelerated corrosion resulting in frequent pump failure. This rapid corrosion coupled with the timing of the onset of iron contamination (months to years after these wells were completed) suggests that the most likely cause of the poor quality water was iron related bacteria and/or sulphate reducing bacteria. This report describes a remedy for iron contamination employed at 5 wells. The remedy involved disinfecting the wells with chlorine and replacing iron pump components with plastic and stainless steel. Iron concentrations in the wells were less than 1 mg/L when the wells were drilled but ranged from 2.5 to 40 mg/L prior to the remedy. After the remedy was applied, the total iron concentrations returned to levels below 1 mg/L. The presence of iron related bacteria was measured in all of these wells using Biological Activity Reaction Tests. Although IRB are still present in all the wells, the dissolved iron concentrations remain less than 1 mg/L. This remedy is practical for rural areas because the work can be performed with only hand tools and costs less than US $850. Because the source of iron contamination is removed in this approach, substantial follow-up maintenance is not necessary.

INVESTIGATION OF AIR JIGGING AND AIR CLASSIFICATION TO RECOVER METALLIC PARTICLES FROM ANALYTICAL SAMPLES

Analyzing “nuggety” gold samples commonly produces erratic fire assay results, due to random inclusion or exclusion of coarse gold in analytical samples. Preconcentrating gold samples might allow the nuggets to be concentrated and fire assayed separately. In this investigation synthetic gold samples were made using similar density tungsten powder and silica, and were preconcentrated using two approaches: an air jig and an air classifier. Current analytical gold sampling method is time and labor intensive and our aim is to design a set-up for rapid testing. It was observed that the preliminary air classifier design showed more promise than the air jig in terms of control over mineral recovery and preconcentrating bulk ore sub-samples. Hence the air classifier was modified with the goal of producing 10-30 grams samples aiming to capture all of the high density metallic particles, tungsten in this case. Effects of air velocity and feed rate on the recovery of tungsten from synthetic tungsten-silica mixtures were studied. The air classifier achieved optimal high density metal recovery of 97.7% at an air velocity of 0.72 m/s and feed rate of 160 g/min. Effects of density on classification were investigated by using iron as the dense metal instead of tungsten and the recovery was seen to drop from 96.13% to 20.82%. Preliminary investigations suggest that preconcentration of gold samples is feasible using the laboratory designed air classifier.

Measurements of the Magnetic Permeabilities of the Iron-Manganese Alloy System Prepared by the Methods of Powder Metallurgy

Powder metallurgy is a branch of metallurgy which produces metallic compacts in their final forms by means of pressure and heat-treatment from the pow­ders. The products of powder metallurgy are being used in our daily lives quite often. For example, the tungsten wires in the electric bulbs to the silver-tin fillings of our teeth.

The Corrosion Resistance of Iron-Tin Compacts as Produced by Powder Metallurgy

The art of Powder Metallurgy deals with the preparation of metal powders and their utilization. As a more pertinent definition, the following has been suggest­ed: "Powder Metallurgy is the art of producing metal powders and shaped objects from individual, mixed, or alloyed metal powders, with or without the inclusion of non-metallic consti­tuents".

Instantaneous RRMI of iron rods in reduced gravity

Standard upward-burning promoted ignition tests (“Standard Test Method for Determining the Combustion Behavior of Metallic Materials in Oxygen-Enriched Atmospheres,” ASTM G4-124 [1] or “Flammability, Odor, Offgassing, and Compatibility Requirements and Test Procedures for Materials in Environments that Support Combustion,” NASA-STD-6001, NASA Test 17 [2]) were performed on cylindrical iron (99.95% pure) rods in various oxygen purities (95.0–99.98%) in reduced gravity onboard NASA JSC's KC-135 to investigate the effect of gravity on the regression rate of the melting interface. Visual analysis of experiments agrees with previous published observations showing distinct motions of the molten mass attached to the solid rod during testing. Using an ultrasonic technique to record the real-time rod length, comparison of the instantaneous regression rate of the melting interface and visual recording shows a non-steady-state regression rate of the melting interface for the duration of a test. Precessional motion is associated with a higher regression rate of the melting interface than for test periods in which the molten mass does not show lateral motion. The transition between the two types of molten mass motion during a test was accompanied by a reduced regression rate of the melting interface, approximately 15–50% of the average regression rate of the melting interface for the entire test.