Magnetostriction of melt-spun Fe(85)Ga(15), Fe(78)Ni(7)Ga(15) and Fe(78)Co(7)Ga(15) stacked ribbon samples

A set of stacked ribbon samples with the compositions Fe(85)Ga(15), Fe(78)Ni(7)Ga(15) and Fe(78)Co(7)Ga(15) were prepared. XRD on these ribbons show that the binary Fe(85)Ga(15) ribbon exhibits the disordered A2 structure where as the addition of Co and Ni leads to the appearance of an additional ordered DO(3) structure. A comparison of the ratio of the XRD-line intensities gave strong evidence of a (100) texture perpendicular to the ribbon surface. The optical studied microstructure supports these results because it shows a columnar grain growth parallel to the solidification direction-which is parallel to ribbon thickness. The highest magnetostriction was found for Fe(78)Ni(7)Ga(15) (370 ppm), while the Fe(78)Co(7)Ga(15) a smaller magnetostriction of 270 ppm was found. The enhancement of the magnetostriction is attributed to the (100) texture in these ribbons. (C) 2009 Elsevier B.V. All rights reserved.

Use of conventional electrochemical techniques to produce crystalline FeRh alloys induced by Ag seed layer

By combining galvanic displacement and electrodeposition techniques, an ordered Fe20Rh80 structure deposited onto brass was investigated by X-ray diffractometry, Mössbauer spectroscopy and magnetization measurements. Mössbauer and X-ray diffraction analyses suggest that the Fe-Rh alloy directly electrodeposited onto brass displays a nanocrystalline state while a similar alloy deposited onto Ag/brass shows a faced centered cubic-like structure, with dendrites-like features. These results directly indicate that the presence of Ag seed layer is responsible for the Fe-Rh alloy crystallization process. In addition, room temperature Mössbauer data indicate firstly paramagnetic states for two Fe-species. In the dominant Fe-species (major fraction of the Mössbauer spectra), Fe atoms are situated at a cubic environment and it can be attributed to the γ-Fe20Rh80 alloy based on their hyperfine parameters. In the second species, Fe atoms are placed in a non-local symmetry, which can be related to Fe atoms at the grain boundaries or/and Fe small clusters. These Fe-clusters are in superparamagnetic state at room temperature, but they may be ordered below 45 K, as suggested by magnetization data. © 2013 Elsevier B.V. All rights reserved.

Pizgrischite, (Cu,Fe)Cu14PbBi17S35, a new sulfosalt from the Swiss Alps: Description, crystal structure and occurrence

Pizgrischite, (Cu,Fe)Cu14PbBi17S35, is a new mineral species named after the type locality, Piz Grisch Mountain, Val Ferrera, Graubunden, Switzerland. This sulfosalt occurs as thin, striated, metallic lead-grey blades measuring up to I cm in length, embedded in quartz and associated with tetrahedrite, chalcopyrite, pyrite, sphalerite, emplectite and derivatives of the aikinite-bismuthinite series. In plane-polarized light, the new species is brownish grey with no perceptible pleochroism; under crossed nicols in oil immersion, it presents a weak anisotropy with dark brown tints. Minimum and maximum reflectance values (in %) in air are: 40.7-42.15 (470 nm), 41.2-43.1 (546 nm), 41.2-43.35 (589 nm) and 40.7-43.3 (650 nm). Cleavage is perfect along 001 I and well developed on {010}. Abundant polysynthetic twinning is observed on (010). The mean micro-indentation hardness is 190 kg/mm(2) (Mohs hardness 3.3), and the calculated density is 6.58 g/cm(3). Electron-microprobe analyses yield (wt%; mean result of seven analyses): Cu 16.48, Pb 2.10, Fe 0.77, Bi 60.70, Sb 0.35, S 19.16, Se 0.04, total 99.60. The resulting empirical chemical formula is (Cu15.24Fe0.80Pb0.60)(Sigma 16.64)(Bi17.07Sb0.17)(Sigma 17.24)(S35.09Se0.03)(Sigma 35.12), in accordance with the formula derived from the single-crystal refinement of the structure, (Cu,Fe)Cu14PbBi17S35. Pizgrischite is monoclinic, space group C2/m, with the following unit-cell parameters: a 35.054(2), b3.91123(I), c43.192(2) angstrom, beta 96.713(4)degrees, V5881.24 angstrom(3), Z=4. The strongest seven X-ray powder-diffraction lines [d in angstrom (I)(hkl)] are: 5.364(40)((6) over bar 04), 4.080(50)((8) over bar 05), 3.120(40)(118), 3.104(68)((3) over bar 18), 2.759(53) ((9) over bar 11),2.752(44)(910) and 1.956(100)(020). The crystal structure is an expanded monoclinic derivative of kupcikite. Pizgrischite belongs to the cuprobismutite series of bismuth sulfosalts but, sensu stricto, it is not a homologue of cuprobismutite. At the type locality. pizarischite is the result of the Alpine metamorphism under greenschist-facies conditions of pre-Tertiary hydrothermal Cu-Bi mineralization.

Nickel incorporation in Fe(II, III) hydroxysulfate Green Rust: effect on crystal lattice spacing and oxidation products

Ni(II)-Fe(II)-Fe(III) layered double hydroxides (LDH) or Ni-containing sulfate green rust (GR2) samples were prepared from Ni(II), Fe(II) and Fe(III) sulfate salts and analyzed with X ray diffraction. Nickel is readily incorporated in the GR2 structure and forms a solid solution between GR2 and a Ni(II)-Fe(III) LDH. There is a correlation between the unit cell a-value and the fraction of Ni(II) incorporated into the Ni(II)-GR2 structure. Since there is strong evidence that the divalent/trivalent cation ratio in GR2 is fixed at 2, it is possible in principle to determine the extent of divalent cation substitution for Fe(II) in GR2 from the unit cell a-value. Oxidation forms a mixture of minerals but the LDH structure is retained if at least 20 % of the divalent cations in the initial solution are Ni(II). It appears that Ni(II) is incorporated in a stable LDH structure. This may be important for two reasons, first for understanding the formation of LDHs, which are anion exchangers, in the natural environment. Secondly, this is important for understanding the fate of transition metals in the environment, particularly in the presence of reduced Fe compounds.

Reaction of 1,1′-diacetylferrocene with hydrazine hydrate: Synthesis and X-ray crystal structures of bis(hydrazine)bis(hydrazinecarboxylato-N′,O)iron(II), [Fe(N2H4)2(O2CNHNH2)2], and the cyclic biferrocene diazine, [N(Me)CC5H4FeC5H4C(Me)N]2

1,1′-Diacetylferrocene reacts with neat hydrate over a period of 72 h at 20°C to give the dihydrazone [H2NN(Me)CC5H4FeC5H4C(Me)NNH2] (6) in almost quantitative yield. Either prolonging the reaction time or reacting 6 with fresh hydrazine causes the iron to be stripped from the metallocene and bis(hydrazine)bis(hydrazinecarboxylato-N′,O) iron(II), [Fe(N2H4)2(OOCNHNH2)2] (11), crystallizes. In the presence of Ba2+ or Mo2+ ions two molecules of complex 6 react to give the cyclic diazine [N(Me)CC5H4FeC5H4C (Me)N]2 (7) in high yield. Hydrazine is liberated in this reaction. Complexes 6 and 11 have been characterized crystallographically. The cyclic voltammograms of complexes 6 and 7 contain essentially non-reversible oxidation peaks.

Metal cluster expansion by addition of low valent group 14 reagents: III. Reaction of bis[bis(trimethylsilyl)methyl]tin with M3(CO)12 or its derivatives (M = Fe, Ru, or Os): the crystal and molecular structures of M3(μ-SnR2)2(CO)10(R = CH(SiMe3)2; M = Ru or Os)

The stannylene [SnR2] (R = CH(SiMe3)2) reacts in different ways with the three dodecacarbonyls of the iron triad: [Fe3(CO)12] gives [Fe2(CO)8(μ-SnR2)], [Ru3(CO)12] gives the planar pentametallic cluster [Ru3(CO)10(μ-SnR2)2], for which a full structural analysis is reported, while [Os3(CO)12] fails to react. Different products are also obtained from three nitrile derivatives: [Fe3-(CO)11(MeCN)] gives [Fe2(CO)6(μ-SnR2)2], which has a structure significantly different from that of known Fe2Sn2 clusters, [Ru3(CO)10(MeCN)2] gives the pentametallic cluster described above, while [Os3(CO)10(MeCN)2] gives the isostructural osmium analogue, which shows the unusual feature of a CO group bridging two osmium atoms.

Synthesis and crystal structures of μ-oxido- and μ-hydroxido-bridged dinuclear iron(III) complexes with an N2O donor ligand - a theoretical study on the influence of weak forces on the Fe-O-Fe bridging angle

The synthesis and crystal structures of three nonheme di-iron(III) complexes with a tridentate N,N,O Schiff-base ligand, 2-({[2-(dimethylamino) ethyl] imino} methyl) phenol (HL), are reported. Complexes [Fe2OL2(NCO)(2)] (1a) and [Fe2OL2(SAL)(2)]center dot H2O [SAL = o-(CHO)C6H4O-] (1b) are unsupported mu-oxido-bridged dimers, and [Fe-2(OH)L-2(HCOO)(2)-(Cl)] (2) is a mu-hydroxido-bridged dimer supported by a formato bridging ligand. All complexes have been characterized by X-ray crystallography and spectroscopic analysis. Complex 1b has been reported previously; however, it has been reinvestigated to confirm the presence of a crucial water molecule in the solid state. Structural analyses show that in 1a the iron atoms are pentacoordinate with a bent Fe-O-Fe angle [142.7(2)degrees], whereas in 2 the metal centers are hexacoordinate with a normal Fe-OH-Fe bridging angle [137.9(2)degrees]. The Fe-O-Fe angles in complexes 1a and 1b differ significantly to those usually shown by (mu-oxido) Fe-III complexes. A theoretical study has been performed in order to rationalize this deviation. Moreover, the influence of the water molecule observed in the solid-state structure of 1b on the Fe-O-Fe angle is also analyzed theoretically.

Crystal structure of the (Mg,Fe)[UO2(P,As)O-4](2) center dot 10H(2)O solid solution - A novel mineral variety of saleeite

The crystal structure of a novel variety {[(Mg0.81Fe0.19)(H2O)(6)](H2O)(4)}{(UO2)[(P0.67As0.33)O-4]}(2) of the mineral saleeite is determined using X-ray diffraction (Bruker Smart diffractometer, lambda MoK alpha, graphite monochromator, 2 theta(max) = 56.62 degrees, R = 0.0321 for 2317 reflections, T = 100 K). The main crystal data are as follows: a = 6.952(6) angstrom, b = 19.865(5) , angstrom, c = 6.969(2) angstrom, beta = 90.806(4)degrees, space group P12(l)/n1, Z = 2, and P-calcd = 3.34 g/cm(3). It is shown that the structure is formed by alternating (along the [010] direction) anionic layers, which are composed of uranium bipyramids and T(P,As) tetrahedra, and cation layers consisting of M(Mg, Fe) octahedra and water molecules, which are joined through a system of asymmetric hydrogen bonds. The hydrogen atoms are located, the scheme of hydrogen bonds is established, and their geometric characteristics are calculated.

Synthesis, electrochemical behavior and X-ray crystal and molecular structures of [Fe(diene)(CO)(2)PPh3] (diene = chalcone, sorbic acid)

The compounds [Fe(ch)(CO)(2)PP3] (1) (ch = chalcone) and [Fe(sba)(CO)(2)PPh3] (2) (sba = sorbic acid) were prepared by irradiating the tetracarbonyltriphenylphosphineiron(0) complex in benzene in the presence of ch or sba. The compounds were characterized by infrared and P-31 NMR spectroscopies. Their electrochemical behavior was investigated by cyclic voltammetry and the results suggest that their oxidations occur by more than one electrochemical step, producing free ch and sba, free PPh3 and solvated Fe(III). It was observed that sba ligand contributes more effectively to the stabilization of metal center in these complexes, the X-ray crystal and molecular structures of 1 and 2 were determined; it was shown that the Fe atom adopts a distorted octahedral coordinated geometry in which three of the sites are occupied by the ch or sba ligand. The [Fe(ch)(CO)(2)PPh3] complex is a monomer and the unit cell of complex 2 contains exist two identical and crystallographically independent molecules of [Fe(sba)(CO)(2)PPh3] which are linked by short hydrogen bonds O-H . . .O (C) 2001 Published by Elsevier B.V. Ltd.

REACTIONS OF MERCURIC ACETATE WITH PENTACARBONYLIRON IN ALCOHOLS - CRYSTAL AND MOLECULAR-STRUCTURES OF HG[FE(COOR)(CO)(4)](2) (R=CH3, C2H5)

Reactions of Hg(CH3COO)(2) with [Fe(CO)(5)] in MeOH and EtOH lead to the compounds Hg[Fe(COOR)(CO)(4)](2) (I for R = CH3 and II for R = C2H5). Crystals of I are triclinic, P (1) over bar, with a = 6.272(2), b = 6.441(3), c = 11.703(4) Angstrom, a = 92.94(3)degrees, beta = 103.77(3)degrees, gamma = 96.10(2)degrees, and Z = 1. Crystals of II are tetragonal, I4(1)/a, with a = 17.906(3) Angstrom, c = 12.756(2) Angstrom, and Z = 8. The geometry around Hg is linear for compound I and approximately linear for compound II. The Hg-Fe distances are 2.5716(8) and 2.575(4) Angstrom for compounds I and II, respectively. The geometry around the Fe in both compounds is approximately octahedral. The carboalkoxy group is cis to Hg in both compounds with Fe-C distances equal to 2.034(6) and 2.05(4) Angstrom for compounds I and II, respectively.

Direct determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by simultaneous GFAAS using integrated platforms pretreated with W-Rh permanent modifier together with Pd plus Mg modifier

A method is proposed for the simultaneous determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by electrothermal atomic absorption spectrometry (ETAAS) using W-Rh permanent modifier together with Pd(NO3)(2) + Mg(NO3)(2) conventional modifier. The integrated platform of a transversely heated graphite atomizer (THGA) was treated with tungsten, followed by rhodium, forming a deposit containing 250 mug W + 200 mug Rh. A 500-muL, volume of fuel ethanol was diluted with 500 muL, of 0.14 mol L-1 HNO3 in an autosampler cup of the spectrometer. Then, 20 muL, of the diluted ethanol was introduced into the pretreated graphite platform followed by the introduction of 5 mug Pd(NO3)(2) + 3 mug Mg(NO3)(2). The injection of this modifier was required to improve arsenic and iron recoveries in fuel ethanol. Calibrations were carried out using multi-element reference solutions prepared in diluted ethanol (1 + 1, v/v) acidified to 0. 14 mol L-1 HNO3. The pyrolysis and atomization temperatures of the heating program were 1200degreesC and 2200degreesC, respectively, which were obtained with multielement reference solutions in acidic diluted ethanol (1 + 1, v/v; 0. 14 mol L-1 HNO3). The characteristic masses for the simultaneous determination in ethanol fuel were 78 pg Al, 33 pg As, 10 pg Cu, 14 pg Fe, 7 pg Mn, and 24 pg Ni. The lifetime of the pretreated tube was about 700 firings. The detection limits (D.L.) were 1.9 mug L-1 Al, 2.9 mug L-1 As, 0.57 mug L-1.Cu, 1.3 mug L-1 Fe, 0.40 mug L-1 Mn, and 1.3 mug L-1 Ni. The relative standard deviations (n = 12) were 4%, 4%, 3%, 1.5%, 1.2%, and 2.2% for Al, As, Cu, Fe, Mn, and Ni, respectively. The recoveries of Al, As, Cu, Fe, Mn, and Ni added to the fuel ethanol samples varied from 81% to 95%, 80% to 98%, 97% to 109%, 85% to 107%, 98% to 106% and 97% to 103%, respectively. Accuracy was checked for the Al, As, Cu, Fe, Mn, and Ni determination in 10 samples purchased at a local gas station in Araraquara-SP City, Brazil. A paired t-test showed that at the 95% confidence level the results were in agreement with those obtained by single-element ETAAS.

57 Fe and 119 Sn Mössbauer studies on new Heusler compounds for spintronic applications

Seit der Entwicklung einer großen Vielfalt von Anwendungsmöglichkeiten der Spintronik auf Basis von Heusler Verbindungen innerhalb der letzten Dekade kann der Forschungsfortschritt an dieser Material Klasse in einer Vielzahl von Publikationen verfolgt werden. Eine typische Heusler Verbindung X2YZ besteht aus zwei Übergangsmetallen (X, Y) und einem Hauptgruppenelement (Z). Diese Arbeit berichtet von Heusler Verbindungen mit besonderem Augenmerk auf deren potentielle halbmetallische Eigenschaften und davon insbesondere solche, die eine richtungsabhängige magnetische Anisotropie (perpendicular magnetic anisotropy- PMA) zeigen könnten. PMA ist insbesondere für Spin transfer Torque (STT) Bauelemente von großem Interesse und tritt in tetragonalrnverzerrten Heusler Verbindungen auf. Bei STT-Elementen werden mittels spinpolarisierter Ströme die magnetische Orientierung von magnetischen Schichten beeinflusst.rnDie signifikantesten Ergebnisse dieser Arbeit sind: die Synthese neuer kubischen Heusler Phasen Fe2YZ, die theoretisch als tetragonal vorausgesagt wurden (Kapitel 1), die Synthese von Mn2FeGa, das in der tetragonal verzerrten Struktur kristallisiert und Potential für STT Anwendungen zeigt (Kapitel 2); die Synthese von Fe2MnGa, das einen magnetischen Phasenübergang mit exchange-bias (EB) Effekt zeigt, der auf einer Koexistenz von ferromagnetischen (FM) und antiferromagnetischen (AFM) Phasen beruht (Kapitel 3); Schlussendlich wird in Kapitel 4 die Synthese von Mn3−xRhxSn diskutiert, in welcher insbesondere tetragonales Mn2RhSn als potentielles Material für Anwendungen in derrnSpintronik vorgestellt wird.rnIn dieser Arbeit wurden hauptsächlich Heusler Verbindungen mit mößbaueraktiven Elementen 57Fe und 119Sn, synthetisiert und untersucht. Im Falle der hier untersuchten Heusler Verbindungen spielt die Charakterisierung durch Mößbauer Spektroskopie eine entscheidende Rolle, da Heusler Verbindungen meistens ein gewisses Maß an Fehlordnung aufweisen, welche deren magnetischen und strukturellen Eigenschaften beeinflussen kann. Die Art der Fehlordnung jedoch kann nur schwer durch standard Pulver-Röntgendiffraktion bestimmt werden, weshalb wir die Vorteile der Mößbauer Spektroskopie als lokale Methode nutzen, um den Typ und den Grad der Fehlordnung aufzuklären. rnDiese Arbeit ist wie folgt gegliedert:rnIn Kapitel 1 wurden die neuen, kubisch-weichferromagnetischen Heuslerphasen Fe2NiGe, Fe2CuGa und Fe2CuAl synthetisiert und charakterisiert. In vorangegangenen theoretischen Studien wurde für deren Existenz in tetragonaler Heuslerstruktur vorhergesagt.rnUngeachtet dessen belegten unsere experimentellen Untersuchungen, dass diese Verbindungen hauptsächlich in der kubischen invers Heusler(X-) struktur mit unterschiedlichen Anteilen an atomarer Fehlordnung kristallisieren. Alle Verbindungen sind weiche Ferromagneten mit hoher Curietemperatur bis zu 900K, weswegen alle als potentielle Materialien für magnetische Anwendungen geeignet sind. In Kapitel 2 wurde Mn2FeGa synthetisiert. Es zeigte sich, dass Mn2FeGa nach Temperatur Nachbehandlung bei 400°C die invers tetragonale Struktur (I4m2) annimmt. Theoretisch wurde die Existenz in der inversen kubischen Heuslerstruktur vorausgesagt. Abhängig von den Synthesebedingungen ändern sich die magnetischen und strukturellen Eigenschaften von Mn2FeGa eklatant. Deshalb ändert sich die Kristallstruktur von M2FeGa bei Temperung bei 800 °C zu einer pseudokubischen Cu3Au-artigen Struktur, in welcher Fe- und Mn-Atome statistisch verteilt vorliegen. Dieser Übergang der Kristallstrukturen wurde durch Mößbauer Spektroskopie anhand des Vorliegens oder Fehlens der Quadrupolaufspaltung im Falle der invers tetragonalen bzw. pseudokubischen Modifikation nachgewiesen. In Kapitel 3 wurde Fe2MnGa ebenfalls erfolgreich synthetisiert und durch verschiedene Methoden charakterisiert. Der Zusammenhang von Kristallstruktur und magnetischen Eigenschaften wurde durch verschiedene Temperungskonditionen und mechanischer Behandlung untersucht. Der Schwerpunkt lag auf einer geschmolzenen Probe ohne weitere Temperung, die einen FM-AFM Phasenübergang zeigte. Diese magnetische Phasenumwandlung führt zu einem starken EB-Verhalten, welches seinen Ursprung hauptsächlich in der Koexistenz von FM- und AFM-Phasen unterhalb der FMAFM- Übergangstemperatur hat. Kapitel 4 ist den neuen Mn-basierten Heusler-Verbindungen Mn3−xRhxSn gewidmet, bei denen wir versuchten, durch den Austausch von Mn durch das größere Rh eine Umwandlung zu einer tetragonalen Struktur von den hexagonalen Mn3Sn-Struktur zu erreichen. Als interessant stellten sich Mn2RhSn und Mn2.1Rh0.9Sn heraus, da sie aus nur einer Phase vorzuliegen scheinen, wohingegen die anderen Verbindungen aus gemischten Phasen mit gleichzeitiger starken Fehlordnung bestehen. Im abschließenden Anhang wurden die Fehlordnung und gelegentliche Mischphasen einer großen Auswahl von Mn3−xFexGa Materialien mit 1≤x≤3, dokumentiert.rn