The Characteristics of Mechanically Activated Mixtures of Copper Hydroxocarbonate With Aluminium

The chemical and physical processes occurring during grinding of copper hydroxocarbonates mixtures with aluminium were studied. A planetary ball mill was used. A thermogravimetry and X-ray powder diffraction method allowed to determine the composition of solid products after mechanical activation. The amount of the Cu₂(OH)₂CO₃ undecomposed andAl₂O₃⋅3H₂O, CuO, Al₂O₃, Cu⁰, Cu_xAl_y alloys and remained Al0 in the systems is strongly dependent on the duration of grinding and on the proportion of components. The comparative results are presented. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis and X-ray crystal structures of bis(3-hydroxy-4-methyl-2(3H)-thiazolethiolato-S 2,O)bis(dimethylsulfoxide-O)M,M = cobalt(II) and nickel(II)

Crystallisation of the divalent nickel and cobalt complexes of 3-hydroxy-4-methyl-2(3H)-thiazolethione (HMTT) from DMSO yields isostructural chelate complexes M(MTT)₂(dmso)₂, M = Co^II/Ni^II. The metal atom adopts distorted octahedral coordination via two bidentate MTT ligands arranged in a trans-conformation and two DMSO molecules coordinated through oxygen. Powder X-ray diffraction (PXRD) and energy-dispersive X-ray (EDX) analysis show that the materials form a continuous solid solution Co _x Ni_1–x (MTT)₂(dmso)₂ over the entire composition range 0 x 1.     

Comparative structural investigation of aluminium fluoride solvates

To get some insight by conclusions of analogy into the drying process of alcoholic aluminium fluoride sol–gels [AlF₃/(ROH)_x], the structures of α- and β-AlF₃3H₂O as well as of the nonahydrate AlF₃9H₂O are reinvestigated and discussed based on X-ray single crystal structural data. In addition, neutron diffraction experiments of the latter allowed the refinement of proton positions. In accordance with crystal structures, low-temperature solid state ²⁷Al-, ¹H- and ¹⁹F-MAS NMR spectra convincingly confirm the structural similarity between α-AlF₃3H₂O and AlF₃9H₂O, while the β-phase material is structurally different forming chain structures. Thermal analysis of AlF₃/(ROH)_x gave evidence for discrete AlF₃:ROH ratios of only 1:0.45 and 1:0.1, and solution NMR showed some similarities between aqueous and alcoholic systems.     

ESR-spectrum of silver atoms stabilized in gamma-irradiated aluminium silicate modified by nickel

ESR technique was used to study the effect of conditions chosen to prepare samples to obtain and stabilize silver atoms forming under the action of⁶⁰Co -irradiation at 77 K in aluminium silicate modified by nickel and containing silver ions. The use of¹⁰⁹Ag isotope made it possible to detect two types of silver atoms Ag_I and Ag_II in -irradiated aluminium silicate modified by nickel and containing silver ions introduced by various techniques. The parameters of the ESR-spectrum of the silver particles under study have been determined and their thermal stability has been investigated.     

Trigonale kristallfelder in oxidischen spinellverbindungen

Zusammenfassung Die Spektren der Spinellmischkristalle Ni_2-x Mg_xGeO₄ (0,0 x 1,2₅) und Co_2-x Mg_xGeO₄ (0,0 x 1,0) im Kristallfeldgebiet zeigen starke Unregelmäßigkeiten, die durch die kristallographisch begründete Annahme gedeutet werden können, daß Ni²⁺ und Co²⁺ sich in entlang der trigonalen Achse gestauchten Koordinationsoktaedem befinden. Es wird ein Kristallfeldformalismus entwickelt, der eine quantitative Behandlung dieser Spektren gestattet. Weiter zeigt sich, daß nicht immer, wenn eine trigonale Kristallfeldkomponente zugegen ist, Aufspaltungen der Oktaederbanden zu beobachten sind.

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The spectra of the spinel type phases Ni_2-x Mg_xGeO₄ (0,0 x 1,2₅) and Co_2-x Mg_xGeO₄ (0,0 x 1,0) in the crystal field region show remarkable band splitting effects. They can be explained by the crystallographically plausible assumption, that the coordination octahedra of Ni²⁺ and Co²⁺ are compressed along their trigonal axes. A crystal field formalism is developed which allows a quantitative treatment of the spectra. Finally examples are given showing that band splittings are not always observed in the presence of a trigonal component.

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Résumé Le spectre des phases de type spinelle Ni_2-x Mg_xGeO₄ (0,0 x 1,2₅) et Co_2-x Mg_xGeO₄ (0,0 x 1,0) dans la région du champ cristallin montre des effets remarquables de séparation de bandes. Ils peuvent être expliqués par l'hypothèse cristallographiquement plausible selon laquelle l'octaèdre de coordination de N²⁺ et de Co²⁺ est comprimé selon l'axe trigonal. Un formalisme de champ cristallin développé ici permet un traitement quantitatif des spectres. Enfin on donne des exemples qui montrent que les séparations de bandes ne sont pas toujours observées en présence d'une composante trigonale.

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Aus der Habilitationsschrift D. Reinen, Bonn 1965.

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Herrn Dr. H. H. Schmidtke habe ich für die kritische Durchsicht des Manuskripts und der Deutschen Forschungsgemeinschaft für die Bereitstellung von Sachbeihilfen zu danken.     

Thermal transformations of the products of partial hydrolysis of hydrous aluminium nitrate

Thermal analysis, mass spectrometry, infrared spectrophotometry, X-ray phase analysis, scanning electron microscopy, and sorption methods were used in the study of thermal transformations of the products of partial hydrolysis of hydrous aluminium nitrate in ammonia medium. It has been found that the process of aluminium nitrate hydrolysis under the conditions applied and in the presence of ammonia gives boehmite as the main product, with some admixture of a basic salt.Aluminium oxide obtained from the products of partial hydrolysis of hydrous aluminium nitrate in ammonia medium at 550°C has a crystalline -Al₂O₃ structure. Its specific surface, as determined by low-temperature adsorption of nitrogen, exceeds 200 m²g^–1. Features of the products are well developed mesopore structure and considerable ability of benzene adsorption. Calcination of the obtained aluminium oxide for 2 h at 900°C reduces its specific surface to about 110 m² g^–1.This revised version was published online in November 2005 with corrections to the Cover Date.     

Application of decarboxylation reactions in catalytic analysis determination of aluminium

Summary The activation of the catalytic decarboxylation of oxaloacetic acid with some pyridine derivatives was studied in order to select suitable activators for increasing the sensitivity of this type of analytical catalytic reactions. The catalytic activity of some bivalent metal ions (Cu²⁺, Zn^2s+, Cd²⁺, Pb²⁺) as well as that of Al³⁺ was also studied. On that ground a catalytic method for determination of aluminium was developed. The sensitivity of the method is 0.5g of aluminium in the sample.

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Zusammenfassung Die Aktivierung der katalytischen Decarboxylierung von Oxalessigsäure durch einige Pyridinderivate wurde untersucht, um geeignete Aktivatoren zur Steigerung der Empfindlichkeit dieser analytisch auswertbaren Reaktion zu finden. Die katalytische Aktivität einiger zweiwertiger Metallionen (Cu, Zn, Cd, Pb) sowie von Al wurde ebenfalls geprüft. Auf dieser Grundlage wurde eine Methode zur Aluminiumbestimmung entwickelt, deren Empfindlichkeit zur Bestimmung von 0,5g Al je Einwaage ausreicht.

     

Synthesis of uniform-sized bimetallic iron–nickel phosphide nanorods

We synthesized uniform-sized nanorods of iron–nickel phosphides from the thermal decomposition of metal–phosphine complexes. Uniform-sized (Fe_xNi_1−x)₂P nanorods (0x1) of various compositions were synthesized by thermal decomposition of Ni–trioctylphosphine (TOP) complex and Fe–TOP complex. By measuring magnetic properties, we found that blocking temperature and coercive field depend on Ni content in the nanorods. Both parameters were more sensitive to doping compared with bulk samples.     

Characteristics of CuAl<Subscript>2</Subscript>-Cu<Subscript>9</Subscript>Al<Subscript>4</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposites synthesized by mechanical treatment

Summary Reactive milling of Cu-hydroxycarbonate - powder aluminium mixture brings many complex chemical reactions such as decomposition, aluminothermic reduction and mechanical alloying resulting in the formation of nanometer size composites that contain intermetallic phases, -Cu₉Al₄ and -CuAl₂, with aluminium oxide.     

Darstellung und Eigenschaften von Heteropolykationenverbindungen,IV: Darstellung und Struktur von Natriumdodekaaluminogalliumsulfat-Ikosihydrat,Na[GaO4Al12(OH)24(H2O)12](SO4)4 ·xH2O mitx∼20

Summary A chemical analyses of Na[GaO₄(Al₁₂(OH)₂₄(H₂O)₁₂](SO₄)₄ ·xH₂O withx20 [a=17.861 (4) Å; F 3 m-T _d ² ;Z=4] in connection with a crystal structure investigation confirmed the tetrahedral coordination of the gallium atom by oxygen atoms, as well as the far extending statistical distribution of the crystal water in the structure. The syntheses was done by neutralization of a satured aqueous aluminium chloride solution, mixed with metallic gallium and sodium sulfate, by an aqueous sodiumhydroxide solution.

     

Untersuchung der magnetostrukturellen Eigenschaften gemeinsam gefällter Hydroxide von Cd2+, Ni2+ und Fe3+

Zusammenfassung Aus einer Reihe gemeinsam gefällter und in siedendem Wasser gealterter Hydroxide, deren Mischungsverhältnis die Bildung von Cd _x Fe_1–x [Ni_1–x Fe_1+x ]O₄-Ferriten möglich machte, wurden Präparate erhalten, welche charakteristische Sättigungs-Magnetísierungskurven zeigen. Röntgenographische Analyse und magnetische Untersuchungen zeigten, daß der primäre Ferromagnetismus dieser Präparate dem -Fe₂O₃ zuzuschreiben ist.

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Studies of the magnetostructural properties of coprecipitated hydroxides of Cd²⁺, Ni²⁺ and Fe³⁺

From a series of coprecipitated hydroxides, aged by boiling in water, and in which the mixing proportions enabled the formation of Cd _x Fe_1–x [Ni_1–x Fe_1+x ]O₄-ferrites, preparations were obtained which show characteristic saturation magnetization curves. X-ray analysis and magnetic studies showed that the primary ferromagnetism of these preparations must be assigned to -Fe₂O₃.

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Mit 6 Abbildungen     

Influence of aluminium precursor on physico-chemical properties of aluminium hydroxides and oxides

The process of hydrolysis of aqueous aluminium sulfate was carried on in ammonia medium at 100°C and for different time intervals (0, 20, 39 or 59 h). The products thus obtained were calcined at 550, 900 or 1200°C for 2 h with the aim to obtain aluminium oxides. The materials were studied with the following methods: thermal analysis, IR spectroscopy, X-ray diffraction, low-temperature nitrogen adsorption, adsorption–desorption of benzene vapours and scanning electron microscopy. Freshly precipitated material was an amorphous basic aluminium sulfate which after prolonged refluxing at elevated temperature in a mother liquor underwent a phase transformation into highly crystalline NH₄Al₁₃(SO₄)₂(OH)₆ containing tridecameric unit Al₁₃. It was accompanied by a decrease of specific surface area and the formation of a porous structure less accessible for benzene molecules. Regardless of the duration of the hydrolysis process, all products were characterised with poorly developed porous structure and hydrophilic character. Their calcination at the temperature up to 1200°C resulted in the formation of α-Al₂O₃ via transition forms of γ/η- and δ-Al₂O₃. The samples of aluminium oxides obtained after calcination at 550 and 900°C had higher values of specific surface area than starting materials due to processes of dehydroxylation and desulfurization. The process of calcination up to 900°C was reflected in developing of not only porous structure but also hydrophobic character of prepared materials. The S _BET values calculated for the oxide samples obtained from aged products of hydrolysis at 1200°C were lower than for the analogous sample prepared without the ageing step. It was concluded that prolonged refluxing at elevated temperature of the products of hydrolysis of aluminium sulfate decreased thermal stability of final aluminium oxides.     

Phases in the Al–Yb–Zn system between 25 and 50 at% ytterbium

Phases YbZn_1−xAl_x, YbZn_2−xAl_x and YbZn_3−xAl_x were studied by electron microprobe analysis and X-ray single crystal and powder methods. The compound YbZn_0.8Al_0.2 crystallizes with the CsCl-type, a=3.635(2) Å. Four phases were investigated by single crystal X-ray diffraction: YbZn_0.996(6)Al_1.004(6), MgNi₂-type, P6₃/mmc, a=5.573(1), c=18.051(3) Å, Z=8, wR2=0.040 and YbZn_0.88(3)Al_1.12(3), MgCu₂-type, , a=7.860(2) Å, Z=8, wR2=0.060, both showing mixed Zn/Al occupancy; YbZn_2.50(1)Al_0.50(1), CeNi₃-type, P6₃/mmc, a=5.496(1), c=17.336(2) Å, Z=6, wR2=0.036 and YbZn_1.92(2)Al_1.08(2), PuNi₃- or NbBe₃-type, , a=5.499(1), c=26.134(5) Å, Z=9, wR2=0.053, where the zinc atoms are ordered in the CaCu₅ segment, while share the sites with aluminium in the Laves phase segment. In the pseudobinary section YbZn_2−xAl_x four structures occur in sequence with increasing the electron concentration: CeCu₂ or KHg₂ (x=0–0.3), MgZn₂ (x=0.33–0.54), MgNi₂ (x=0.68–1.01) and MgCu₂ (x=1.12–2). This sequence agrees with the results of first-principles calculations, already reported in the literature for other similar series. In the YbZn_3−xAl_x section CeNi₃-type compounds occur with x=0.40–0.88 followed by PuNi₃-type compounds with x=0.92–1.10. The stability ranges of these phases are related to the valence electron concentration.     

Aminophenolates of aluminium,gallium and zinc: Synthesis,characterization and polymerization activity

Complexes containing aminophenolate ligands are considered as very efficient initiators of ring‐opening polymerization (ROP). Our systematic studies of the reactions of two selected aminophenols, 2‐[(p ‐tolylamino)methyl]‐4‐(2,4,4‐trimethylpentan‐2‐yl)phenol (L'H₂) and 2‐cyclohexylaminomethyl‐4‐methylphenol (L″H₂), with alkyl compounds of aluminium, gallium and zinc resulted in the formation of a variety of products depending on the type of metallic centre and alkyl groups bonded to metal atoms. New trinuclear aluminium complexes (Me₅Al₃(L′)₂ ( 1 ) and Me₅Al₃(L″)₂ ( 2 )), monomeric aluminium (^t Bu₂Al(L'H) ( 3 ) and ^t Bu₂Al(L″H) ( 5 )) and gallium (^t Bu₂Ga(L'H) ( 4 ) and ^t Bu₂Ga(L″H) ( 6 )) compounds, and dinuclear gallium (Et₂Ga(L″H)·Et₃Ga ( 7 )) and zinc (^t BuZn(L″H)]₂ ( 8 )) complexes were isolated and characterized. The molecular and crystal structures of 7 and 8 were determined on the basis of an X‐ray diffraction study. Polymerization tests showed that only three complexes ( 6 – 8 ) had activity in the ROP of ε ‐caprolactone, whereas 1 – 5 were inactive in ROP.     

Ni-intAlx催化剂的化学合成及萘选择加氢性能

非（类）金属掺杂金属形成金属间隙或金属间化合物是一种设计高效、高选择性催化剂的重要手段.我们以萘基锂为强还原剂,NiCl₂与AlCl₃为原料,在室温下化学合成了Ni-^intAl_x纳米催化剂,并采用pXRD、N₂物理吸附、XPS、TEM、H₂-TPR、H₂-TPD等手段对催化剂进行表征.以萘选择加氢为探针反应,结果显示Ni-^intAl_x催化剂对萘选择加氢制四氢萘具有高活性及单一选择性.其中Ni-^intAl₁催化剂具有比Ni样品更纯的FCC晶型,比Ni-^intAl_1/3更适宜的铝掺杂量,及比Ni-^intAl₃更适宜的活性组分含量.镍铝之间的电子效应在一定程度上可调变中间产物四氢萘的吸附性能,避免过度加氢,在优化条件下萘转化率和四氢萘选择性分别达97%和98%,铝可用作第二金属掺杂以提高金属位点的活性和对中间产物的选择性.     

Investigations on zirconium-containing conversion layers on aluminium

Summary Conversion layers on technical aluminium produced by a no-rinse process for the purposes of food wrapping products are based on the application of aqueous solutions containing mainly zirconium compounds and polyacrylic acid. By the combined use of the methods TEM, AES, XPS and ISS, in-depth profiling of the elements Al, Zr, C, O and F are achieved, the existence of the chemical compounds Al₂O₃, ZrO₂ or the respective mixed oxides and polyacrylic acid or the fragments are detected. The layer thicknesses are determined amounting to 10–40 nm, and the surface-related mass of zirconium is estimated to 10–35 mg/m².

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Untersuchungen an zirkonhaltigen Konversionsschichten auf Aluminium

     

Morphology, structure and constitution of metastable single-phase Ti1-xAlxN films grown by reactive MSIP

Metastable, single phase, polycrystalline Ti_1–x Al _x N hard layers were deposited on HSS-substrates with reactive magnetron sputtering ion plating (MSIP). The substrate temperature was 400 °C, the bias –60 V, the argon pressure 1.2 Pa and the sputter power 6 W cm^–2. Compound targets with a Ti:Al ratio of 75/25, 50/50 and 25/75, expressed in at-%, were sputtered. The nitrogen reactive gas pressure during sputtering was 8.4 × 10^–2 Pa for the 7525 target and 1.08 × 10^–1 Pa for the 5050 and 2575 targets. The Ti_1–x Al _x N layers grew with x=0.26, 0.54 and 0.75, as determined with EPMA. Thin film XRD and HEED structure analysis showed that the Ti_0.74Al_0.26N layer had grown as B1 structure (a₀0.4214 nm) with [211] texture, the Ti_0.46Al_0.54N layer likewise as B1 structure (a₀0.4154) with [111] texture, but the Ti_0.25Al_0.75N as B4 structure (a₀0.317 nm and c₀0.5014 nm) with [110] texture. Pronounced columnar growth was observed with HR-SEM in the fractured surface of the cubic layers. The mean grain size, and consequently the surface roughness, diminished with increasing Al-content of the layer.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

High-pressure synthesis of solid solutions between trigonal LiNiO2 and monoclinic Li[Li1/3Ni2/3]O2

High-pressure synthesis in an oxygen-rich atmosphere yields solid solutions between LiNiO₂ and Li₂NiO₃ over the whole concentration range. Structural characterization of the high-pressure oxides was performed using powder XRD, SEM analysis, IR spectroscopy, EPR spectroscopy at 9.23 and 115 GHz and magnetic susceptibility measurements. The crystal structure of Li[Li_xNi_1−x]O₂ ,, changes from trigonal R-3m to monoclinic C2/m at Li-to-Ni ratio of 2 (or ). The incorporation of Li into NiO₂-layers causes a decrease in the mean Li-O and Ni_1-xLi_x-O bond distance. Li and Ni ions in the mixed Ni_1-xLi_xO₂-layers display a tendency to order at a short length scale in such a way that mimics the Li_1/3Ni_2/3-arrangment of the end Li[Li_1/3Ni_2/3]O₂ composition. The charge distribution in these oxides proceeds via Ni³⁺ and Ni⁴⁺ ions.     

Metallreiche Phasen im ternären System Ni-Se-Te

Zusammenfassung Die metallreichen Phasen im System Ni-Se-Te wurden durch Röntgenaufnahmen bei Zimmertemp. und bei höheren Temperaturen sowie durchDTA untersucht. Bei Zimmertemp. wurden im pseudo-binären Schnitt Ni₃(Se_1-x , Te _x )₂ Phasen mit den folgenden Strukturen gefunden: rhomboedrischer Ni₃S₂-Typ fürx=0; tetragonaler (Ni,Fe)₁₁Se₈-Typ für 0,15x0,35; tetragonaler Rickardit-Typ für 0,50x0,80; Überstrukturen des Rickardit-Typs für 0,95x1. Bei höheren Temperaturen verbreitert sich das Homogenitätsgebiet der Phase mit der tetragonalen Rickardit-Struktur. Über 600–770°C tritt im ganzen Gebiet 0x1 eine kubisch.

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Metal-rich phases in the ternary system Ni-Se-Te

The metal-rich phases in the system Ni-Se-Te have been studied by X-ray diffraction at room temperature and elevated temperatures, and byDTA. At room temperature phases with the following structures were found in the pseudo-binary section Ni₃(Se_1-x , Te _x )₂: rhombohedral Ni₃S₂ type forx=0; tetragonal (Ni,Fe)₁₁Se₈ type for 0,15x0,35; tetragonal rickardite type for 0,50x0,80; superstructures of the rickardite type for 0,95x1. At higher temperatures the homogeneity range of the phase with the tetragonal rickardite structure broadens. Above 600–770°C a face-centered cubic phase exists in the whole range 0x1; a model for the structure of this phase is proposed. The compound Ni_2,6Te₂ is orthorhombic at room temperature; it becomes hexagonal at 720°C and disproportionates at 820°C; by partial substitution of Te by Se the hexagonal form is stabilized at room temperature. Similarly, the compound Ni₆Se₅ which is stable above 440°C only, is stabilized at room temperature by partial substitution of Se by Te. The phase Ni₆(Se_1-x , Te _x )₅ decomposes by a peritectoid reaction at 650° (x=0) to 590°C (x=0,3).

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Herrn Prof. Dr.H. Nowotny gewidmet.     

Analysis of intermetallic particles in aluminium by dissolution of the sample in butanol

Summary A new method for the quantitative analysis of intermetallic particles in aluminium has been developed. 0.3–5 g samples are dissolved in absolute 1-butanol. The content, the chemical composition, the structure, the shape and the size distribution of the undissolved particles have been determined by means of a series of methods including weight measurements, X-ray fluorescence, inductively coupled argon plasma spectrometry, Coulter Counter analysis and X-ray diffraction. The materials investigated were samples of 99.999 wt% aluminium, 99.5 wt% aluminium and aluminium — 0.4 wt% magnesium — 0.4 wt% silicon — 0.2 wt% iron alloy. Cast samples of the latter alloy contained mainly -AlFeSi and samples homogenized at 580°C - AlFeSi and 1-AlFe(Ni,Cu)Si. Al₁₃Fe₄-particles were dominant in the intermetallic phase present in the 99.5 wt% aluminium samples investigated. The results have been compared and found in agreement with emission spectrometric measurement of the alloys' chemical composition, transmission electron microscopy of the intermetallic phases of thin foils and light microscopy analysis of particles in polished samples.

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Analyse intermetallischer Partikel in Aluminium durch Auflösung der Probe in Butanol

Zusammenfassung Zur Analyse wurden 0,3–5 g der Probe in absolutem 1-Butanol gelöst. Gehalt, chemische Zusammensetzung, Struktur, Form und Größenverteilung der ungelösten Partikel wurden mit Hilfe verschiedener Methoden bestimmt (Gewichtsmessungen, Röntgenfluorescenzanalyse, ICP, Coulter Counter-Analyse, Röntgendiffraktion). Die untersuchten Proben waren 99,999%iges Al, 99,5%iges Al sowie Al-Legierung mit 0,4% Mg, 0,4% Si und 0,2% Fe. Gußproben dieser Legierung enthielten hauptsächlich -AlFeSi, bei 580° C homogenisierte Proben -AlFeSi und 1-AlFe(Ni,Cu)Si. In der intermetallischen Phase der 99,5%- igen Al-Probe überwogen Al₁₃Fe₄-Partikel. Die erhaltenen Ergebnisse stimmen überein mit emmissionsspektrometrischen Bestimmungen der chemischen Zusammensetzung, mit transmissions-elektromikroskopischen Messungen der intermetallischen Phasen dünner Folien sowie der lichtmikroskopischen Analyse der Partikel in polierten Proben.