Synthesis of Ti–Sn–Nb alloy by powder metallurgy

The microstructural evolution and characteristics of the Ti–16Sn–4Nb powder particles and bulk alloys sintered from the powders ball-milled for various periods of time were studied. Results indicated that ball milling to 8 h led to the development of a supersaturated hcp α-Ti and partial amorphous phase due to the solid solution of Sn and Nb into Ti lattice. The bulk Ti–16Sn–4Nb alloy made from the powders ball milled for a short time, up to 2 h, exhibited a primary α and a Widmanstätten structure consisting of interlaced secondary α and β. With an increase in ball milling time up to 10 h, the microstructure evolved into a fine β phase dispersed homogeneously within α phase matrix. The microhardness values of the bulk alloy in both α- and β-phases increased with the increasing of the ball milling time and reached a plateau value at 8 h and longer, i.e. 687 and 550 HV for α- and β-phases, respectively. Likewise, the microhardness of the α phases was always higher than that of the β phases in the bulk alloys made from the powders ball milled for the same milling time.

Inorganic-organic hybrids of the p,p'-diphenylmethylenediphosphinate, pcp2-. synthesis, characterization and XRPD structures of [Sn(pcp)] and [Cu(pcp)]

Two new inorganic-organic polymeric hybrids [Sn(pcp)] and [Cu(pcp)], pcp = CH₂(PhPO₂)₂^2-, have been synthesized and structurally chracterized. The tin derivative has been obtained by reaction of the p,p'-diphenylmethylenediphosphinic acid (H₂pcp) in water with SnCl₂·2H₂O, while the copper derivative has been synthesized through a hydrothermal reaction from the same H₂pcp acid and Cu(O₂CMe)₂·H₂O. The structures of these compounds have been solved "ab initio" by X-ray powder diffraction (XRPD) data. [Sn(pcp)] has a ladder-like polymeric structure, with tin(II) centers bridged by diphenylmethylenediphosphinate ligands, and alternating six- and eight-membered rings. The hemilectic coordination around the metal shows the tin(II) lone pair to be operative, resulting in significant interaction mainly with a C-C bond of one phenyl ring. The [Cu(pcp)] complex displays a polymeric columnar structure formed by two intersecting sinusoidal ribbons of copper(II) ions bridged by the bifunctional phosphinate ligands. The intersections of the ribbons are made of dimeric units of pentacoordinated copper ions. Crystal data for [Sn(pcp)]: monoclinic, space group P2₁Ic, a = 11.2851(1), b = 15.4495(6), c = 8.6830(1) Å, ^β= 107.546(1)°, V = 1443.44(9) Å, Z = 4. Crystal data for [Cu(pcp)]: triclinic, space group P, a = 10.7126(4), b = 13.0719(4), c = 4.9272(3) Å, α= 92.067(5), β= 95.902(7), γ= 87.847(4)°, V = 685.47(7), Z = 2. The tin compound has been characterized by ¹¹⁹Sn MAS NMR (magic-angle spinning NMR), revealing asymmetry in the valence electron cloud about tin. Low-temperature magnetic measurements of the copper compound have indicated the presence of weak antiferromagnetic interactions below 50 K.

Mechanochemical synthesis of nanocrystalline SnO2-ZnO photocatalysts

Mechanochemical processing of anhydrous chloride precursors with Na₂CO₃ has been investigated as a means of manufacturing nanocrystalline SnO₂ doped ZnO photocatalysts. High-energy milling and heat-treatment of a 0.1SnCl₂+0.9ZnCl₂+Na₂CO₃+4NaCl reactant mixture was found to result in the formation of a composite powder consisting of oxide grains embedded within a matrix of NaCl. Subsequent washing with deionized water resulted in removal of the NaCl matrix phase and partial hydration of the oxide reaction product with the consequent formation of ZnSn(OH)₆. The extent of this hydration reaction was found to decrease in a linear fashion with the temperature of the post-milling heat-treatment over the range of 400–700 °C. For a heat-treatment temperature of 700 °C, the SnO₂ doped ZnO powder was found to exhibit significantly higher photocatalytic activity than either single-phase SnO₂ or ZnO powders that were synthesized using similar processing conditions. The heightened photocatalytic activity of the SnO₂ doped ZnO was attributed to its higher specific surface area and the enhanced charge separation arising from the coupling of ZnO with SnO₂.

Mechanochemical synthesis of nanoparticles

The results of recent investigation of the mechanochemical synthesis of inorganic nanoparticles are reviewed. It was demonstrated that, by selecting suitable chemical reaction paths, stoichiometry of starting materials and milling conditions, mechanochemical processing can be used to synthesise a wide range of nanocrystalline particles dispersed within a soluble salt matrix. Selective removal of the matrix phase by washing the resulting powder with appropriate solvents can yield nanoparticles of the desired phase. This technique has been shown to have advantages over other methods of producing nanoparticles in terms of low cost, small particle sizes, low agglomeration, narrow size distributions and uniformity of crystal structure and morphology.

Synthesis of ultrafine ceria powders by mechanochemical processing

The synthesis of ultrafine cerium dioxide (CeO₂) powders via mechanochemical reaction and subsequent calcination was studied. Anhydrous CeCl₃ and NaOH powders, along with NaCl diluent, were mechanically milled. A solid-state displacement reaction—CeCl₃+ 3NaOH → Ce(OH)₃+ 3NaCl—was induced during milling in a steady-state manner. Calcination of the as-milled powder in air at 500°C resulted in the formation of CeO₂ nanoparticles in the NaCl matrix. A simple washing process to remove the NaCl yielded CeO₂ particles ∼10 nm in size. The particle size was controlled in the range of ∼10–500 nm by changing the calcination temperature.

Synthesis of Al3BC from mechanically milled and spark plasma sintered Al-MgB2 composite materials

The aluminium-rich ternary aluminium borocarbide, Al₃BC was synthesised for the first time by solid-state reactions occurring during heat treatments after mechanical milling (MM) of pure aluminium with 15 or 50 at% MgB₂ powder mixtures in the presence of the process control agent (PCA).

The solid-state reactions in the Al–15 and 50 at% MgB₂ composite materials occurred between the MMed powders and process control agent (PCA) after heating at 773–873 K for 24 h. The products of the solid-state reaction induced Al₃BC, AlB₂, γ-Al₂O₃ and spinel MgAl₂O₄. MM processing time and heating temperatures in the Al–15 and 50 at% MgB₂ composite materials affected the selection of those intermetallic compounds. When MM processing time was increased for a given composition, the formation of the Al₃BC compound started at lower heat treatment temperatures. However, when the amount of MgB₂ was increased in the 4 h MM processing regime, the formation of the Al₃BC compound during heating was suppressed. As a result of the solid-state reactions in MMed powders the hardness was observed to increase after heating at 573–873 K for 24 h.

The fully dense bulk nano-composite materials have been successfully obtained through the combination of the MM and spark plasma sintering (SPS) processes for the 4 h or 8 h MMed powders of the Al–15 at% MgB₂ composite materials sintered under an applied pressure of 49 MPa at 873 K for 1 h.

Fabrication of porous TiAl intermetallic compound by self-propagating high temperature synthesis

The present paper describes processing of a lotus-structured porous Ti-Al/Ti composite by SHS with Ti powder and Al rods. Ti-Al intermetallic compound was formed in a range of 200-300μm around the pore by SHS of reaction between Ti and Al, resulting in formation of a lotus-structured porous Ti-Al/Ti composite.

One-Step synthesis of the pine-shaped nanostructure of aluminum nitride and its photoluminescence properties

An array of pine-shaped nanostructures of aluminum nitride (AlN) was synthesized through direct reaction between Al vapor and nitrogen gas in direct current (DC) arc discharge plasma without any catalyst or template. The as-prepared nanostructure consists of many pine-needle-shaped leaves with conical shape tips. The structure, morphology, and optical property of the nanostructure have been characterized by X-ray powder diffraction, energy-dispersive X-ray spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, Raman spectroscopy, and photoluminescence. A possible growth mechanism of the pine-shaped nanostructure was discussed. Two factors were found to be essential for branched nanostructure growth, i.e., the reaction time and N2 pressure. The photoluminescence spectrum of the nanostructure of AlN revealed an intense emission band, suggesting that there may be potential applications in electronic and optoelectronic nanodevices.

Resistance of nanocrystalline vis-à-vis microcrystalline Fe–Cr alloys to environmental degradation and challenges to their synthesis

This paper presents a hypothesis and its experimental validation that a nanostructure can bring about dramatic improvements in the oxidation/corrosion resistance of iron–chromium alloys. More specifically, a nanocrystalline Fe–10 wt% Cr alloy was found to undergo oxidation at a rate that was an order of magnitude lower than its microcrystalline counterpart. Importantly, the oxidation resistance of nanocrystalline Fe–10 wt% Cr alloy was comparable with that of the common corrosion-resistant microcrystalline stainless steels (having 18–20 wt% chromium). The findings have the potential of leading to the next generation of oxidation-resistant alloys. However, due to poor thermal stability of nanocrystalline structure, synthesis/processing of such alloys is a challenge. Discs of nanocrystalline Fe–10% Cr alloy were produced by ball-milling of Fe and Cr powders and compaction of the powder without considerable grain growth by processing within a suitable time–temperature window. The paper also presents a theoretical treatise to arrive at the minimum chromium content required for establishing a protective layer of chromium oxide in an Fe–Cr alloy of a given nanometric grain size.

Synthesis and structural properties of Anhydrous Rare Earth Cinnamates, [RE(cinn)3]

Anhydrous rare earth tris(cinnamates) [RE(cinn)3] (RE = La–Lu, Y and Sc and cinnH = trans-cinnamic acid) were prepared by metathesis in water and by direct reaction of the metal with cinnamic acid in a 1,2,4,5-tetramethylbenzene flux at ca. 200 °C. X-ray crystal structure determinations and X-ray powder data show that, in the solid state, the larger lanthanoids (La–Dy) form an isomorphous polymeric series consisting of homoleptic nine-coordinate metal centres bonded to three chelating and bridging tridentate cinnamates. The late REIII cinnamate (RE = Dy, Ho–Lu, Y) complexes also form linear one-dimensional polymeric chains with all RE metal atoms being seven-coordinate. The cinnamates are either bound tridentate bridging in a μ-η2:η1 fashion, or μ-η1:η1syn-syn bidentate bridging. A structural break occurs at dysprosium which has been characterised in both crystallographic forms, and gives solely the late RE form when precipitated at 80 °C. ScIII cinnamate was also isolated as an analytically pure precipitate which was, again, found to be anhydrous in nature. A structural change was identified by powder XRD between the late REIII cinnamates and ScIII cinnamate.

Controlled modification of the inorganic and organic bricks in an Al-based MOF by direct and post-synthetic synthesis routes

Four new porous CAU-1 derivatives CAU-1–NH2 ([Al4(OH)2(OCH3)4(BDC–NH2)3]·xH2O, BDC–NH22− = aminoterephthalate), CAU-1–NH2(OH) ([Al4(OH)6(BDC–NH2)3]·xH2O), CAU-1–NHCH3 ([Al4(OH)2(OCH3)4(BDC–NHCH3)3]·xH2O) and CAU-1–NHCOCH3 ([Al4(OH)2(OCH3)4(BDC–NHCOCH3)3]·xH2O) all containing an octameric [Al8(OH)4+y(OCH3)8−y]12+ cluster, with y = 0–8, have been obtained by MW-assisted synthesis and post-synthetic modification. The inorganic as well as the organic unit can be modified. Heteronuclear 1H–15N, 1H–13C and homonuclear 1H–1H connectivities determined by solid-state NMR spectroscopy prove the methylation of the NH2 groups when conventional heating is used. Varying reaction times and temperatures allow controlling the degree of methylation of the amino groups. Short reaction times lead to non-methylated CAU-1 (CAU-1–NH2), while longer reaction times result in CAU-1–NHCH3. CAU-1–NH2 can be modified chemically by using acetic anhydride, and the acetamide derivative CAU-1–NHCOCH3 is obtained. Thermal treatment permits us to change the composition of the Al-containing unit. Methoxy groups are gradually exchanged by hydroxy groups at 190 °C in air. Solid-state NMR spectra unequivocally demonstrate the presence of the amino groups, as well as the successful post-synthetic modification. Furthermore 1H–1H correlation spectra using homonuclear decoupling allow the orientation of the NHCOCH3 groups within the pores to be unravelled. The influence of time and temperature on the synthesis of CAU-1 was studied by X-ray powder diffraction, elemental analyses, and 1H liquid-state NMR and IR spectroscopy.