Solid-state synthesis alloying

According to the aggregation state of the component elements and the method selected for starting and performing their reaction, several preparative procedures can be considered, such as melting (direct reaction in the liquid state), solid-state synthesis (mechanical alloying), combustion synthesis, etc. 

Interest in the synthesis of transition metal carbonyl clusters incorporating interstitial main-group atoms is because they provide a conceptual bridge between or-ganometallic chemistry and the areas of inorganic solid-state and surface chemistry. In addition to serving as useful models for either solid-state binary alloys or for the chemisorption of heteroatoms on the step-site of a metal surface, these discrete molecular clusters are often markedly more stable, especially toward the temperatures and pressures required for catalytic reactions. 

The synthesis and stmctnral characterization of a series of spirocyclic organozincates containing two five- or six-membered metallacycles in which zinc is the central spiro atom, is shown in Scheme 1. Compound 8a was prepared via an elegant one-pot synthesis, starting from 1,5-dichloropentane, ZnCl2 and a lithium/sodinm alloy (1% sodinm) in diethyl ether as a solvent (eqnation 4 in Scheme 1). Snbseqnent treatment of a soln-tion of 8a with TMEDA afforded the corresponding TMEDA complex 8b of which the structnre in the solid state was unambiguously established by an X-ray crystal structnre determination. 

Most modern materials are formed empirically by solid-state methods. These methods generally involve more processing activity than chemical synthesis (for example, sintering of ceramic powders, modifying concrete by polymers, thermomechanical processing of alloys, layering polymeric membranes for... 

Gas-solid reactive sintering can also be used in the oxidation of most metals or, more important, mixtures of metals. After oxidation, solid state sintering takes place. With mixtures of metals, a mixed oxide is produced which can be sintered by either solid state or liquid phase sintering. One example of alloy oxidation to produce a ceramic is in the synthesis of the superconductor YBa2Cu3Q. ... 

Like certain combinations of metallic elements which show degrees of mutual solubility, so organic polymer blocks show varying tendencies to "alloy" in the solid state. The synthesis and properties of block polymers is a developing science which leads to important materials and engineering applications.(65) In this section we describe the preparation of a BAB block terpolymer of f-methylstyrene and styrene.(66) Sodium atoms are used to initiate polymerization in liquid tetrahydrofuran solutions of monomer cooled... 

There is a close relationship between the solution-based syntheses of the naked clusters, as described above, and pure solid state chemistry. This relationship stems from the fact that homonuclear bonding and discrete clusters in many cases also exist within alloys of the type used in the synthesis of Zintl ions in solution. Indeed, such alloys are often to be regarded as well-defined intermetallic compounds. ... 

Fewer EXAFS works have been devoted to the study of catalytic systems under reaction conditions due, as already said, to inherent limitations of the technique at high, working temperatures characteristic of catalytic reactions. Among these, a majority include studies of Cu/ZnO (Cu/Si02) in methanol synthesis.The solid state physics of the active copper phase in methanol synthesis is a rather intriguing problem which has not achieved consensus concerning the oxidation state and the hosting of the Cu phase characteristics. The EXAFS works mentioned above elucidated mainly the importance of the metallic state in the reaction. Similarly, the metallic state has been shown to be of importance in the water gas shift reaction (WGS) in Cu, Au, and bimetallic Pd-Cu systems supported on ceria. The importance of ceria vacancies on the activation of water and of the metal (and more precisely, of the metal at support boundaries) for CO activation appear as key elements for this reaction. The bimetallic Pd-Cu work analyses the modulation of Pd behaviour by effect of the alloy with the base... 

B. Neppolian, V. Saez, J.-G. Garcia, F. Grieser, R. Gomez, M. Ashokkumar, Sonochemical synthesis of graphene oxide supported Pt-Pd alloy nanocrystals as efficient electrocatalysts for methanol oxidation. J. Solid State Electrochem. 18, 3163-3171 (2014)... 

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