Alkali-flux method

The use of strong alkaline media, either in the form of solid fluxes or molten (or aqueous) solutions, has enabled the synthesis of novel oxides. The alkali flux method stabilizes higher oxidation states of the metal by providing an oxidizing atmosphere. Alkali car-... 

Several other novel strategies have been employed for the synthesis of superconducting cuprates some of them were mentioned earlier while discussing the various methods. Especially noteworthy are the use of the combustion method and the alkali-flux method for cuprate synthesis. Superconducting infinite-layered cuprates seem to be possible only when prepared under high pressures because of bonding (structural) considerations [87, 88]. In Table 7 we list the various cuprate superconductors along with their properties and the preferred methods of synthesis. 

In this book, we briefly examine the different types of reactions and methods employed in the synthesis of inorganic solid materials. Besides the traditional ceramic procedures, we discuss precursor methods, combustion method, topochemical reactions, intercalation reactions, ion-exchange reactions, alkali-flux method, sol-gel method, mechanochemical synthesis, microwave synthesis, electrochemical methods, pyrosol process, arc and skull methods and high-pressure methods. Hydrothermal and solvothermal syntheses are discussed separately and also in sections dealing with specific materials. Superconducting cuprates and intergrowth structures are discussed in separate sections. Synthesis of nanomaterials is dealt with in some detail. Synthetic methods for metal borides, carbides, nitrides, fluorides, sili-cides, phosphides and chalcogenides are also outlined. 

The preparation of some polychalcogenide solids can be achieved at 200-450 °C by molten salt (flux) methods. The reaction of tin with alkali metal sulfides in the presence of Ss at 200-450 °C gives a variety of alkali metal tin sulfides depending on the ratio of the starting materials, the reaction temperature, and the alkah metals (Scheme 30) [90]. These alkali metal tin sul-... 

Aluminum borate whiskers are produced commercially by an external flux method. Chlorides, sulfates, or carbonates of alkali metals are added to alumina and boric oxide (or boric acid) and the mixture is heated to 800°C-1000°C to produce aluminum borate whisker (length 10-30 pm and diameter 0.5-1.0 pm). It has a melting point of 1440°C, a very low coefficient of thermal expansion, and an excellent chemical resistance toward acids. The aluminum borate whisker was reported to be effective in improving not only the thermal degradation but also the glass transition temperature of epoxy76... 

An interesting combination of methods is the polysulfide flux method, which can be usedforthe preparation of Ln202S (Ln trivalent rare-earth ion)-based luminescent materials (e.g. Y202S Eu or Gd202S Pr) [5.228]. In this method, the mixed oxides of the metals are mixed with excess sulfur and an alkali metal carbonate. On heating, the alkaline carbonate decomposes and reacts with sulfur to form a Uquid polysulfide flux. The oxides react with the polysulfide flux to form the oxysulfide. Flux residues can be removed by washing the reaction product in water. 

The flux method is a well-known method used for single crystal growth. It has not been applied to the synthesis of fine powders because usually high temperature heating is necessary to obtain molten salts. However, the modified flux method has been reported for the preparation of fine panicles of Ce,. Pr Oj solid solutions.In the preparation of the powders by the flux method, molten salts of alkali metal hydroxides, nitrates, and chlorides are used as solvents. The use of molten salts. 

This means that addition of elemental E to alkali metal polychalcogenide fluxes (200-600°C) will promote the formation of longer chains as potential ligands, when such molten salts are employed as reaction media for the preparation of polychalcogenide complexes. Speciation analysis for polychalcogenides in solution has been performed by a variety of physical methods including UV/vis absorption spectroscopy, Raman spectroscopy, Se, Te and Te NMR, electron spin resonance and electrospray mass spectrometry. 

The synthesis of chalcogenides such as those of the rare earth elements has traditionally been performed through the reaction of rare earth metals or oxides with a molten or vaporous chalcogen source in a high-temperature environment. Soft synthetic methods utilizing lower temperature conditions, such as hydrothermal or flux syntheses, can allow access also to thermodynamically metastable phases. Flux syntheses of R chalcogenides via an alkali poly-chalcogenide flux have been shown to be extremely versatile for the preparation of many new structures, some of which cannot be obtained by direct synthesis from the elements. 

Fusion with anhydrous potassium fluoride in a platinum dish is undoubtedly the simplest, most effective and reliable method available for the complete dissolution of a wide variety of siliceous materials. The potassium fluoride cake can then be transposed in the same container to a pyrosulfate fusion with rapid and complete volatilisation of both hydrogen fluoride and silicon tetrafluoride [54]. Except for a small quantity of barium sulfate, the pyrosulfate cake will dissolve completely in dilute hydrochloric acid. The resulting pyrosulfate fusion is one of the simplest and most effective methods available for rapid, complete and dependable dissolution of nonsiliceous materials, particularly high-fired oxides. This fusion has the distinct advantage that the flux can be obtained by simply adding easily purified alkali metal sulfates to sulfuric acid, and the fusion can be carried out in either borosilicate flasks or platinum vessels with very little contamination from either reagents or containers. 

This is a method solely used to obtain crystals of the borides. The raw materials of the borides are mixed into large amount of a low melting metal (e.g. Al, Cu, Sn) which will function in the role of the flux for the crystal growth, and then the mixture is heated. The flux is removed by an acid or alkali leaving the crystals as a solid residue. 

---