Aluminosilicates cation ordering

In aluminosilicates, too, including epidote and the Al2SiOs polymorphs andalusite, kyanite and sillimanite, Al3+ ions occupy several coordination sites. Again, trivalent cations such as Cr3+, V3+, Mn3+ and Fe3+ may show cation ordering and be relatively enriched in one specific Al3+ site in a crystal structure. 

Several of the well-known polymorphic structural phase transitions that occur in minerals at low to moderate temperatures, particularly in framework aluminosilicates, have since been studied by NMR techniques a brief review of these studies is provided here. Also included is a review of NMR studies of quenchable cation ordering reactions, which further illustrate the types of information on mineral transformations available from NMR experiments. NMR spectroscopy has also been used extensively to study glass transitions and glass-to-liquid transitions, which have been recently reviewed by Stebbins (1995b). We begin with a brief description of NMR spectroscopy, focusing on those aspects that are most useful for studying transitions in minerals... 

The sizes of the voids decrease in order Cs, Rb, Na, K These differences are ascribed to the different influence of cation on the surrounding reactive species that changes the nature of alkali cation - aluminosilicate anion complexes. On the other hand, in the case that the cations are introduced in the matrix by ion exchange, (procedure b) the r3 lifetimes are approximately the same for all the cations (Table 2) and the size of cation does not have such pronounced influence. The calculated radii are shown in Table 4. 

Role of alkali and NH cations in the crystallization of ZSM-5 Introduced in an aqueous (alumino) silicate gel (sol), the bare alkali cations will behave in various ways firstly, they will interact with water dipoles and increase the (super) saturation of the sol. Secondly, once hydrated, they will interact with the aluminosilicate anions with, as a result, the precipitation of the so formed gel (salting-out effect). Thirdly, if sufficiently small, they also can order the structural subunits precursors to nucleation species of various zeolites (template function-fulfilled by hydrated Na+ in the case of ZSM-5 (11,48)). ... 

The determination of surface properties of particles is an important key to understanding interactions of trace elements and organic compounds between particulate and dissolved phases in estuarine and coastal systems. Specific surface area (SSA), cationic exchange capacity (CEC) and heat of immersion (AH) have been measured on native and treated suspended sediment and after oxidation with 15% H202- SSA and A H have also been measured on samples leached with NaOH and Na-dithionite in order to remove amorphous aluminosilicates. 

Figure 12 Changes in the unit-cell edge lengths (A) of sodiiun aluminosilicate natrolite as a function of pressure. Polyhedral representations of natrolite at (a) 0.40 GPa and (b) 1.51 GPa viewed along [001], the chain/channel axis. Each representation is repeated on the right without the framework component to emphasize the channel contents. Note the formation of the hydrogen-bonded water nanotubes at 1.51 GPa. Red circles represent the oxygen of the water molecules yellow ones sodium cations. Blue (azure) tetrahedra dlustrate an ordered distribution of Si (Al) atoms in the framework...

Recent work in Versailles and Santa Barbara has led to the synthesis of several nanoporous nickel(II) phosphates. A zeolitic nickel(II) phosphate, VSB-1 (Versailles/Santa Barbara-1), was prepared under simple hydrothermal conditions [22] and has a unidimensional pore system delineated by 24 NiO and PO4 poly-hedra with a free diameter of approximately 0.9 nm (Figure 18.7). It becomes microporous on calcination in air at 350 °C, yielding BET surface areas up to 160 m g and is stable in air to approximately 500 °C. The surface area appears low compared with aluminosilicate zeolites, but the density of VSB-1 is twice that of a zeolite and the channel walls are particularly thick. VSB-1 can be prepared in both ammonium and potassium forms, and exhibits ion-exchange properties that lead, for example, to the formation of the lithium and sodium derivatives. Other cations (e.g. Mn, Fe, Co, and Zn) can be substituted for Ni in VSB-1, up to a level as high as 30 atomic%. The parent compound shows canted antiferromagnetic order at Tn = 10.5 K with 6 = —71 K on doping with Fe, Tn increases to 20 K and 6 decreases to —108 K. 

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