A convenient and quantitative route to Sn(IV)-M M = Ti(IV), Nb(V), Ta(V) heterobimetallic precursors for dense mixed-metal oxide ceramics

Abstract : The strategy of reacting SnCl4 with M(OR)(x) provided a convenient and quantitative approach to new heterobimetallics with a simple addition formula, [SnCl4M(OR)(x)(HOR)(y)] (M = Ti, Nb, Ta; R = Et, Pr-i, x = 4, 5; y = 0-2) or sometimes an oxo complex [SnCl3(O)Ti-2(OPri)(7)(HOPri)(2)]. The alcoholysis reactions of these heterometallics afforded mixed alkoxo complexes [SnCl4(mu-OEt)(2)M((PrO)-O-i)(x)((PrOH)-O-i)(y)] [M = Ti (x = y = 2), Nb, Ta (x = 3, y = 1)] under mild conditions, or a planar rectangular oxo product [SnCl3(mu-OEt)(2)Nb-(OEt)(2)(EtOH)(mu-O)](2) at refluxing/extended stirring time. DFT calculations shed light on the stability and reactivity of these complexes. The use of these thoroughly characterized heterometallics as sol-gel precursors suppresses the formation of the undesired SnO2 grains, which are difficult to be sintered to a high density. The combined approach of using bottom-up synthesis of mixed Ti0.5Sn0.5O2 nanoparticles and Spark Plasma Sintering allowed the successful densification of chloride-free mixed-metal oxide ceramics. The influence of thermal treatment before sintering on the density and spinodal decomposition of the TiO2-SnO2 pellets is reported.
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Submitted on : Wednesday, May 6, 2015 - 10:24:39 AM
Last modification on : Wednesday, December 12, 2018 - 3:26:58 PM

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Shashank Mishra, Erwann Jeanneau, Stéphane Mangematin, Henry Chermette, Mahboubeh Poor Kalhor, et al.. A convenient and quantitative route to Sn(IV)-M M = Ti(IV), Nb(V), Ta(V) heterobimetallic precursors for dense mixed-metal oxide ceramics. Dalton Transactions, Royal Society of Chemistry, 2015, 44 (15), pp.6848-6862. ⟨10.1039/c5dt00339c⟩. ⟨hal-01149007⟩

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