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Title: Materials synthesized via solid state and solution metathesis reactions

Miscellaneous ·
OSTI ID:7275041

Metathesis (or exchange) reactions are used as new synthetic routes for producing materials in both solid-state and solution reactions. Solid-state metathesis reactions produce transition metal phosphides. Solution exchange reactions synthesize nanocrystalline metal tellurides. Transition metal phosphides, normally produced in long, high-temperature reactions (days at >800[degrees]C), are formed in solid-state metathesis reactions in only seconds. Transition metal halides vigorously react with sodium phosphide to form metal phosphide, byproduct salt that is easily washed away with water, and elemental phosphorus which is boiled from the system by the reaction's great exothermicity. MoP and WP reactions spontaneously ignite upon mixing the precursors producing metal phosphides and Mo or W. Incomplete mixing of the precursors causes the formation of the metal. The ZrP and HfP reactions, however, do not spontaneously ignite because of the stability of ZrCl[sub 4] and HfCl[sub 4]. Group IV phosphide sealed-tube reactions form the low-temperature, hexagonal phases of ZrP and HfP. However, application of a hot wire to the precursors initiates a self-propagating reaction that produces the high-temperature, cubic phases of ZrP and HfP. The high-temperature phases are formed by the rapid cooling that occurs after the reaction, quenching the system and isolating the cubic phases. These are the first extensive studies of solid-state metathesis reactions forming metastable compounds. CdTe, HgTe, and Hg[sub 1-x]Cd[sub x]Te are difficult materials to produce stoichiometrically because of the high vapor pressures of Hg and Cd above 200[degrees]C. However, CdI[sub 2] was previously reacted with Na[sub 2]Te in solution to form CdTe and byproduct NaI. This solution exchange synthesis has now been extended to include reactions of Na[sub 2]Te with HgI[sub 2] or mixtures of HgI[sub 2] and CdI[sub 2] to form HgTe and Hg[sub 1-x]Cd[sub x]Te, respectively.

Research Organization:
California Univ., Los Angeles, CA (United States)
OSTI ID:
7275041
Resource Relation:
Other Information: Thesis (Ph.D.)
Country of Publication:
United States
Language:
English