Copper nitride, decomposition

The extensive surface reconstruction in the presence of N has implications for our discussion of the recombination process, since we must consider whether N2 forms from recombination on the unreconstructed Cu(l 1 1) surface or is formed by decomposition of copper nitride islands. In the latter case N recombination may either leave the local Cu atoms in a metastable (100) arrangement or else recombination might be associated with substantial motion of the Cu atoms as they relax from the nitride adsorption geometry. If N recombination occurs at nitride islands then the dynamics of recombinative desorption will sample a phase space which is completely different to that for dissociation on clean flat Cu terraces, making it impossible to relate these two processes by detailed balance. This is the behaviour of H recombination on Si where the large change in the Si equilibrium geometry induced by H adsorption ensures that the adsorption and desorption processes sample very different channels [13]. 

The two phase model describes all the principle features of the desorption kinetics, suggesting that recombinative desorption under conditions where the coverage is less than saturation occurs by the recombination of N atoms from a dilute phase on the Cu(l 11) surface. This behaviour is the same as that observed for H recombinative desorption on many surfaces [63]. Desorption from the dilute phase is preferred over direct decomposition of the nitride islands because this leaves the copper surface in its equilibrium (111) orientation, rather than as an unstable Cu(l 00) overlayer [99]. As a result we expect that detailed balance can be used to relate measurements of recombination from the N covered Cu(l 1 1) surface with nitrogen dissociation on bare Cu(l 1 1) terraces. In contrast, if desorption occurred via decomposition of reconstructed copper nitride islands then detailed balance arguments would not reveal anything about the energetics or dynamics of N2 dissociation on a Cu(l 1 1) surface. 

The reaction of copper metal with ammonia [42] between 540 and 570 K gave copper nitride, CujN. A reactant containing a high proportion of CujN (92%) was more stable than that containing more copper metal (70% CujN). Decomposition occurred at 700 K and above in nitrogen. Reaction (- NHj) commenced at about 380 K in Hj and above 650 K in NH,. Nickel metal reacted with ammonia to give NijN at 623 K and the main decomposition occurred at 723 K. NijN was stable only... 

Alone, or Metals, or Metal compounds Mellor, 1940, Vol. 8, 327 1967, Vol. 8, Suppl. 2.2, 84, 96 It is an explosive of positive oxygen balance, less stable than ammonium nitrate, and has been studied in detail. Stable on slow heating to 300°C, it decomposes explosively on rapid heating or under confinement. Presence of zinc, copper, most other metals and their acetylides, nitrides, oxides or sulfides cause flaming decomposition above the m.p. (70°C). Commercial cobalt (cubes) causes an explosion also. 

Acetone-Pis an unstable, white powder or crystalline mass with a melting point of 90 to 93 Celsius. The solid is insoluble in water, but soluble in ether and tetrahydrofuran. It is quite unstable and is rarely used in military or commercial explosives. However it can be utilized as a primary explosive in blasting caps or detonators when desensitized with appropriate materials. To do so, it should be mixed with gum Arabic, carbon black, tri sodium phosphate, chalk, or silicon dioxide powder, and then mixed with a small amount of paraffin s or saturated oils prior to use. Acetone-P can also be slurried with 10% water and 5% hexane for use in blasting caps or detonators. Pure acetone-P should not be used by itself, as it will decay over time potentially leading to explosions. Acetone-P is rather volatile, and a small sample left out in the open will completely evaporate after several days—partly due to decomposition. Acetone-P can also be used in initiating compositions when mixed with sulfur nitride or other primary explosives, and then added to a small amount of a saturated oil. The sulfur nitride and other primary explosives can be replaced by bari urn chromate, copper perchlorate, or lead chromate. Even when acetone-P has been successfully desensitized, it should be used withi n 2 weeks of preparation. ... 

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