NITRIDES surface area

Composition Nitridation temperature (K) Nitridation Surface area time (h) (m2.g-l) Total N (wt.%) Surface N (wt.%)... 

P/M steels can be heat treated in the same manner as cast or wrought steels. They may be austenitized, quenched, and tempered. Surface hardening includes pack or gas carburization or nitriding, ie, heating in a nitrogen-containing atmosphere. Because of the greater amount of exposed surface area in the form of porosity, a protective atmosphere is needed (see Metal surface treatments). 

Catalysis. The development of high surface area porous M02N and W2N has spurred interest in nitrides for catalytic appHcations (52—58). High... 

The new method produces TiN powders with surface areas exceeding 200 m g that are otherwise only accessible using a forced flow reactor and a microwave plasma activator in which titanium metal is reacted with N2 in the gas phase [14]. TiN powders with considerably lower specific surface area (Sg<60m g ) were also synthesized using the nitridation of 10-15 nm-sized... 

Re-use of the catalyst The high activity of the solid catalysts also allows one to re-use high surface area titanium nitride several times. By centrifugation, the solid can be separated and used in a new reaction. The catalyst was used up to four times. Figure 19.10 shows the conversion of DPE with time. 

Mechanism The understanding of mechanisms in catalytic reactions is sometimes crucial for the creative development of new applications. In a first approach, the main interest was to develop high surface area titanium nitride as a material for catalytic applications and, therefore, evaluation of catalysts prepared under different conditions was performed. 

Sample Nitrid- ation Temp (K) H2 NH3 ratio Time (hr) BET surface area Particle dispersion (%) Active particle diameter (nm)... 

Composition, nitridation temperature and time, surface area and nitrogen content of the "AlPONs"... 

The macrostructure of the boron nitride obtained here is porous with pores 2 pm in diameter. There is no evidence for microporosity and the BET surface area 1s 35 m2 g-1. Transmission electron micrographs (Figure 4) show regions of well developed crystallinity. The crystalling grains are 5—10 nm on a side and 30-40 nm long. The BN (002) lattice fringes are clearly visible. 

The material is impact-sensitive when dry and is supplied and stored damp with ethanol. It is used as a saturated solution and it is important to prevent total evaporation, or the slow growth of large crystals which may become dried and shock-sensitive. Lead drains must not be used, to avoid formation of the detonator, lead azide. Exposure to acid conditions may generate explosive hydrazoic acid [1], It has been stated that barium azide is relatively insensitive to impact but highly sensitive to friction [2], Strontium, and particularly calcium azides show much more marked explosive properties than barium azide. The explosive properties appear to be closely associated with the method of formation of the azide [3], Factors which affect the sensitivity of the azide include surface area, solvent used and ageing. Presence of barium metal, sodium or iron ions as impurities increases the sensitivity [4], Though not an endothermic compound (AH°f —22.17 kJ/mol, 0.1 kj/g), it may thermally decompose to barium nitride, rather than to the elements, when a considerable exotherm is produced (98.74 kJ/mol, 0.45 kJ/g of azide) [5]. 

Generally, metal nitride and oxynitride catalysts have been prepared by the temperature programmed ammonolysis method. This technique was originally applied by Volpe and Boudart to M0O3 precursors to produce y-Mo2N which was pseudomOrphic with the precursor, with surface areas up to 225 m g The resultant surface area of materials is known to be a strong function of the synthesis parameters as demonstrated in Table 1. ... 

Table 1 The influence of ammonolysis parameters on the surface area of molybdenum nitride adapted from reference 18...

When controlled nitridation of surface layers is required, as for example in the modification of the chemical properties of the surface of a support, the atomic layer deposition (ALD) technique can be applied." This technique is based upon repeated separate saturating reactions of at least two different reactants with the surface, which leads to the controlled build-up of thin films via reaction of the second component with the chemisorbed residues of the first reactant. Aluminium nitride surfaces have been prepared on both alumina and silica supports by this method wherein reaction cycles of trimethylaluminium and ammonia have been performed with the respective supports, retaining their high surface areas." This method has been applied to the modification of the support composition for chromium catalysts supported on alumina." ... 

The first syntheses of transition metal nitrides and carbides were derived from metallurgical processes,1,3 and consisted in the nitridation or carburization of the metal or of the oxide at severe conditions, in particular at high temperatures (>1500 K). Consequently, the resulting powders generally had low specific surface areas (Sg). 

In earlier work, it was found for borides, silicides and nitrides that specific activity, expressed as total rate of methane consumption per unit surface area, plummeted with increasing surface area of the catalyst samples.1718 The same relationship was also found for transition metals carbides (Figure 16.4). It should be noted the dependence of specific activity on surface area rather than catalyst composition is unusual for heterogeneous catalytic reactions. In addition, it can be found that the reaction order in the oxidant is perceptibly in excess of 1 (Tables 16.8 and 16.9). Such an order is hard to explain in terms of common mechanism schemes for heterogeneous catalytic oxidative reactions. 

---