Metal nitrides forms

Entry Reagent Metal nitride formed Product Co-product... 

As we first saw in Section 9.5, nitrogen molecules have a triple bond between the two N atoms. The strength of the triple bond makes N2 very stable, and attempts to break the bond have not been commercially successful. When nitrogen gas is heated with oxygen or hydrogen, nitric oxide (NO) or ammonia (NH3), respectively, form with low yields. When nitrogen gas is heated with active metals, metal nitrides form. Aside from this, however, nitrogen gas is relatively unreactive. 

Hafnium has been successfully alloyed with iron, titanium, niobium, tantalum, and other metals. Hafnium carbide is the most refractory binary composition known, and the nitride is the most refractory of all known metal nitrides (m.p. 3310C). At 700 degrees C hafnium rapidly absorbs hydrogen to form the composition HfHl.86. 

As a future alternative to glassed steel there is ceramics-coated steel which is resistant to abrasion, corrosion and high temperatures. The base metal is coated with silicon nitride formed in situ. Silicon nitride has resistance to both acid and alkali and it is durable at temperatures up to 1 000°C, suggesting a promising future coating in aggressive operating environments. 

Ni3C decomposition is included in this class on the basis of Doremieux s conclusion [669] that the slow step is the combination of carbon atoms on reactant surfaces. The reaction (543—613 K) obeyed first-order [eqn. (15)] kinetics. The rate was not significantly different in nitrogen and, unlike the hydrides and nitrides, the mobile lattice constituent was not volatilized but deposited as amorphous carbon. The mechanism suggested is that carbon diffuses from within the structure to a surface where combination occurs. When carbon concentration within the crystal has been decreased sufficiently, nuclei of nickel metal are formed and thereafter reaction proceeds through boundary displacement. 

The number of oxides is large since most metallic elements form stable compounds with oxygen, either as single or mixed oxides. However, the CVD of many of these materials has yet to be investigated and generally this area of CVD has lagged behind the CVD of other ceramic materials, such as metals, carbides, or nitrides. The CVD of oxides has been slower to develop than other thin-film processes, particularly in optical applications where evaporation. 

This is why companies like Berstorff use PVD-coated screws for this purpose as they exhibit better wear protection than screws with nitrided or stellited surfaces. PVD stands for physical vapor deposition and refers to the evaporation of chrome and its accelerated application onto the surface. In combination with nitrogenous gases, the metal ions form hard nitrides that multiply the wear resistance of the screws. 

Li3(BN2) have already demonstrated the decomposition of (BN2) ions into boron nitride. The remaining nitride can lead to the formation of a binary metal nitride or reduce the transition metal ion under the formation of N2. Both mechanisms have been obtained experimentally, depending on the stability of the metal nitride. For instance niobium pentachloride forms NbN, titanium trichloride forms TiN, and nickel dichloride forms Ni, plus BN and nitrogen, respectively, in reactions with Li3(BN)2 (at 300-600°C) [24]. 

We note that the valence orbitals of metal atoms order in energy as AE>Ln>M. The d-levels of transition elements (M) range the lowest, and are therefore most sensitive for reduction, or to form a stable binary metal nitride. This may also explain the virtual absence of d-element compounds with 16 (valence) electron species, such as [N=N=N] , [N=C=N] , [N=B=N] T [C=C=CfT or [C=B=C] T at least through high-temperature syntheses. 

Structures of the lanthanide nitridoborates appear as layered structures with approximate hexagonal arrangements of metal atoms, and typical coordination preferences of anions. As in many metal nitrides, the nitride ion prefers an octahedral environment such as in lanthanum nitride (LaN). As a terminal constituent of a BNx anion, the nitrogen atom prefers a six-fold environment, such as B-N Lns, where Ln atoms form a square pyramid around N. Boron is typically surrounded by a trigonal prismatic arrangement of lanthanide atoms, as in many metal borides (Fig. 8.10). All known structures of lanthanide nitridoborates compromise these coordination patterns. 

Potassium nitride and other alkali metal nitrides react with sulfur to form a highly flammable mixture, which evolves ammonia and hydrogen sulfide in contact with water. 

Hydrides of variable composition are not only formed with pure metals as solvents. A large number of the binary metal hydrides are non-stoichiometric compounds. Non-stoichiometric compounds are in general common for d,f and some p block metals in combination with soft anions such as sulfur, selenium and hydrogen, and also for somewhat harder anions like oxygen. Hard anions such as the halides, sulfates and nitrides form few non-stoichiometric compounds. Two factors are important the crystal structures must allow changes in composition, and the transition metal must have accessible oxidation states. These factors are partly related. FeO,... 

Nitrogen can be liquefied easily, making it useful in many applications wherein sustained cooling is needed. At high temperatures, nitrogen reacts with many metals to form nitrides. 

Molybdenum In its pure form, without additions, it is the most efficient catalyst of all the easily obtainable and reducible substances, and it is less easily poisoned than iron. It catalyzes in another way than iron, insofar as it forms analytically easily detectable amounts of metal nitrides (about 9% nitrogen content) during its catalytic action, whereas iron does not form, under synthesis conditions, analytically detectable quantities of a nitride. In this respect, molybdenum resembles tungsten, manganese and uranium which all form nitrides during their operation, as ammonia catalysts. Molybdenum is clearly promoted by nickel, cobalt and iron, but not by oxides such as alumina. Alkali metals can act favorably on molybdenum, but oxides of the alkali metals are harmful. Efficiency, as pure molybdenum, 1.5%, promoted up to 4% ammonia. 

When the rate of the chemical reaction occurring at the surface is the rate-limiting step, the principles we have described to this point apply. The reaction rate can have any order, and the gas reacts with the ceramic substrate to produce products. Although our discussion to this point has focused on oxide ceramics, there are a number of nonoxide ceramics, such as carbides, nitrides, or borides, that are of importance and that undergo common decomposition reactions in the presence of oxygen. These ceramics are particularly susceptible to corrosion since they are often used at elevated temperatures in oxidizing and/or corrosive enviromnents. For example, metal nitrides can be oxidized to form oxides ... 

Transition metal nitrides and carbides can be described, generally speaking, as insertion compounds of nitrogen or carbon in the metal network.1 In fact, strong metal-nonmetal interactions exist which induce structural modifications.1,2 These compounds form a class of materials with unique physical3,4 and catalytic1,5,6 properties. The term platinoids has been used to illustrate their potential in reactions traditionally catalysed by noble metals. 

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