Compounds interstitial

Small atoms such as C and N have radii less than 2/3 of some of the transitional metals and can form interstitial compounds. The C and N atoms form covalent bonds with transition metals, such as Ti, V, Zr, Nd, Flf, and Ta, to form carbides and nitrides that are extremely hard and have very high melting points. The best-known example of a transitional metal-carbide is Fe3C, also known as cementite, which is the primary hardening component in steel. It has a complex DOn structure similar to Al3Ni. There is another form of Fe3C known as bainite (Pearson symbol hP8—apparently no Strukturbericht symbol) which forms in steels at a lower temperature than cementite. 

A-15 structure of A3B compounds. The A-atoms form aligned chains on the faces of the bcc lattice. 

When discussing metal alloys (Section 4.3), we saw that atoms of non-metallic elements such as H, B, C, and N can be inserted into the interstices (tetrahedral and octahedral holes) of a lattice of metal atoms to form metal-like compounds that are usually nonstoichiometric and have considerable technological importance. These interstitial compounds are commonly referred to as metal hydrides, borides, carbides, or nitrides, but the implication that they contain the anions H, B , C , or is misleading. To clarify this point, we consider first the properties of truly ionic hydrides, carbides, and nitrides. 

In interstitial compounds, however, the nonmetal is conveniently regarded as neutral atoms inserted into the interstices of the expanded lattice of the elemental metal. Obviously, this is an oversimplification, as the electrons of the nonmetal atoms must interact with the modified valence and conduction bands of the metal host, but this crude picture is adequate for our purposes. On this basis, Hagg made the empirical observation that insertion is possible when the atomic radius of the nonmetal is not greater than 0.59 times the atomic radius of the host metal—there is no simple geometrical justification for this, however, as the metal lattice is concomitantly expanded by an unknown amount. These interstitial compounds are sometimes called Hagg compounds. They are, in effect, interstitial solid solutions of the nonmetal in the metal (as distinct from substitutional solid solutions, in which actual lattice atoms are replaced, as in the case of gold-copper and other alloys Section 4.3). 

As we go from left to right across the transition metals in the periodic table, the metal atoms become smaller, much as in the lanthanide contraction (Section 2.6). Furthermore, the atoms of elements of the first transition series are smaller than those of corresponding members of the second and third. Consequently, interstitial carbides are particularly important for metals toward the lower left of the series, as with TiC, ZrC, TaC, and the extremely hard tungsten carbide WC, which is used industrially as an abrasive or cutting material of almost diamond like hardness. The parallel with trends in chemisorption (Section 6.1) will be apparent. 

The typical structure for the composition MH2 is a cubic closest-packing of metal atoms in which all tetrahedral interstices are occupied by H atoms this is the CaF, type. The surplus hydrogen in the lanthanoid hydrides MH2 to MH3 is placed in the octahedral interstices (L Bi type for LaH3 to NdH3, cf. Fig. 15.3, p. 161). 

The interstitial hydrides of transition metals differ from the salt-like hydrides of the alkali and alkaline-earth metals MH and MH2, as can be seen from their densities. While the latter have higher densities than the metals, the transition metal hydrides have expanded metal lattices. Furthermore, the transition metal hydrides exhibit metallic luster and are semiconducting. Alkali metal hydrides have NaCl structure MgH2 has rutile structure. 

The carbides and nitrides of the elements Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Th, and U are considered to be typical interstitial compounds. Their compositions frequently correspond to one of the approximate formulas M2X or MX. As a rule, they are nonstoichiometric compounds with compositions ranging within certain limits. This fact, the limitation to a 

The nitrides can be prepared by heating a metal powder in an N2 or NHj atmosphere to temperatures above 1100 °C. The carbides form upon heating mixtures of the metal powders with carbon to temperatures of about 2200 °C. Both the nitrides and carbides can also be made by chemical transport reactions by the van Arkel-de Boer method if the metal deposition takes place in an atmosphere of N2 or a hydrocarbon. Their remarkable properties are  

Values for comparison melting point of W 3420 °C (highest melting metal), sublimation point of graphite approximately 3350 °C. 

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The transition metal structures consist of close-packed (p. 26) arrays of relatively large atoms. Between these atoms, in the holes , small atoms, notably those of hydrogen, nitrogen and carbon, can be inserted, without very much distortion of the original metal structure. to give interstitial compounds (for example the hydrides, p. 113). 

Pig-iron or cast iron contains impurities, chiefly carbon (up to 5 ). free or combined as iron carbides. These impurities, some of which form interstitial compounds (p. I I3i with the iron, make it hard and brittle, and it melts fairly sharply at temperatures between 1400 and 1500 K pure iron becomes soft before it melts (at 1812 K). Hence cast iron cannot be forged or welded. 

The many possible oxidation states of the actinides up to americium make the chemistry of their compounds rather extensive and complicated. Taking plutonium as an example, it exhibits oxidation states of -E 3, -E 4, +5 and -E 6, four being the most stable oxidation state. These states are all known in solution, for example Pu" as Pu ", and Pu as PuOj. PuOl" is analogous to UO , which is the stable uranium ion in solution. Each oxidation state is characterised by a different colour, for example PuOj is pink, but change of oxidation state and disproportionation can occur very readily between the various states. The chemistry in solution is also complicated by the ease of complex formation. However, plutonium can also form compounds such as oxides, carbides, nitrides and anhydrous halides which do not involve reactions in solution. Hence for example, it forms a violet fluoride, PuFj. and a brown fluoride. Pup4 a monoxide, PuO (probably an interstitial compound), and a stable dioxide, PUO2. The dioxide was the first compound of an artificial element to be separated in a weighable amount and the first to be identified by X-ray diffraction methods. 

Interstitial Compounds. Tungsten forms hard, refractory, and chemically stable interstitial compounds with nonmetals, particularly C, N, B, and Si. These compounds are used in cutting tools, stmctural elements of kilns, gas turbines, jet engines, sandblast nozzles, protective coatings, etc (see also Refractories Refractory coatings). 

Cr C Cr C chromium iton(l l) [12052-89-0] CrFe (c phase), and chromium iron molybdenum(12 36 10) [12053-58-6] Cr 2F 36 o Q phase), are found as constituents in many alloy steels Ct2Al23 and CoCr ate found in aluminum and cobalt-based alloys, respectively. The chromium-rich interstitial compounds, Ci2H, chromium nitrogen(2 l) [12053-27-9] Ct2N, and important role in the effect of trace impurities on the... 

Nitrides. Among the elements of the 15th group, the particular behaviour of nitrogen is notable. Several are the analogies with carbon in the formation, for instance, of interstitial compounds. A number of these phases, such as the refractory solid solution MeN. phases, have been described in 3.8.4 ff. 

Polycrystalline oxide materials, both undoped and doped, have been extensively examined for use as photoanodes. Ti02 electrodes have been prepared by thermal oxidation of a Ti plate in an electric furnace in air at 300-800°C (15-60 min) and in a flame at 1300°C (20 min) [27-30]. XRD analysis of thermally oxidized samples indicates the formation of metallic sub-oxide interstitial compounds, i.e. TiOo+x (x < 0.33) or Ti20i y (0 < y < 0.33) and Ti30 together with rutile Ti02 [27]. The characteristic reflection of metallic titanium decreases in intensity after prolonged oxidation (60 min) at 800° C indicating the presence of a fairly thick oxide layer (10-15 pm). Oxidation at 900°C leads to poor adhesion of the oxide film... 

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