Abstract
It is proposed to consider in the following Chapters the true interstitial compounds, as distinct from primary solid solutions or stages intermediate to both, in some more detail than was possible within the framework of Chapter 2. We shall, in sequence, deal with carbides (Chapter 4); nitrides Chapter (5); borides (Chapter 6); suicides (Chapter 7) and oxides, in as far as these are interstitial (Chapter 8); then with hydrides (Chapter 9). Mixed interstitials, e.g. carbonitrides, carbosilicides or-oxides, which in some respects have assumed a new and independent importance, will follow in Chapter 10.
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Selected Literature
I. Binary Metal-Carbon Systems (cf. Section 4.6)
The thermal expansion of the Group IV carbides has been determined73,74 and, more recently, that of Group IV and V carbides387; in studying the melting-point characteristics 388 in the systems (Ti, Zr, Hf, Nb, Ta,)-C, eutectics were confirmed, also in the ternaries combining some of these metals. The Hall coefficient and low-temperature resistivity of TiC were investigated70 as well as its frictional properties and deformation at high temperatures78; this paper gives much detail on the more technological properties of TiC for use in ceramics.
The superconductive properties of the Group V hemicarbides (V2C, Nb2C, Ta2C) have also been discussed389.
For some field-emission microscopy work on TaC, see 110.
Kelley (e.g.145) has also contributed much thermodynamic data of the refractory carbides more generally.
A recent critical review on the Group IV, V, VI and actinide binary carbide systems has been given by Storms261, whilst Richardson’s paper on the thermodynamics of carbides and carbon390 now has become a classic.
The proceedings of a symposium held at A.E.R.E., Harwell, 1963 (Carbides in Nuclear Energy 208) include further information on the U, Np, Pu systems, on physical and chemical properties of U, Pu, and Th carbides and their technological use and behaviour, specifically on U-C vaporization 208c, high-temperature property data208d and thermal conductivity208e.
For a discussion of high-temperature thermodynamic properties of the carbides of Th, U and Pu, see391.
In connection with the Rare Earth carbides, neutron diffraction work252 on the La-carbides, as well as on YC2, (R.E.)C2 and (R.E.)2C3 has elucidated these structures. A review of the magneto-chemistry and x-ray absorption of the R.E. carbides was given by Vickery241 who also published an earlier chemical survey251 (see also 250).
II. Ternary Carbide Systems (cf. Section 4.10)
The following papers represent further work on systems between pseudo-binary pairs of carbides or on ternaries M 1 -M 2-carbon; the sequence is from Group IV to VIIIA. TiC-HfC, ZrC-HfC and HfC-base systems with Group V and VI carbides260; Ti-Mo-C and Mo-W-C287; Ti-Mo-C287; Zr-Cr-C392a,b; Zr-Mo-C138,392c; Ti-W-C393,394; Zr-W-C395; VC-WC396; NbC-TaC and ZrC-NbC397; Hf-Ta-C398; Ta-W-C399; (TiC, TaC, WC)-Cr7C3 277.
For the carbide constitutions underlying hard metals: WC-TiC-TaC-Co, see also400.
The converse case of the solubility in cobalt of TiC, NbC, TaC, Mo2C, WC and their combinations has more recently been studied401; for dilatometric and structure studies on WC-Co alloys, see also 402.
Uranium carbide-based mixed systems have been extensively investigated in relation to atomic reactor materials, e.g.
UC-PuC403 (only preliminary at that stage); 279,280.
U-Pu-C404 (full survey); 208h (especially U2C3-Pu2C3 section); property data208.
UC-HfC405 (complete solubility confirmed at high temperatures, but with possible miscibility gap at lower ones).
U-Zr-C and U-Nb-C 208b (melting points, crystallographic and property data on ternary phases UMC2).
Kinetics and diffusion rates of reactions (at 400–600°C) between U carbides and added metals: Ti, Zr, Th, V, Nb, Cr, Mo, Fe, Al and stainless steel406; U-Nb-C, U-W-C, U-Re-C and U-Y-C208c: (structure, hardness, metallography); U-Cr-C, U-Ni-C, U-Fe-Cr-C208j (phase equilibria); U-Fe-C, Pu-Fe-C and (limited) U-Pu-Fe-C208k: (equilibria extensively studied); UC-ZrC, UC-NbC and UC-TaC278 (continuous series of solutions, with good conformance to Vegard’s law); UC,UC2- (and UN-) based systems407.
For inter-carbide lattice parameter measurements (see e.g. Figure 4.22), cf.268,408–410.
Further Plansee (Kieffer, Benesovsky, etc.) and Vienna (Nowotny) studies have been devoted to Cr-W-C386; U-Zr-C, U-Hf-C, U-Th-C, U-Nb-C, U-Ta-C, V-Mo-C, V-W-C, Nb-Mo-C, Ta-W-C411,412; HfC + other MC270; V-Mo-C413; Zr-Th-C414a; Hf-Ta-C398; Th-Mo-C and U-Mo-C414a,c.
Some of the pseudo-binary monocarbide systems had been presented in earlier work408.
The equilibria of UC2 with UC on the one hand and, with carbon, of ZrC, HfC, NbC and TaC on the other, were given in414c.
The study on HfC270 also presents more general thermodynamic work on ternary carbide equilibria, including calculations of their enthalpies of formation and of the carbide-carbide and carbide-metal solubilities411’415. Partial reviews are contained in other papers by Nowotny416.
III. Hard metals applications and development (cf. Section 4.13.2)
Review books or papers: on metal ceramics (‘Cermets’), including carbide hard metals 91 ’ 263 ’ 417–24; the earlier classic2630 was succeeded by263b; with more emphasis on the technological side of carbide hard metals421. A handbook on hard-metal tools 423 presents a recent survey of the high-temperature chemistry of the refractory carbides, whilst424 reviews the technology and properties of refractory materials, including carbides, from the aspect of rocket propulsion uses.
As to some special properties of hard carbides: thermal expansion 425; hardness at high temperatures426 (also borides); thermophysical properties427,428a; thermodynamic stabilities 428b; electrical properties 428c; various high-temperature properties418; structure and properties of WC-Co-base alloys429; vapour pressures and vaporization rates 430; non-stoichiometry and its implications in hard carbides431; a survey of carbide solid solution, properties and production 432.
Becker’s early work88, industrially orientated, with evident success, covered the refractory carbides more generally and was basic to the subject, as were Moissan’s numerous publications (around 1900).
IV. High- Temperature Steels and ‘Super alloys’, with carbides as frequent constituents: developments (cf. Section 4.13.3)
Some further literature on the function of alloying elements in steels 433 (a classic treatise); stainless steels 307; tool steels 434; high-strength steels 45,435; precipitation in alloy steels (generally, but largely carbides315,436, the latter containing e.g. reviews of work of Quarrell, Honey-combe, Nutting, McLean, etc., on particular aspects in this field; processes during creep 437; high-temperature gas turbine alloys 438 and other high-temperature materials 439,441
Note.—The ‘Nimonic’ type of Ni-Cr-based alloys depends substantially on intermetallic (Ni3Al, etc.), not so much on carbide precipitation; compare, however,442.
On austenitic (e.g. ‘G18B’ type) and ferritic heat-resisting steels, for gas-turbines, etc.2j,438,443,444.
Precipitation mechanisms in iron, cobalt and nickel-based refractory alloys445–450.
Cobalt-based alloys (e.g. ‘Vitallium’ type)334’451–453; the journal ‘Cobalt’, published by the Cobalt Information Centre at Brussels), contains many other papers in this field.
Nickel-based alloys454–456 (typical of many); see also 442.
General structural metallurgy of steels 25,213,457,458 and other papers, e.g. from Nutting’s, Honeycombe’s, Grant’s and Cohen’s (MIT) schools.
V. Atomic Energy Applications of Carbides (cf. Section 4.13.4).
The Proceedings of the 1963 Harwell Conference208 provide 74 papers on uranium and allied carbide applications; Vol. 2 gives the more technological aspects: preparation and fabrication, irradiation behaviour, while Vol. 1 deals with basic properties. Similar information is contained in a (1963) East Hartford (U.S.A.) Conference210; the 4th (1961) Plansee Symposium232 and the (1958) United Nations Symposium459; besides carbides of uranium, etc. these also include nitrides, oxides, borides, etc. A review of properties of uranium carbides, including temperature variations460, is useful also for retrieving earlier references, while a later one461 surveys the thermophysical properties of uranium carbide at high temperatures. An AIME Symposium428 also includes papers concerning carbides.
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Goldschmidt, H.J. (1967). Carbides. In: Interstitial Alloys. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-5880-8_4
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