Of titanium metal

Other methods iaclude hydrogen reduction of TiCl to TiCl and TiCl2 reduction above the melting poiat of titanium metal with sodium, which presents a container problem plasma reduction, ia which titanium is collected as a powder, and ionized and vaporized titanium combine with chlorine gas to reform TiCl2 on cool-down and aluminum reduction, which reduces TiCl to lower chlorides (19,20). 

The U.S. titanium market distribution is shown in Table 18. Before 1970, more than 90% of the titanium produced was used for aerospace, which feU to ca 70—80% by 1982. Mihtary use has continually decreased from nearly 100% in the early 1950s to 20% in the 1990s. In contrast to the United States, aerospace uses in Western Europe and Japan account for only 40—50% of the demand (58). The CIS s consumption of titanium metal prior to the breakup was about one-half of the world consumption. In the 1980s, considerable amounts were used for submarine constmction. Since the breakup of the former Soviet Union, the internal consumption of titanium in the CIS is beheved to be a modest fraction of its former capacity, thus leaving a large capacity available for export. The world production faciUties for titanium metal and extraction are given in Table 19. 

Titanium Monoxide. Titanium monoxide [12137-20-17, TiO, has a rock-salt stmcture but can exist with both oxygen and titanium vacancies. For stoichiometric TiO, the lattice parameter is 417 pm, but varies from ca 418 pm at 46 atom % to 4I62 pm at 54 atom % oxygen. Apparendy, stoichiometric TiO has ca 15% of the Ti and O sites vacant. At high temperatures (>900° C), these vacancies are randomly distributed at low temperatures, they become ordered. Titanium monoxide may be made by heating a stoichiometric mixture of titanium metal and titanium dioxide powders at 1600°C... 

Titanium Sesc uioxide. Ti202 has the comndum stmcture. At room temperature it behaves as a semiconductor having a small (0.2 eV) band gap. At higher temperatures, however, it becomes metallic. This is associated with marked change in the mean Ti—Ti distance. As with TiO, titanium sesquioxide, Ti202, may be made by heating a stoichiometric mixture of titanium metal and titanium dioxide powders at 1600°C under vacuum in an aluminum or molybdenum capsule. 

Both anatase and mtile are broad band gap semiconductors iu which a fiUed valence band, derived from the O 2p orbitals, is separated from an empty conduction band, derived from the Ti >d orbitals, by a band gap of ca 3 eV. Consequendy the electrical conductivity depends critically on the presence of impurities and defects such as oxygen vacancies (7). For very pure thin films, prepared by vacuum evaporation of titanium metal and then oxidation, conductivities of 10 S/cm have been reported. For both siugle-crystal and ceramic samples, the electrical conductivity depends on both the state of reduction of the and on dopant levels. At 300 K, a maximum conductivity of 1 S/cm has been reported at an oxygen deficiency of... 

Alternatively, the TiCl may be reduced using hydrogen, sodium, or magnesium. It follows that TiCl2 is the first stage in the KroU process for the production of titanium metal from titanium tetrachloride. A process for recovery of scrap titanium involving the reaction of scrap metal with titanium tetrachloride at >800° C to form titanium dichloride, collected in a molten salt system, and followed by reaction of the dichloride with magnesium to produce pure titanium metal, has been patented (122,123). 

Titanium Silicides. The titanium—silicon system includes Ti Si, Ti Si, TiSi, and TiSi (154). Physical properties are summarized in Table 18. Direct synthesis by heating the elements in vacuo or in a protective atmosphere is possible. In the latter case, it is convenient to use titanium hydride instead of titanium metal. Other preparative methods include high temperature electrolysis of molten salt baths containing titanium dioxide and alkalifluorosiUcate (155) reaction of TiCl, SiCl, and H2 at ca 1150°C, using appropriate reactant quantities for both TiSi and TiSi2 (156) and, for Ti Si, reaction between titanium dioxide and calcium siUcide at ca 1200°C, followed by dissolution of excess lime and calcium siUcate in acetic acid. 

Perhaps because of inadequate or non-existent back-bonding (p. 923), the only neutral, binary carbonyl so far reported is Ti(CO)g which has been produced by condensation of titanium metal vapour with CO in a matrix of inert gases at 10-15 K, and identified spectroscopically. By contrast, if MCI4 (M = Ti, Zr) in dimethoxy-ethane is reduced with potassium naphthalenide in the presence of a crown ether (to complex the K+) under an atmosphere of CO, [M(CO)g] salts are produced. These not only involve the metals in the exceptionally low formal oxidation state of —2 but are thermally stable up to 200 and 130°C respectively. However, the majority of their carbonyl compounds are stabilized by n-bonded ligands, usually cyclopentadienyl, as in [M(/j5-C5H5)2(CO)2] (Fig. 21.8). 

The ease of oxidation of magnesium is important in the commercial manufacture of titanium metal. Titanium, when quite pure, shows great promise as a structural metal, but the economics of production have thus far inhibited its use. One of the processes currently used, the Kroll process, involves the reduction of liquid titanium tetrachloride with molten metallic magnesium ... 

Another reductant, magnesium, is used in the industrial production of titanium metal as follows ... 

Fig. 19.S Comparison of titanium metal and titanium nitride-doped NaAlH4 in hydrogen storage.

The vapor pressure of titanium monoxide is much higher than that of zirconium monoxide and hafnium monoxide. However, sacrificial deoxidation is not feasible for titanium because of the relatively high vapor pressure of titanium metal itself. The limiting R value for the titanium-oxygen system is equal to 0.1. 

Vol. 9 Analytical Chemistry of Titanium Metals and Compounds. By Maurice Codell... 

Vol. 9 Analytical Chemistry of Titanium Metals and Compounds. By Maurice Codell Vol. 10 The Chemical Analysis of Air Pollutants. By the late Morris B. Jacobs Vol. 11 X-Ray Spectrochemical Analysis. Second Edition. By L. S. Birks Vol. 12 Systematic Analysis of Surface-Active Agents. Second Edition. By Milton J. Rosen and Henry A. Goldsmith... 

Pyrophoricity and detonation behaviour of titanium hydride powders of various particle sizes were studied in comparison with those of titanium metal powders [1]. Maximum dust explosion pressures of 8.2 bar, with a maximum rate of rise of 816 bar/s have been recorded [2]. 

Titanium (IV) iodide may be prepared by a variety of methods. High-temperature methods include reaction of titanium metal with iodine vapor,1-3 titanium carbide with iodine,4 titanium(IV) oxide with aluminum (III) iodide,5 and titanium (IV) chloride with a mixture of hydrogen and iodine. At lower temperatures, titanium (IV) iodide has been obtained by the combination of titanium and iodine in refluxing carbon tetrachloride7 and in hot benzene or carbon disulfide 8 a titanium-aluminum alloy may be used in place of titanium metal.9 It has been reported that iodine combines directly with titanium at room temperature if the metal is prepared by sodium reduction of titanium (IV) chloride and is heated to a high temperature before iodine is... 

Reaction of titanium metal with a 3% excess of iodine in refluxing carbon tetrachloride (24 hours) gave titanium (IV) iodide in only 30 to 50% yield. 

The electrochemistry of Ti2+ in 66.7 m/o AlCl3-NaCl has been investigated wherein the electroactive Ti2+ was prepared by the oxidation of Ti metal with liquid A1C13 [176, 185] and by the electrochemical dissolution of titanium metal [120, 177], The authors of both studies concluded that Ti2+ may be oxidized stepwise to Ti3+ and Ti4+ and that both processes are reversible at platinum and tungsten electrodes. However, anomalous voltammetric behavior at high Ti2+ concentrations (greater than 50 mmol L ) suggests the formation of polymeric Ti2+ species in the melt. The reduction of Ti2+ to the metal was not observed at potentials more positive than that required for aluminum deposition. 

Fia. 23. Spectra of titanium metal, of metallic appearing TiSi-z phase, of organome-tallic compound of divalent titanium, and of the tetravalent titanium lactate. 

The spectrum of titanium metal foil is in Fig. 23. The foil, originally of 12/t thickness, was reduced by etching in HF to about 4/. A corresponding spectrum of titanium metal powder (not shown here) contained the same peaks but with only about half the amplitude, and with greater scatter of data points. This is an illustration of the advantages of having uniformity of thickness, which is especially difficult to achieve with metal powders. The titanium metal spectrum appears to be Kronig type fine structure. 

The high reactivity of titanium metal is disguised in normal use by its unusually corrosion-resistant protective oxide film (Chapter 16), but it must always be borne in mind by users of Ti process or laboratory equipment. In particular, titanium should not be used with pressurized oxygen pressures of oxygen of as little as 0.4 MPa have been reported to lead to ignition of Ti at ambient temperature if the oxide film is penetrated. 

The largest titanium reserves in the world are in the form of anatase and titano-magnetite, but these cannot be worked economically at the present time. About 95 % of the world s production of ilmenite and rutile is used to produce TiOz pigments, the remainder for the manufacture of titanium metal and in welding electrodes. 

PROBLEM 20.17 How many liters of Cl2 at 20°C and 740 mm Hg pressure would be needed to produce 1.00 X 105 tons of titanium metal from Ti02 if the overall yield is 93.5% ... 

This material, made of titanium metal joined to a biocompatible substance, is used for hip and knee replacements. (Daculsi-CNRS/Photo Researchers, Inc.)... 

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