Metals titanium

Titanium forms dihalides TiXj, for example titanium(II) chloride, formed by heating titanium metal and the tetrachloride to about 1200 K. TiCl2 is a black solid, which disproportionates on standing to TiCl4 + Ti. Since it reduces water to hydrogen, there is no aqueous chemistry for titanium(II). A solid oxide TiO is known. 

Titanium metal is considered to be physiologically inert. When pure, titanium dioxide is relatively clear and has an extremely high index of refraction with an optical dispersion higher than diamond. 

Titanium Metals Corp. of America Henderson, Nev. Vulcan Chemicals 1943 LG. Farben magnesium 9... 

Titanium trifluoride [13470-08-17, TiF, is a blue crystalline solid that undergoes oxidation to Ti02 upon heating in air at 100°C (see Titanium compounds). In the absence of air, disproportionation occurs above 950°C to give TiF and titanium metal. TiF decomposes at 1200°C, has a density of 2.98 g/cm, and is insoluble in water but soluble in acids and alkafles. The magnetic moment is 16.2 x 10 J/T (1.75 -lB). 

Titanium trifluoride is prepared by dissolving titanium metal in hydrofluoric acid (1,2) or by passing anhydrous hydrogen fluoride over titanium trihydrate at 700°C or over heated titanium powder (3). Reaction of titanium trichloride and anhydrous hydrogen fluoride at room temperature yields a cmde product that can be purified by sublimation under high vacuum at 930—950°C. 

Titanium tetrafluoride may be prepared by the action of elemental fluorine on titanium metal at 250°C (5) or on Ti02 at 350°C. The most economical and convenient method is the action of Hquid anhydrous HF on commercially available titanium tetrachloride in Teflon or Kynar containers. Polyethylene reacts with TiCl and turns dark upon prolonged exposure. The excess of HF used is boiled off to remove residual chloride present in the intermediates. 

Titanium(lV) fluoride dihydrate [60927-06-2] TiF 2H20, crystals can be prepared by the action of aqueous HF on titanium metal. The solution is carefully evaporated to obtain the crystals. Neutral solutions when heated slowly hydroly2e and form titanium(lV) oxyfluoride [13537-16-17, TiOF2 (6). Upon dissolution in hydrogen fluoride, TiF forms hexafluorotitanic acid [17439-11-17, ll]TiF. ... 

The iodide or van Arkel-de Boer process is a volatilization process involving transfer of an involatile metal as its volatile compound. It is used for the purification of titanium. The reaction of iodine gas with impure titanium metal at 175°C yields gaseous titanium iodide and leaves the impurities in the sohd residue. 

The 1990s reduction process was based on work started in the early 1930s. A magnesium vacuum reduction process was developed for reduction of titanium tetrachloride to metal. Based on this process, the U.S. Bureau of Mines (BOM) initiated a program in 1940 to develop commercial production. Some years later, the BOM pubHcized its work on titanium and made samples available to the industrial community. By 1948, the BOM produced batch sizes of 104 kg. In the same year, Du Pont aimounced commercial availabiHty of titanium, thus beginning the modem titanium metals industry (1). 

Optimism foUowed by disappointment has characterized the titanium metals industry. In the late 1960s, the future again appeared bright. 

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). 

Titanium metal was first used as a material for aerospace. In the late 1970s, new appHcations developed that utilize the metal s exceUent corrosion... 

Titanium metal is especially utilised ia environments of wet chlorine gas and bleaching solutions, ie, in the chlor—alkaH industry and the pulp and paper industries, where titanium is used as anodes for chlorine production, chlorine—caustic scmbbers, pulp washers, and CI2, CIO2, and HCIO storage and piping equipment (see Alkali and cm ORiNE products Paper Pulp). 

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 for industrial Brine and Sea Water Service, Titanium Metal Corporation of America, Denver, Colo., 1968. 

Titanium Nitride. Titanium nitride [25583-20-4] has the cubic NaCl stmeture, but the stmeture is stable over a wide range of either anion or cation deficiency (TINq 25 = 421 pm TiN q, = 423.5 pm). The nitride is a better conductor of electricity than titanium metal. It becomes... 

Direct synthesis from nitrogen and finely divided titanium metal can be achieved at temperatures of >ca 1200° C (4). Typically, titanium sponge or powder is heated in an ammonia- or nitrogen-filled furnace and the product is subsequently milled and classified. 

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... 

Titanium trifluoride may be prepared ia 90% yield by the reaction of gaseous hydrogen fluoride, ia practice ia a 1 4 ratio of hydrogen HF, with either titanium metal or titanium hydride at 900°C. 

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 tetraiodide can be prepared by direct combination of the elements at 150—200°C it can be made by reaction of gaseous hydrogen iodide with a solution of titanium tetrachloride in a suitable solvent and it can be purified by vacuum sublimation at 200°C. In the van Arkel method for the preparation of pure titanium metal, the sublimed tetraiodide is decomposed on a tungsten or titanium filament held at ca 1300°C (152). There are frequent hterature references to its use as a catalyst, eg, for the production of ethylene glycol from acetylene (153). 

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. 

Titanium Phosphides. The titanium phosphides (154) include Ti P [12037-66-0], Ti P, and TiP (163). Titanium monophosphide [12037-65-9] TiP, can be prepared by beating phosphine with titanium tetrachloride or titanium sponge. Alternatively, titanium metal may be heated with phosphoms ia a sealed tube. The gray metallic TiP is slightly phosphoms-deficient (TiPQ has a density of 408(0) kg/m, and displays considerable... 

Titanium disulfide can also be made by pyrolysis of titanium trisulfide at 550°C. A continuous process based on the reaction between titanium tetrachloride vapor and dry, oxygen-free hydrogen sulfide has been developed at pilot scale (173). The preheated reactants ate fed iato a tubular reactor at approximately 500°C. The product particles comprise orthogonally intersecting hexagonal plates or plate segments and have a relatively high surface area (>4 /g), quite different from the flat platelets produced from the reaction between titanium metal and sulfur vapor. The powder, reported to be stable to... 

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