Titanium illustration

Titanium. The metallurgy of titanium illustrates the purification of one metal by another. The major titanium ores are mtile (Ti02) and ilmenite (FeTi03). Either is converted to titanium(IV) chloride by a redox reaction with... 

A recent successful application of carbon/carbon composites is the tool for superplastic forging of titanium illustrated by Figure 6 tubes up to 1.5 m in length can be forged at temperatures up to 1000°C, thus offering a rapid alternative fabrication technique to present production methods, e.g., riveted tubes (15). Contact brushes for electrical commutators, made with carbon fibers and carbon/carbon composites (16), are opening another new field of application. Furthermore, pistons in diesel engines have been proposed to be made from carbon/carbon composites (17). 

The monometallic mechanism is illustrated in Fig. 7.13a. It involves the monomer coordinating with an alkylated titanium atom. The insertion of the monomer into the titanium-carbon bond propagates the chain. As shown in... 

Figure 7.14a illustrates the insertion of a propylene monomer into an edge vacancy in a crystal adjacent to an alkylated titanium atom. In Fig. 7.14b a cross-sectional view of the same site shows how the preferential orientation of the coordinated monomer is dictated by constraints imposed by the protuberances on the crystal surface. 

The bimetallic mechanism is illustrated in Fig. 7.13b the bimetallic active center is the distinguishing feature of this mechanism. The precise distribution of halides and alkyls is not spelled out because of the exchanges described by reaction (7.Q). An alkyl bridge is assumed based on observations of other organometallic compounds. The pi coordination of the olefin with the titanium is followed by insertion of the monomer into the bridge to propagate the reaction. 

Titanium raw-material utilization can be broken down as illustrated in Figure 9. About 4% of the titanium mined is used as metal, 94% is used as pigment-grade Ti02, and 2% as ore-grade mtile for fluxes and ceramics. In 1995, the estimated U.S. Ti02 pigment production was valued at 2.6 biUion and was produced by five companies at 11 plants in nine states. About 47% was used in paint, 18% in plastics, 24% in paper, and 18% in other misceUaneous appHcations (56). 

Surface cleaning/etches. As with aluminum and titanium, the most critical test for bonded steel joints is durability in hostile (i.e., humid) environments. The fact that the problem is a serious one for steel was illustrated in a study [117] that compared solvent cleaned (smooth) 1010 cold-rolled steel surfaces with FPL aluminum (microrough) substrates. Although the dry lap-shear strengths were not markedly different, stressed lap-shear joints of steel adherends that were exposed to a humid environment failed in less than 30 days, whereas the aluminum joints lasted for more than 3000 days. 

In 1980, Katsuki and Sharpless communicated that the epoxidation of a variety of allylic alcohols was achieved in exceptionally high enantioselectivity with a catalyst derived from titanium(IV) isopropoxide and chiral diethyl tartrate. This seminal contribution described an asymmetric catalytic system that not only provided the product epoxide in remarkable enantioselectivity, but showed the immediate generality of the reaction by examining 5 of the 8 possible substitution patterns of allylic alcohols all of which were epoxidized in >90% ee. Shortly thereafter. Sharpless and others began to illustrate the... 

Numerous theoretical and experimental studies have dealt with the properties of rutile (see 3 and references therein), while the other polymorphs have attracted less attention. This is due to the fact that rutile is easier to grow and characterize, and has a simpler structure that can be readily investigated using a variety of theoretical techniques. The fact that the experimentally reported bulk modulus of anatase is in the range from 59 GPa to 360 GPa illustrates the need for further studies of titanium dioxide polymorphs. 

Similar phenomena were observed on the high-strength industrial titanium alloys, as illustrated for the Ti-6A1-4.5V alloy in Fig. 4. 

Mechanical properties of hydrogenated titanium alloys are strongly dependent on the applied stress tensor, especially on its hydrostatic component. This was illustrated by the high-pressure tensile and extrusion tests on the Ti-6Al-2.5Mo-2Cr alloy and the same alloy hydrogenated to a = 0.15 wt.%H. Tests were carried out using the apparatus at the Institute of Metal Physics UD RAS operating at hydrostatic pressures of machine oil to 15 kbax and temperatures to 250°C. 

This example of aluminium illustrates the importance of the protective him, and hlms that are hard, dense and adherent will provide better protection than those that are loosely adherent or that are brittle and therefore crack and spall when the metal is subjected to stress. The ability of the metal to reform a protective him is highly important and metals like titanium and tantalum that are readily passivated are more resistant to erosion-corrosion than copper, brass, lead and some of the stainless steels. There is some evidence that the hardness of a metal is a signihcant factor in resistance to erosion-corrosion, but since alloying to increase hardness will also affect the chemical properties of the alloy it is difficult to separate these two factors. Thus althou copper is highly susceptible to impingement attack its resistance increases with increase in zinc content, with a corresponding increase in hardness. However, the increase in resistance to attack is due to the formation of a more protective him rather than to an increase in hardness. 

The titanium-catalyzed AE reaction is a fairly robust system and it can be performed on substrates containing a wide range of different functional groups (FGs) (Table 6.3) [13]. However, it is important to point out that an intramolecular reaction with the formed epoxide is possible whenever the FG present in the molecule has a favorable position to facilitate such a transformation. An illustration of this phenomenon is presented in Eq. (1) [28]. 

The formation of surface defects of a crystal lattice. It was observed while using crystal compounds of transition metals as catalysts [e.g. as was shown by Arlman (171, 173), for a TiCl3 surface defects appear on the lateral faces of the crystal]. In this case low surface concentration of the propagation centers should be expected, as is illustrated in the case of polymerization by titanium dichloride (158). The observed... 

A demonstration of the feasibility of a reaction is illustrated in the following example regarding the formation of titanium diboride using either diborane or boron trichloride as a boron source, as shown in the following reactions ... 

The formation of a bis(guanidinate)-supported titanium imido complex has been achieved in different ways, two of which are illustrated in Scheme 90. The product is an effective catalyst for the hydroamination of alkynes (cf. Section V.B). It also undergoes clean exchange reactions with other aromatic amines to afford new imide complexes such as [Me2NC(NPr )2]2Ti = NC6F5. ... 

Tridentate amido-amidinate ligands have also been constructed starting from (lR,2R)-diaminocyclohexane (cf. Section IV.D). Scheme 181 illustrates the use of such ligand in the preparation of novel amidinato-titanium alkoxide com-plexes. ... 

Amidinate complexes of copper(I) and copper(II) have been found to catalyze the polymerization of carbodiimides. The copper catalysts are highly active even under air and oxygen. It was shown that the catalytic activity of an air-stable copper(II) amidinato complex is almost equal to that of reported air-sensitive titanium(IV) amidinate initiators. Scheme 225 illustrates the proposed reaction mechanism. ... 

Considerable attention has been directed to dehalogenation mediated by corrinoids and porphyrins in the presence of a chemical reductant (references in Gantzer and Wackett 1991 Glod et al. 1997 Workman et al. 1997). Illustrations are provided by the dechlorination and elimination reactions carried out by titanium(III) citrate and hydroxocobala-min (Bosma et al. 1988 Glod et al. 1997). The involvement of corrinoids and porphyrins is consistent with the occurrence of analogous mechanisms for biological reactions that... 

Reaction conditions that involve other enolate derivatives as nucleophiles have been developed, including boron enolates and enolates with titanium, tin, or zirconium as the metal. These systems are discussed in detail in the sections that follow, and in Section 2.1.2.5, we discuss reactions that involve covalent enolate equivalents, particularly silyl enol ethers. Scheme 2.1 illustrates some of the procedures that have been developed. A variety of carbon nucleophiles are represented in Scheme 2.1, including lithium and boron enolates, as well as titanium and tin derivatives, but in... 

These examples and those in Scheme 2.6 illustrate the key variables that determine the stereochemical outcome of aldol addition reactions using chiral auxiliaries. The first element that has to be taken into account is the configuration of the ring system that is used to establish steric differentiation. Then the nature of the TS, whether it is acyclic, cyclic, or chelated must be considered. Generally for boron enolates, reaction proceeds through a cyclic but nonchelated TS. With boron enolates, excess Lewis acid can favor an acyclic TS by coordination with the carbonyl electrophile. Titanium enolates appear to be somewhat variable but can be shifted to chelated TSs by use of excess reagent and by auxiliaries such as oxazolidine-2-thiones that enhance the tendency to chelation. Ultimately, all of the factors play a role in determining which TS is favored. 

Scheme 2.9 gives some examples of use of enantioselective catalysts. Entries 1 to 4 are cases of the use of the oxazaborolidinone-type of catalyst with silyl enol ethers and silyl ketene acetals. Entries 5 and 6 are examples of the use of BEMOL-titanium catalysts, and Entry 7 illustrates the use of Sn(OTf)2 in conjunction with a chiral amine ligand. The enantioselectivity in each of these cases is determined entirely by the catalyst because there are no stereocenters adjacent to the reaction sites in the reactants. 

Apart from chlorine (without or with carbon), carbon tetrachloride, phosgene, hydrogen chloride, and sulfur dioxide-chlorine mixtures, some of the metal chlorides can also function as chlorinating agents. The chlorinating action of metal chlorides is dramatically illustrated by the behavior of the silica lining in reactors used for the chlorination of titanium dioxide and beryllium dioxide. 

Two processes are used in the manufacture of titanium dioxide pigments the sulfate process and the chloride process. The chemistry of the sulfate process, the longer established of the two methods, is illustrated schematically in Scheme 9.1. In this process, crude ilmenite ore, which contains titanium dioxide together with substantial quantities of oxides of iron, is digested with concentrated sulfuric acid, giving a solution containing the sulfates of Ti(iv), Fe(m) and Fe(n). Treatment of this... 

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