Titanium and Zirconium

Small amounts of yttrium (0.1 to 0.2%) can be used to reduce the grain size in chromium, molybdenum, zirconium, and titanium, and to increase strength of aluminum and magnesium alloys. 

Flame-Retardant Treatments For Wool. Although wool is regarded as a naturally flame-resistant fiber, for certain appHcations, such as use in aircraft, it is necessary to meet more stringent requirements. The Zirpro process, developed for this purpose (122,123), is based on the exhaustion of negatively charged zirconium and titanium complexes on wool fiber under acidic conditions. Specific agents used for this purpose are potassium hexafluoro zirconate [16923-95-8] [16923-95-8] K ZrF, and potassium hexafluoro titanate [16919-27-0], K TiF. Various modifications of this process have been... 

Hafnium [7440-58-6] Hf, is in Group 4 (IVB) of the Periodic Table as are the lighter elements zirconium and titanium. Hafnium is a heavy gray-white metallic element never found free in nature. It is always found associated with the more plentiful zirconium. The two elements are almost identical in chemical behavior. This close similarity in chemical properties is related to the configuration of the valence electrons, and for zirconium and... 

Electrolysis. Electro winning of hafnium, zirconium, and titanium has been proposed as an alternative to the KroU process. Electrolysis of an all chloride hafnium salt system is inefficient because of the stabiHty of lower chlorides in these melts. The presence of fluoride salts in the melt increases the StabiHty of in solution and results in much better current efficiencies. Hafnium is produced by this procedure in Erance (17). 

In this process, catalysts, such as boric acid, molybdenum oxide, zirconium, and titanium tetrachloride or ammonium molybdate, are used to accelerate the reaction. The synthesis is either carried out in a solvent (aUphatic hydrocarbon, trichlorobenzene, quinoline, pyridine, glycols, or alcohols) at approximately 200°C or without a solvent at 300°C (51,52). 

Sodium ethoxide was the first metal alkoxide described in 1837 (1). The alkoxides of many transition metals were developed after World War II (2—5). Today some alkoxides, including those of sodium, potassium, magnesium, aluminum, zirconium, and titanium, are commercially important. The name metal alkoxides is preferred, although metal alcoholates is also used. 

Borides are inert toward nonoxidizing acids however, a few, such as Be2B and MgB2, react with aqueous acids to form boron hydrides. Most borides dissolve in oxidizing acids such as nitric or hot sulfuric acid and they ate also readily attacked by hot alkaline salt melts or fused alkaU peroxides, forming the mote stable borates. In dry air, where a protective oxide film can be preserved, borides ate relatively resistant to oxidation. For example, the borides of vanadium, niobium, tantalum, molybdenum, and tungsten do not oxidize appreciably in air up to temperatures of 1000—1200°C. Zirconium and titanium borides ate fairly resistant up to 1400°C. Engineering and other properties of refractory metal borides have been summarized (1). 

Various inorganic esters have been claimed as coupling agents for reinforced plastics, including aminobenzyl phosphonates, dicetylisopropylborate, alkoxy compounds of aluminum, zirconium and titanium, zircoaluminates, and numerous substituted titanates [1]. These metal alkoxides could function in a similar manner to the orthosilicates by reacting with hydroxylated substrates. Like the simple orthosilicates such as tetraethyl orthosilicate (TEOS), it is less evident how an-... 

Niobium-Zirconium-Titanium Niobium alloys containing zirconium and titanium have improved resistance to high-temperature water and have been evaluated for use in pressurised-water nuclear reactors. 

Other Binary Compounds.—Scandium nitride and zirconium and titanium carbide do not conform with the theoretical radii. It is possible that these crystals do not consist essentially of Sc+3, N 3, Ti+4, Zr+4 and C-4 ions, especially since zirconium and titanium nitride, ZrN and TiN, also form crystals with the sodium chloride structure but possibly also the discrepancy can be attributed to deformation of the anions, which have very high mole refraction values. 

The cyclopentadienyl triflate complexes of zirconium and titanium 51 and 52 (Figure 3.7) are also active catalysts [51]. Their activity has been tested in a wide variety of dienes and dienophiles. It is noteworthy that even at low catalyst loadings, rate accelerations between 10 and > 10 times have been observed. No special precautions were taken to dry the solvents or the substrates, in contrast with the traditional Lewis acids which require either predried solvents or high catalyst loadings. 

Metallothermic reduction of chlorides has been the basis of some very important processes for reactive metals production. Examples include the Kroll and Hunter processes for the preparation of zirconium and titanium, and calcium or lithium reduction processes for the rare earths. 

The highest ethylene polymerization activity for a tetradentate salen-type group 4 complex was reported for silica supported (64) (600gmmol-1h bar ).193 Activities for a range of related zirconium and titanium complexes such as (65)-(67) are typically an order of magnitude lower.194-196... 

Alkoxides and imido are used as anionic ligands in zirconium and titanium catalysts for the polymerisation of alkenes, sometimes as the only anions, but often in combination with cyclopentadienyl ligands. Imides linked to cyclopentadienyl groups form part of the single-site catalyst developed by Dow (Chapter 10) (Figure 1.9, 1). In very different titanium catalysts, namely those used for epoxidation of alkenes, also alkoxide ligands are used (Chapter 14). 

Ruthenium, cobalt and halogen are the key elements of this catalysis (2), although ruthenium in combination with halogen-containing zirconium and titanium derivatives is also effective (3). In the case of the Ru-Oo couple, the highest yields of acetic acid may generally be achieved with ruthenium oxide, carbonyls and complex derivatives in combination with various cobalt halides dispersed in low-melting quaternary phosphonium halide salts (2). 

In the search for substitutes, other considerations than just sulfide stability have to be considered. These include the possible interference of the newly introduced element with other steel porperties, the plasticity of the new sulfides, the physical alloyability of the additive and, of course, the cost effectiveness of the additive. Zirconium and titanium interfere with other properties of the steel because of the excessive stability of their nitrides. Figure 9, and carbides. Figure 10. Although considerable usage of these two elements has played a part in sulfide substitution — over 500 metric tons of nuclear zircalloy scrap were used in — it appears that their role will progressively fade away primarily because of poor low temperature impact properties of steels treated with Zr and Ti. 

The initial success with early transition metals, such as zirconium and titanium, reported by the Buchwald group, included an indirect cycloaddition between an enyne and isocyanides. The first protocol that used [Gp2Ti(PMc3)2] or Ni(GOD) together with triphenylphosphine failed to cyclize the enynes under the pressure of GO, but provided the cyclic imines with trialkylsilyl isocyanides, and bicyclic enones were obtained by hydrolysis of the resultant imine products (Equation (9)). ... 

Toxicity Variable. The hydrides of phosphorus, arsenic, sulfur, selenium, tellurium and boron which are highly toxic, produce local irritation and destroy red blood cells. They are particularly dangerous because of their volatility and ease of entry into the body. The hydrides of the alkali metals, alkaline earths, aluminum, zirconium and titanium react with moisture to evolve hydrogen and leave behind the hydroxide of the metallic element. This hydroxide is usually caustic. See also sodium hydroxide... 

In contrast to V-heteroaldehyde and -ketone complexes, r -heteroalde-hyde complexes are less prone to cyclo addition reactions. The reactivity of these complexes is characterized by the insertion of C N, C=0, and C=N bonds into the M-C(heteroaldehyde) bond as has been demonstrated with the examples of zirconium and titanium complexes. 

The coupling agents which have been most extensively used are various organo-silicon compounds, although several other types of compound of quite different chemistry, including zirconium and titanium comlexes [1], have also been used. It is with silane materials that we are concerned here. 

Miedaner [11] in several patents has disclosed that zirconium and titanium complexes of orthofunctional aromatic compounds (monomeric or polymeric) could be used as coupling agents for phenolic or resorcinol resins and glass. 

Modification by acetylacetone is a powerful route, that allows precursor solutions to be stabilized. Interaction of titanium alkoxides with acetylacetone was extensively studied and reviewed in [1391,86]. Study ofreactions, occurring on interaction of Zr(OPrn)4 and Ti-Zr alkoxide mixture with acetylacetone, was performed in [1448] and allowed the authors to simplify the technique for preparation of precursor solution for PZT films application and to overcome the requirement of prolonged refluxing, which certainly decreases reproducibility. After dissolution of titanium and zirconium alkoxides in methoxyethanol, acetylacetone is added to form stable zirconium and titanium stock solutions. The introduction of acetylacetone allowed aqueous lead acetate (and lanthanum acetate for PLZT films) solutions to be added to mixed titanium and zirconium solutions. No reaction steps involving elevated temperatures or distillation or long reaction times are required. The solution could be used both immediately on mixing or after storage for several months. Such solutions were successfully used for application of ferroelectric films. 

Zirconium and titanium have close-packed hexagonal structures at room temperatures. 

Syntheses of MPc from phthalodinitrile or phthalic anhydride in the presence of urea are the two most important laboratory and industrial methods. They were also used originally by Linstead et al. [8,9], This procedure allows the production of many phthalocyanine compounds [35-37], Catalysts such as boric acid, molybdenum oxide, zirconium and titanium tetrachloride, or ammonium molybdate are used to accelerate the reaction and improve the yield [36,37], Ammonium molybdate is especially effective. Reaction is carried out either in a solvent or by heating the solid components. When metal chlorides and phthalodinitrile are used as starting materials, the reaction products are partially chlorinated (e.g.,7). 

The environments, along with the cracking modes of zirconium and titanium, are given in Table 4.88. It is obvious from the table that zirconium alloys are susceptible to stress-corrosion cracking in a variety of environments. It is necessary to subject the weld to heat treatment in order to lower the stress in the weld. The most serious problem encountered in the nuclear applications is delayed hydride cracking in addition to stress-corrosion cracking, particularly in Zr-2.5% Nb alloy. 

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