Zirconium oxidations

Figure Bl.25.9(a) shows the positive SIMS spectrum of a silica-supported zirconium oxide catalyst precursor, freshly prepared by a condensation reaction between zirconium ethoxide and the hydroxyl groups of the support [17]. Note the simultaneous occurrence of single ions (Ff, Si, Zr and molecular ions (SiO, SiOFf, ZrO, ZrOFf, ZrtK. Also, the isotope pattern of zirconium is clearly visible. Isotopes are important in the identification of peaks, because all peak intensity ratios must agree with the natural abundance. In addition to the peaks expected from zirconia on silica mounted on an indium foil, the spectrum in figure Bl. 25.9(a)...

Zirconium is found in abundance in S-type stars, and has been identified in the sun and meteorites. Analysis of lunar rock samples obtained during the various Apollo missions to the moon show a surprisingly high zirconium oxide content, compared with terrestrial rocks. 

Zincite, see Zinc oxide Zincosite, see Zinc sulfate Zincspar, see Zinc carbonate Zirconia, see Zirconium oxide... 

Lead Ammonium nitrate, chlorine trifluoride, hydrogen peroxide, sodium azide and carbide, zirconium, oxidants... 

The equilibrium is more favorable to acetone at higher temperatures. At 325°C 97% conversion is theoretically possible. The kinetics of the reaction has been studied (23). A large number of catalysts have been investigated, including copper, silver, platinum, and palladium metals, as well as sulfides of transition metals of groups 4, 5, and 6 of the periodic table. These catalysts are made with inert supports and are used at 400—600°C (24). Lower temperature reactions (315—482°C) have been successhiUy conducted using 2inc oxide-zirconium oxide combinations (25), and combinations of copper-chromium oxide and of copper and silicon dioxide (26). 

The heavy mineral sand concentrates are scmbbed to remove any surface coatings, dried, and separated into magnetic and nonmagnetic fractions (see Separation, magnetic). Each of these fractions is further spHt into conducting and nonconducting fractions in an electrostatic separator to yield individual concentrates of ilmenite, leucoxene, monazite, mtile, xenotime, and zircon. Commercially pure zircon sand typically contains 64% zirconium oxide, 34% siUcon oxide, 1.2% hafnium oxide, and 0.8% other oxides including aluminum, iron, titanium, yttrium, lanthanides, uranium, thorium, phosphoms, scandium, and calcium. 

Decomposition of Zircon. Zircon sand is inert and refractory. Therefore the first extractive step is to convert the zirconium and hafnium portions into active forms amenable to the subsequent processing scheme. For the production of hafnium, this is done in the United States by carbochlorination as shown in Figure 1. In the Ukraine, fluorosiUcate fusion is used. Caustic fusion is the usual starting procedure for the production of aqueous zirconium chemicals, which usually does not involve hafnium separation. Other methods of decomposing zircon such as plasma dissociation or lime fusions are used for production of some grades of zirconium oxide. 

Alkaline-Earth Titanates. Some physical properties of representative alkaline-earth titanates ate Hsted in Table 15. The most important apphcations of these titanates are in the manufacture of electronic components (109). The most important member of the class is barium titanate, BaTi03, which owes its significance to its exceptionally high dielectric constant and its piezoelectric and ferroelectric properties. Further, because barium titanate easily forms solid solutions with strontium titanate, lead titanate, zirconium oxide, and tin oxide, the electrical properties can be modified within wide limits. Barium titanate may be made by, eg, cocalcination of barium carbonate and titanium dioxide at ca 1200°C. With the exception of Ba2Ti04, barium orthotitanate, titanates do not contain discrete TiO ions but ate mixed oxides. Ba2Ti04 has the P-K SO stmcture in which distorted tetrahedral TiO ions occur. 

Tubes for dynamic membranes ate usually smaller (ca 6-mm ID). Typically, the tubes ate porous carbon or stainless steel with inorganic membranes (sihca, zirconium oxide, etc) formed in place. 

Baddeleyite, a naturally occurring zirconium oxide, has been found in the Poco de Caldas region of the states of Sao Paulo and Minas Geraes in Brazil, the Kola Peninsula of the former USSR, and the northeastern Transvaal of the Repubflc of South Africa. BraziUan baddeleyite occurs frequently with zircon, and ore shipments are reported to contain 65—85% zirconium oxide, 12—18% siUca, and 0.5% uranium oxide. Veryhttle of this ore is exported now because all radioactive minerals are under close control of the BraziUan government. 

The Phalaborwa complex ia the northeastern Transvaal is a complex volcanic orebody. Different sections are mined to recover magnetite, apatite, a copper concentrate, vermicuhte, and baddeleyite, Hsted in order of aimual quantities mined. The baddeleyite is contained in the foskorite ore zone at a zirconium oxide concentration of 0.2%, and at a lesser concentration in the carbonatite orebody. Although baddeleyite is recovered from the process tailings to meet market demand, the maximum output could be limited by the requirements for the magnetite and apatite. The baddeleyite concentrate contains ca 96% zirconium oxide with a hafnium content of 2% Hf/Zr + Hf. A comminuted, chemically beneficiated concentrate containing ca 99% zirconium oxide is produced also. 

Eudialyte, (Na,Ca)gZr0H(Si20 )2, from a large deposit near Narssaq in southwest Greenland, is the source of pure zirconium oxide. The hafnium ratio in the ore is 2.2% Hf/Zr + Hf. 

Similarly, fusion of milled zircon with dolomite or lime forms CaSiO and MgZrO [12032-31 -4] CaZrO [12013-47-7] and CaO Ca2SiO or CaSiO and Zr02, and is used to prepare zirconium oxide, usually as calcia-stabiUzed cubic zirconia because of the calcia left in soHd solution in the zirconia (27-29). 

Finely divided zirconium powder is made by bomb reduction of zirconium oxide with magnesium or calcium. The powder is separated by leaching... 

Zirconium oxide is fused with alurnina in electric-arc furnaces to make alumina—zirconia abrasive grains for use in grinding wheels, coated-abrasive disks, and belts (104) (see Abrasives). The addition of zirconia improves the shock resistance of brittle alurnina and toughens the abrasive. Most of the baddeleyite imported is used for this appHcation, as is zirconia produced by burning zirconium carbide nitride. 

Zirconium oxide is used in the production of ceramic colors or stains for ceramic tile and sanitary wares. Zirconia and siHca are fired together to form zircon in the presence of small amounts of other elements which are trapped in the zircon lattice to form colors such as tin—vanadium yellow, praseodymium—zircon yellow [68187-15-5] vanadium—zircon blue [12067-91 -3] iron—zircon pink [68412-79-3] indium—vanadium orange (105—108). 

Zirconium oxide increases the refractive index of some optical glasses, and is used for dispersion hardening of platinum and mthenium. Very fine zirconium oxide has been used for polishing glass but ceria seems to be preferred. 

Zirconium tetrafluoride [7783-64-4] is used in some fluoride-based glasses. These glasses are the first chemically and mechanically stable bulk glasses to have continuous high transparency from the near uv to the mid-k (0.3—6 -lm) (117—118). Zirconium oxide and tetrachloride have use as catalysts (119), and zirconium sulfate is used in preparing a nickel catalyst for the hydrogenation of vegetable oil. Zirconium 2-ethyIhexanoate [22464-99-9] is used with cobalt driers to replace lead compounds as driers in oil-based and alkyd paints (see Driers and metallic soaps). 

Hydrides. Zirconium hydride [7704-99-6] in powder form was produced by the reduction of zirconium oxide with calcium hydride in a bomb reactor. However, the workup was hazardous and many fires and explosions occurred when the calcium oxide was dissolved with hydrochloric acid to recover the hydride powder. With the ready availabiHty of zirconium metal via the KroU process, zirconium hydride can be obtained by exothermic absorption of hydrogen by pure zirconium, usually highly porous sponge. The heat of formation is 167.4 J / mol (40 kcal/mol) hydrogen absorbed. 

Carbide. Zirconium carbide [12020-14-3] nominally ZrC, is a dark gray brittle soHd. It is made typically by a carbothermic reduction of zirconium oxide in a induction-heated vacuum furnace. Alternative production methods, especially for deposition on a substrate, consist of vapor-phase reaction of a volatile zirconium haHde, usually ZrCl, with a hydrocarbon in a hydrogen atmosphere at 900—1400°C. 

Zirconium nitride is dissolved by concentrated hydrofluoric acid, dissolved slowly by hot concentrated sulfuric acid, and oxidizes to zirconium oxide above 700°C in air. 

ZrSe [12166-53-9] and ZrTe [39294-10-5] (138). Zirconium disulfide [12039-15-5] is made from the elemental powders and by the action of carbon disulfide on zirconium oxide above 1200°C (139) some ZrOS [12164-95-3] is usually also obtained. The higher sulfides disproportionate at ca 700°C synthesis reactions at 900—1000°C with S Zr ratios between 0.2 and 2.3 produced crystals that were identified as Zr S2 [12595-12-9] ... 

Zircon is synthesized by heating a mixture of zirconium oxide and silicon oxide to 1500°C for several hours (163). The corresponding hafnium silicate, hafnon, has been synthesized also. Zircon can be dissociated into the respective oxides by heating above 1540°C and rapidly quenching to prevent recombination. Commercially, this is done bypassing closely sized zircon through a streaming arc plasma (38). 

Zirconium tetrachloride, ZrCl, is prepared by a variety of anhydrous chlorination procedures. The reaction of chlorine or hydrogen chloride with zirconium metal above 300°C, or phosgene or carbon tetrachloride on zirconium oxide above 450°C, or chlorine on an intimate mixture of zirconium oxide and carbon above 700°C are commonly used. 

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