Zirconium, properties

Hafnium is a ductile metal with a brilliant silver luster. Its properties are considerably influenced by presence of zirconium impurities. Of all the elements, zirconium and hafnium are... 

Because the element not only has a good absorption cross section for thermal neutrons (almost 600 times that of zirconium), but also excellent mechanical properties and is extremely corrosion-resistant, hafnium is used for reactor control rods. Such rods are used in nuclear submarines. 

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... 

Zirconium i dride. Zirconium hydride [7704-99-6] ZrH2, is a britde, metaUic-gray soHd that is stable in air and water, and has a density of 5.6 g/cm. The chemical properties of ZrH2 closely resemble those of titanium hydride. Thermal decomposition in vacuum (1 mPa (7.5 x 10 //mHg)) begins at 300°C and is nearly complete at 500—700°C. It is prepared in the same manner as T1H2. 

Another important class of titanates that can be produced by hydrothermal synthesis processes are those in the lead zirconate—lead titanate (PZT) family. These piezoelectric materials are widely used in manufacture of ultrasonic transducers, sensors, and minia ture actuators. The electrical properties of these materials are derived from the formation of a homogeneous soHd solution of the oxide end members. The process consists of preparing a coprecipitated titanium—zirconium hydroxide gel. The gel reacts with lead oxide in water to form crystalline PZT particles having an average size of about 1 ]lni (Eig. 3b). A process has been developed at BatteUe (Columbus, Ohio) to the pilot-scale level (5-kg/h). 

Lead zirconate [12060-01 -4] PbZrO, mol wt 346.41, has two colorless crystal stmctures a cubic perovskite form above 230°C (Curie point) and a pseudotetragonal or orthorhombic form below 230°C. It is insoluble in water and aqueous alkaUes, but soluble in strong mineral acids. Lead zirconate is usually prepared by heating together the oxides of lead and zirconium in the proper proportion. It readily forms soHd solutions with other compounds with the ABO stmcture, such as barium zirconate or lead titanate. Mixed lead titanate-zirconates have particularly high piezoelectric properties. They are used in high power acoustic-radiating transducers, hydrophones, and specialty instmments (146). 

Eabrication techniques must take into account the metallurgical properties of the metals to be joined and the possibiUty of undesirable diffusion at the interface during hot forming, heat treating, and welding. Compatible alloys, ie, those that do not form intermetaUic compounds upon alloying, eg, nickel and nickel alloys (qv), copper and copper alloys (qv), and stainless steel alloys clad to steel, may be treated by the traditional techniques developed for clads produced by other processes. On the other hand, incompatible combinations, eg, titanium, zirconium, or aluminum to steel, require special techniques designed to limit the production at the interface of undesirable intermetaUics which would jeopardize bond ductihty. 

Additions of selected alloying elements raise the recrystaUization temperature, extending to higher temperature regimes the tensile properties of the cold-worked molybdenum metal. The simultaneous additions of 0.5% titanium and 0.1% zirconium produce the TZM aUoy, which has a corresponding... 

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. 

Zirconium is a hard, shiny, ductile metal, similar to stainless steel in appearance. It can be hot-worked to form slabs, rods, and rounds from arc-melted ingot. Further cold-working of zirconium with intermediate annealings produces sheet, foil, bar wire, and tubing. Physical properties are given in Table 3. 

Corrosion Resistance. Zirconium is resistant to corrosion by water and steam, mineral acids, strong alkaUes, organic acids, salt solutions, and molten salts (28) (see also Corrosion and corrosion control). This property is attributed to the presence of a dense adherent oxide film which forms at ambient temperatures. Any break in the film reforms instantly and spontaneously in most environments. 

Zirconium and hafnium have very similar chemical properties, exhibit the same valences, and have similar ionic radii, ie, 0.074 mm for, 0.075 mm for (see Hafniumand hafnium compounds). Because of these similarities, their separation was difficult (37—40). Today, the separation of zirconium and hafnium by multistage counter-current Hquid—Hquid extraction is routine (41) (see Extraction, liquid—liquid). 

Above 40 wt % hydrogen content at room temperature, zirconium hydride is brittle, ie, has no tensile ductiHty, and it becomes more friable with increasing hydrogen content. This behavior and the reversibiHty of the hydride reaction are utilized ki preparing zirconium alloy powders for powder metallurgy purposes by the hydride—dehydride process. The mechanical and physical properties of zirconium hydride, and thek variation with hydrogen content of the hydride, are reviewed in Reference 127. 

As a hard, high melting carbide and possible constituent of UC-fueled reactors, zirconium carbide has been studied extensively. The preparation, behavior, and properties of zirconium and other carbides are reviewed in Reference 132, temperature-correlated engineering property data in Reference 133 (see also Carbides). 

The physical properties of zirconium tetrafluoride ate Hsted in Table 7. 

Zirconium tetrachloride is a tetrahedral monomer in the gas phase, but the soHd is a polymer of ZrCl octahedra arranged in zigzag chains in such a way that each zirconium has two pairs of bridging chlorine anions and two terminal or t-chlorine anions. The octahedra are distorted with unequal Zr—Cl bridge bonds of 0.2498 and 0.2655 nm. The physical properties of zirconium tetrachloride are given in Table 7. 

Zirconium tetrabromide [13777-25-8] ZrBr, is prepared direcdy from the elements or by the reaction of bromine on a mixture of zirconium oxide and carbon. It may also be made by halogen exchange between the tetrachloride and aluminum bromide. The physical properties are given in Table 7. The chemical behavior is similar to that of the tetrachloride. 

Zirconium tetraiodide [13986-26-0], Zrl, is prepared directly from the elements, by the reaction of iodine on zirconium carbide, or by halogen exchange with aluminum triiodide. The reaction of iodine with zirconium oxide and carbon does not proceed. The physical properties are given in Table 7. 

Zirconium chloride and bromide have closely related but dissimilar stmctures. Both contain two metal layers enclosed between two nonmetal layers which both have hexagonal stmcture. In ZrCl, the four-layer sandwich repeats in layers stacked up according to /abca/bcab/cabc/, whereas the ZrBr stacking order is /abca/cabc/bcab/ (188). Both are metallic conductors, but the difference in packing results in different mechanical properties the bromide is much more brittle. 

The main interest in zirconium phosphates relates to their ion-exchange properties. If amorphous zirconium phosphate is equiUbrated with sodium hydroxide to pH 7, one hydrogen is displaced and ZrNaH(P0 2 3H20 [13933-56-7] is obtained. The spacing between the zirconium layers is increased from 0.76 to 1.18 nm, which allows this phosphate to exchange larger ions. 

The properties and behavior of double phosphates such as — Y)3 (216), sodium—zirconium phosphate—siUcates (217), and... 

Zirconium—ally complexes also have catalytic properties. Tetraally zirconium [12090-34-5] on a siUca substrate catalyzes ethylene polymerization (265). Supported on sihca, ZrR (R = allyl or neopentyl) catalyzes olefin isomerization (266). 

O. Kubaschewski, ed.. Zirconium Physico-Chemical Properties of its Compound and Alloys, International Atomic Energy Agency, Vieima, 1976, p. 8. 

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). 

Uses. In spite of unique properties, there are few commercial appUcations for monolithic shapes of borides. They are used for resistance-heated boats (with boron nitride), for aluminum evaporation, and for sliding electrical contacts. There are a number of potential uses ia the control and handling of molten metals and slags where corrosion and erosion resistance are important. Titanium diboride and zirconium diboride are potential cathodes for the aluminum Hall cells (see Aluminum and aluminum alloys). Lanthanum hexaboride and cerium hexaboride are particularly useful as cathodes ia electronic devices because of their high thermal emissivities, low work functions, and resistance to poisoning. 

The physical properties of ZrC are Hsted in Table 2. Zirconium carbide is much less important than TiC for cemented carbides. 

B. R. Rossing, L. H. Cadoff, and T. K. Gupta, "The Fabrication and Properties of Electrodes Based on Zirconium Dioxide," Vol. 2, 6th International Conference onMHD Electrical Power Generation, Washington, D.C., June 1975, pp. 105—117. 

Many elemental additions to copper for strengthening and other properties also deoxidize the alloy. A side benefit of such additions is elimination of susceptibihty to hydrogen embrittlement. Such deoxidizing additions include beryllium, aluminum, siUcon, chromium, zirconium, and magnesium. 

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