Zirconium corrosion resistant alloys

Zirconium is used as a containment material for the uranium oxide fuel pellets in nuclear power reactors (see Nuclearreactors). Zirconium is particularly usehil for this appHcation because of its ready availabiUty, good ductiUty, resistance to radiation damage, low thermal-neutron absorption cross section 18 x 10 ° ra (0.18 bams), and excellent corrosion resistance in pressurized hot water up to 350°C. Zirconium is used as an alloy strengthening agent in aluminum and magnesium, and as the burning component in flash bulbs. It is employed as a corrosion-resistant metal in the chemical process industry, and as pressure-vessel material of constmction in the ASME Boiler and Pressure Vessel Codes. 

The corrosion behaviour of amorphous alloys has received particular attention since the extraordinarily high corrosion resistance of amorphous iron-chromium-metalloid alloys was reported. The majority of amorphous ferrous alloys contain large amounts of metalloids. The corrosion rate of amorphous iron-metalloid alloys decreases with the addition of most second metallic elements such as titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel, copper, ruthenium, rhodium, palladium, iridium and platinum . The addition of chromium is particularly effective. For instance amorphous Fe-8Cr-13P-7C alloy passivates spontaneously even in 2 N HCl at ambient temperature ". (The number denoting the concentration of an alloy element in the amorphous alloy formulae is the atomic percent unless otherwise stated.)... 

Water The corrosion resistance of pure niobium in water and steam at elevated temperatures is not sufficient to allow its use as a canning material in water-cooled nuclear reactors. Alloys of niobium with molybdenum, titanium, vanadium and zirconium however have improved resistance and have possibilities in this application. Whilst the Nb-lOTi-lOMo alloy offers... 

Additions of zirconium confer a significant increase in corrosion resistance, particularly in sulphuric and hydrochloric acids . At alloying additions of the order of 50% Zr, however, there can be a significant diminution in resistance to oxidation and the welding of titanium to zirconium is not advisable, because within the welded zone the proportion of titanium to zirconium will almost inevitably fall within the sensitive composition range. 

The growth of nuclear engineering with its specialised demands for materials having a low neutron absorption coupled with adequate strength and corrosion resistance at elevated temperatures, has necessitated the production of zirconium in relatively large commercial quantities. This specific demand has resulted in development of specially purified zirconium, and certain zirconium alloys, for use in particular types of nuclear reactor. 

Zirconium alloys have been much less thoroughly studied than titanium alloys. The main application of interest has been for nuclear reactor components where good corrosion resistance combined with a low neutron capture cross-section has been required. Corrosion fatigue crack growth in these alloys in high temperature (260-290°C) aqueous environments typical of... 

Another characteristic that makes zirconium useful is the production of zircaloy, which does not absorb neutrons as does stainless steel in nuclear reactors. Thus, it is ideal to make nuclear fuel tubes and reactor containers. Zircaloy is the blend (alloy) of zirconium and any of several corrosion resistant metals. 

Zirconium alloys are used as in-reactor materials because of their very low neutron absorption, high strength and excellent corrosion resistance. However, they do absorb hydrogen freely. 

The most important applications of zirconium involve its alloys, Zircaloy. The aUoy offers excellent mechanical and heat-transfer properties and great resistance to corrosion and chemical attack. This, in conjunction with the fact that zirconium has a low neutron absorption cross section, makes this ahoy a suitable choice as a construction material for thermal nuclear reactors and nuclear power plants. Other uses are as an ingredient of explosive mixtures, as getter in vacuum tubes, and in making flash bulb, flash powder (historical), and lamp filaments, in rayon spinnerets, and in surgical appliances. 

Tantalum-hafnium and tantalum-zirconium alloys are less suitable for aggressive acid environments. Compared with tantalum-tungsten alloys, tantalum rhenium alloys are superior in corrosion resistance and to hydrogen embrittlement, but the major disadvantage is the high cost of rhenium. 

The most important application of zirconium is in the formulation of the base metal in an alloy of 98% zirconium. 1.5% tin, 0.35% lron-chromium-mckel. and 0.15% oxygen, This alloy is widely used in water-cooled nuclear reactors because of its excellent corrosion resistance up to about 350 in H 0, and its low neutron cross section. Currendy, about 90% of the zirconium produced is used for this application. The excellent corrosion resistance of zirconium to both strong acids and alkalis, particularly its resistance to strong caustic solutions at all concentrations and temperatures, is attracting increasing attention for application in chemical processing equipment, See also Nuclear Power Technology. 

A problem of obtaining zirconium with lowest possible contents of hafnium comes from construction requirements when using zirconium and its alloys in building nuclear reactors. The construction material must have good mechanical properties and must be resistant to corrosion in contact with heat carriers. Since reactor power is proportional to the quantity of neutrons, their absorption into construction materials should be as small as possible. Zirconium and its alloys are unique materials that satisfy these requirements. However, hafnium has approximately the same chemical characteristics as zirconium but it absorbs neutrons strongly. 

Because hafnium has a high absorption cross-section for thermal neutrons (almost 600 times that of zirconium), has excellent mechanical properties, and is extremely corrosion resistant, it is used to make the control rods of nuclear reactors. It is also applied in vacuum lines as a getter —a material that combines with and removes trace gases from vacuum tubes. Hafnium has been used as an alloying agent for iron, titanium, niobium, and other metals. Finely divided hafnium is pyrophoric and can ignite spontaneously in air. 

The low cross-section for absorption of neutrons and high-temperature (330-350°C) aqueous corrosion resistance as well as its good mechanical properties promote the use of zirconium alloys in the nuclear reactors. In the development of zirconium alloys care must be taken that the added minor elements do not posses high cross-sections for the absorption of neutrons and contribute to greater corrosion resistance and improved mechanical properties. The good corrosion resistance of the alloys in acids and bases favors the use of zirconium alloys in chemical plants. 

Materials such as metals, alloys, steels and plastics form the theme of the fourth chapter. The behavior and use of cast irons, low alloy carbon steels and their application in atmospheric corrosion, fresh waters, seawater and soils are presented. This is followed by a discussion of stainless steels, martensitic steels and duplex steels and their behavior in various media. Aluminum and its alloys and their corrosion behavior in acids, fresh water, seawater, outdoor atmospheres and soils, copper and its alloys and their corrosion resistance in various media, nickel and its alloys and their corrosion behavior in various industrial environments, titanium and its alloys and their performance in various chemical environments, cobalt alloys and their applications, corrosion behavior of lead and its alloys, magnesium and its alloys together with their corrosion behavior, zinc and its alloys, along with their corrosion behavior, zirconium, its alloys and their corrosion behavior, tin and tin plate with their applications in atmospheric corrosion are discussed. The final part of the chapter concerns refractories and ceramics and polymeric materials and their application in various corrosive media. 

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