Zirconium alloys are

solid solution A solid solution, a term popularly used for metals, is a homogenous mixture of two different kinds of atoms in solid state and have a single crystal structure. Many examples can be found in metallurgy, geology, and solid-state chemistry. The wor ...

s of

zirconium Zirconium is a chemical element with the symbol Zr and atomic number 40. The name ''zirconium'' is taken from the name of the mineral zircon, the most important source of zirconium. The word is related to Persian '' zargun'' (zircon; ''zar-gun'' ...

or other

metal A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typicall ...

s, a common subgroup having the trade mark Zircaloy. Zirconium has very low absorption cross-section of

thermal neutron The neutron detection temperature, also called the neutron energy, indicates a free neutron's kinetic energy, usually given in electron volts. The term ''temperature'' is used, since hot, thermal and cold neutrons are moderated in a medium wi ...

s, high hardness,

ductility Ductility is a mechanical property commonly described as a material's amenability to drawing (e.g. into wire). In materials science, ductility is defined by the degree to which a material can sustain plastic deformation under tensile str ...

and

corrosion resistance Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosion engin ...

. One of the main uses of zirconium alloys is in nuclear technology, as

cladding Cladding is an outer layer of material covering another. It may refer to the following: *Cladding (boiler), the layer of insulation and outer wrapping around a boiler shell *Cladding (construction), materials applied to the exterior of buildings ...

fuel rod Nuclear fuel is material used in nuclear power stations to produce heat to power turbines. Heat is created when nuclear fuel undergoes nuclear fission. Most nuclear fuels contain heavy fissile actinide elements that are capable of undergoing ...

s in

nuclear reactor A nuclear reactor is a device used to initiate and control a fission nuclear chain reaction or nuclear fusion reactions. Nuclear reactors are used at nuclear power plants for electricity generation and in nuclear marine propulsion. Heat fr ...

s, especially water reactors. A typical composition of nuclear-grade zirconium alloys is more than 95 weight percent zirconium and less than 2% of

tin Tin is a chemical element with the symbol Sn (from la, stannum) and atomic number 50. Tin is a silvery-coloured metal. Tin is soft enough to be cut with little force and a bar of tin can be bent by hand with little effort. When bent, t ...

, niobium,

iron Iron () is a chemical element with Symbol (chemistry), symbol Fe (from la, Wikt:ferrum, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 element, group 8 of the periodic table. It is, Abundanc ...

, chromium,

nickel Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow ...

and other metals, which are added to improve mechanical properties and corrosion resistance. The water cooling of reactor zirconium alloys elevates requirement for their resistance to oxidation-related

nodular corrosion Galvanic corrosion (also called bimetallic corrosion or dissimilar metal corrosion) is an electrochemical process in which one metal corrodes preferentially when it is in electrical contact with another, in the presence of an electrolyte. A simi ...

. Furthermore, oxidative reaction of zirconium with water releases

hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic ...

gas, which partly diffuses into the alloy and forms

zirconium hydride Zirconium hydride describes an alloy made by combining zirconium and hydrogen. Hydrogen acts as a hardening agent, preventing dislocations in the zirconium atom crystal lattice from sliding past one another. Varying the amount of hydrogen and th ...

s. The hydrides are less dense and are weaker mechanically than the alloy; their formation results in blistering and cracking of the cladding – a phenomenon known as

hydrogen embrittlement Hydrogen embrittlement (HE), also known as hydrogen-assisted cracking or hydrogen-induced cracking (HIC), is a reduction in the ductility of a metal due to absorbed hydrogen. Hydrogen atoms are small and can permeate solid metals. Once absorbed ...

.Delayed hydride cracking in zirconium alloys in pressure tube nuclear reactors
Final report of a coordinated research project 1998–2002, IAEA, October 2004

Production and properties

Commercial non-nuclear grade zirconium typically contains 1–5% of

hafnium Hafnium is a chemical element with the symbol Hf and atomic number 72. A lustrous, silvery gray, tetravalent transition metal, hafnium chemically resembles zirconium and is found in many zirconium minerals. Its existence was predicted by Dmitri M ...

, whose neutron absorption cross-section is 600 times that of zirconium. Hafnium must therefore be almost entirely removed (reduced to < 0.02% of the alloy) for reactor applications. Nuclear-grade zirconium alloys contain more than 95% Zr, and therefore most of their properties are similar to those of pure

. The absorption cross section for thermal neutrons is 0.18

barn A barn is an agricultural building usually on farms and used for various purposes. In North America, a barn refers to structures that house livestock, including cattle and horses, as well as equipment and fodder, and often grain.Alle ...

for zirconium, which is much lower than that for such common metals as iron (2.4 barn) and nickel (4.5 barn). The composition and the main applications of common reactor-grade alloys are summarized below. These alloys contain less than 0.3% of iron and chromium and 0.1–0.14% oxygen. ^*ZIRLO stands for zirconium low oxidation.

Microstructure

At temperatures below 1100 K, zirconium alloys belong to the

hexagonal crystal family In crystallography, the hexagonal crystal family is one of the six crystal families, which includes two crystal systems (hexagonal and trigonal) and two lattice systems (hexagonal and rhombohedral). While commonly confused, the trigonal crystal ...

(HCP). Its microstructure, revealed by chemical attack, shows needle-like grains typical of a

Widmanstätten pattern Widmanstätten patterns, also known as Thomson structures, are figures of long nickel–iron crystals, found in the octahedrite iron meteorites and some pallasites. They consist of a fine interleaving of kamacite and taenite bands or ribbons ...

. Upon annealing below the phase transition temperature (α-Zr to β-Zr) the grains are equiaxed with sizes varying from 3 to 5 μm.

Development

Zircaloy 1 was developed after Zirconium was selected by Admiral H.G. Rickover as the structural material for high flux zone reactor components and cladding for fuel pellet tube bundles in prototype submarine reactors in the late 1940s. The choice was owing to a combination of strength, low neutron cross section and corrosion resistance. Zircaloy-2 was inadvertently developed, by melting Zircaloy-1 in a crucible previously used for stainless steel. Newer alloys are Ni-free, including Zircaloy-4, ZIRLO and M5 (with 1% niobium).

Oxidation of zirconium alloy

Zirconium alloys readily react with

oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as ...

, forming a nanometer-thin passivation layer. The corrosion resistance of the alloys may degrade significantly when some impurities (e.g. more than 40 ppm of

carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—its atom making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table. Carbon mak ...

or more than 300 ppm of

nitrogen Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...

) are present. Corrosion resistance of zirconium alloys is enhanced by intentional development of thicker passivation layer of black lustrous

zirconium oxide Zirconium dioxide (), sometimes known as zirconia (not to be confused with zircon), is a white crystalline oxide of zirconium. Its most naturally occurring form, with a monoclinic crystalline structure, is the mineral baddeleyite. A dopant stabi ...

Nitride In chemistry, a nitride is an inorganic compound of nitrogen. The "nitride" anion, N3- ion, is very elusive but compounds of nitride are numerous, although rarely naturally occuring. Some nitrides have a find applications, such as wear-resistant ...

coatings might also be used. Whereas there is no consensus on whether zirconium and zirconium alloy have the same oxidation rate, Zircaloys 2 and 4 do behave very similarly in this respect. Oxidation occurs at the same rate in air or in water and proceeds in ambient condition or in high vacuum. A sub-micrometer thin layer of zirconium dioxide is rapidly formed in the surface and stops the further diffusion of oxygen to the bulk and the subsequent oxidation. The dependence of oxidation rate R on temperature and pressure can be expressed as :R = 13.9·P^1/6·exp(−1.47/k_BT) The oxidation rate R is here expressed in gram/(cm²·second); P is the pressure in atmosphere, that is the factor P^1/6 = 1 at ambient pressure; the

activation energy In chemistry and physics, activation energy is the minimum amount of energy that must be provided for compounds to result in a chemical reaction. The activation energy (''E''a) of a reaction is measured in joules per mole (J/mol), kilojoules p ...

is 1.47 eV; k_B is the

Boltzmann constant The Boltzmann constant ( or ) is the proportionality factor that relates the average relative kinetic energy of particles in a gas with the thermodynamic temperature of the gas. It occurs in the definitions of the kelvin and the gas constant, ...

(8.617 eV/K) and T is the

absolute temperature Thermodynamic temperature is a quantity defined in thermodynamics as distinct from kinetic theory or statistical mechanics. Historically, thermodynamic temperature was defined by Kelvin in terms of a macroscopic relation between thermodynamic w ...

kelvin The kelvin, symbol K, is the primary unit of temperature in the International System of Units (SI), used alongside its prefixed forms and the degree Celsius. It is named after the Belfast-born and University of Glasgow-based engineer and phy ...

s. Thus the oxidation rate R is 10⁻²⁰ g per 1 m² area per second at 0 °C, 6 g m⁻² s⁻¹ at 300 °C, 5.4 mg m⁻² s⁻¹ at 700 °C and 300 mg m⁻² s⁻¹ at 1000 °C. Whereas there is no clear threshold of oxidation, it becomes noticeable at macroscopic scales at temperatures of several hundred °C.

Oxidation of zirconium by steam

One disadvantage of metallic zirconium is that in the case of a

loss-of-coolant accident A loss-of-coolant accident (LOCA) is a mode of failure for a nuclear reactor; if not managed effectively, the results of a LOCA could result in reactor core damage. Each nuclear plant's emergency core cooling system (ECCS) exists specifically t ...

in a nuclear reactor. Zirconium cladding rapidly reacts with water steam above . Oxidation of zirconium by water is accompanied by release of

gas. This oxidation is accelerated at high temperatures, e.g. inside a reactor core if the fuel assemblies are no longer completely covered by liquid water and insufficiently cooled. Metallic zirconium is then oxidized by the protons of

water Water (chemical formula ) is an Inorganic compound, inorganic, transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living ...

to form

gas according to the following redox reaction: : Zr + 2 H₂O → ZrO₂ + 2 H₂ Zirconium cladding in the presence of D₂O deuterium oxide frequently used as the moderator and coolant in next gen pressurized heavy water reactors that CANDU designed nuclear reactors use would express the same oxidation on exposure to deuterium oxide steam as follows: : Zr + 2 D₂O → ZrO₂ + 2 D₂ This exothermic reaction, although only occurring at high temperature, is similar to that of alkali metals (such as

sodium Sodium is a chemical element with the symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 of the periodic table. Its only stable ...

potassium Potassium is the chemical element with the symbol K (from Neo-Latin ''kalium'') and atomic number19. Potassium is a silvery-white metal that is soft enough to be cut with a knife with little force. Potassium metal reacts rapidly with atmosph ...

) with water. It also closely resembles the anaerobic oxidation of

by water (reaction used at high temperature by

Antoine Lavoisier Antoine-Laurent de Lavoisier ( , ; ; 26 August 17438 May 1794),
CNRS (

Three Mile Island Nuclear Generating Station Three Mile Island Nuclear Generating Station (commonly abbreviated as TMI) is a closed nuclear power plant on Three Mile Island in Londonderry Township, Dauphin County, Pennsylvania on Lake Frederic, a reservoir in the Susquehanna River jus ...

in 1979 that did not damage the containment building. This same reaction occurred in

boiling water reactor A boiling water reactor (BWR) is a type of light water nuclear reactor used for the generation of electrical power. It is a design different from a Soviet graphite-moderated RBMK. It is the second most common type of electricity-generating nu ...

s 1, 2 and 3 of the

Fukushima Daiichi Nuclear Power Plant The is a disabled nuclear power plant located on a site in the towns of Ōkuma and Futaba in Fukushima Prefecture, Japan. The plant suffered major damage from the magnitude 9.0 earthquake and tsunami that hit Japan on March 11, 2011. The ...

(Japan) after reactor cooling was interrupted by related earthquake and tsunami events during the disaster of March 11, 2011, leading to the Fukushima Daiichi nuclear disaster. Hydrogen gas was vented into the reactor maintenance halls and the resulting explosive mixture of hydrogen with air

detonated. The explosions severely damaged external buildings and at least one containment building. The reaction also occurred during the Chernobyl Accident, when the steam from the reactor began to escape. Many water cooled reactor containment buildings have

catalyst Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...

-based

passive autocatalytic recombiner Passive autocatalytic recombiner (PAR) is a device that removes hydrogen from the containment of a nuclear power plant during an accident. Its purpose is to prevent hydrogen explosions. Recombiners come into action spontaneously as soon as the hyd ...

units installed to rapidly convert hydrogen and oxygen into water at room temperature before the explosive limit is reached.

Formation of hydrides and hydrogen embrittlement

Zirconium Hydride in the microstructure of Zircaloy-4

In the above oxidation scenario, 5–20% of the released hydrogen diffuses into the zirconium alloy cladding forming

s.DOE-HDBK-1017/2-93, January 1993
DOE Fundamentals Handbook, Material Science, Volume 2 of 2, U.S. Department of Energy, January 2003, pp. 12, 24. The hydrogen production process also mechanically weakens the rods cladding because the hydrides have lower ductility and density than zirconium or its alloys, and thus blisters and cracks form upon hydrogen accumulation. This process is also known as

. It has been reported that the concentration of hydrogen within hydrides is also dependent on the nucleation site of the precipitates. In case of loss-of-coolant accident ( LOCA) in a damaged nuclear reactor, hydrogen embrittlement accelerates the degradation of the zirconium alloy cladding of the fuel rods exposed to high temperature steam.Nuclear Fuel Behaviour in Loss-of-coolant Accident (LOCA) Conditions. State-of-the-art Report. OECD 2009, NEA No. 6846. https://www.oecd-nea.org/nsd/reports/2009/nea6846_LOCA.pdf

Applications

Zirconium alloys are corrosion resistant and

biocompatible Biocompatibility is related to the behavior of biomaterials in various contexts. The term refers to the ability of a material to perform with an appropriate host response in a specific situation. The ambiguity of the term reflects the ongoing de ...

, and therefore can be used for body implants. In one particular application, a Zr-2.5Nb alloy is formed into a knee or hip implant and then oxidized to produce a hard ceramic surface for use in bearing against a polyethylene component. This oxidized zirconium alloy material provides the beneficial surface properties of a ceramic (reduced friction and increased abrasion resistance), while retaining the beneficial bulk properties of the underlying metal (manufacturability, fracture toughness, and ductility), providing a good solution for these medical implant applications. Reduction of zirconium demand in Russia due to nuclear demilitarization after the end of the cold war resulted in the exotic production of household zirconium items such as the vodka shot glass shown in the picture.