Zircaloy
Encyclopedia
Zirconium alloys are solid solution
Solid solution
A solid solution is a solid-state solution of one or more solutes in a solvent. Such a mixture is considered a solution rather than a compound when the crystal structure of the solvent remains unchanged by addition of the solutes, and when the mixture remains in a single homogeneous phase...

s of zirconium
Zirconium
Zirconium is a chemical element with the symbol Zr and atomic number 40. The name of zirconium is taken from the mineral zircon. Its atomic mass is 91.224. It is a lustrous, grey-white, strong transition metal that resembles titanium...

 or other metal
Metal
A metal , is an element, compound, or alloy that is a good conductor of both electricity and heat. Metals are usually malleable and shiny, that is they reflect most of incident light...

s, a common subgroup having the trade mark Zircaloy. Zirconium has very low absorption cross-section
Nuclear cross section
The nuclear cross section of a nucleus is used to characterize the probability that a nuclear reaction will occur. The concept of a nuclear cross section can be quantified physically in terms of "characteristic area" where a larger area means a larger probability of interaction...

 of thermal neutrons, high hardness, ductility
Ductility
In materials science, ductility is a solid material's ability to deform under tensile stress; this is often characterized by the material's ability to be stretched into a wire. Malleability, a similar property, is a material's ability to deform under compressive stress; this is often characterized...

 and corrosion resistance. Therefore, one of the main uses of zirconium alloys is in nuclear technology
Nuclear technology
Nuclear technology is technology that involves the reactions of atomic nuclei. Among the notable nuclear technologies are nuclear power, nuclear medicine, and nuclear weapons...

, as cladding of fuel rods in nuclear reactor
Nuclear reactor
A nuclear reactor is a device to initiate and control a sustained nuclear chain reaction. Most commonly they are used for generating electricity and for the propulsion of ships. Usually heat from nuclear fission is passed to a working fluid , which runs through turbines that power either ship's...

s, especially water reactors
Light water reactor
The light water reactor is a type of thermal reactor that uses normal water as its coolant and neutron moderator. Thermal reactors are the most common type of nuclear reactor, and light water reactors are the most common type of thermal reactor...

. A typical composition of nuclear-grade zirconium alloys is more than 95 weight percent zirconium and less than 2% of tin
Tin
Tin is a chemical element with the symbol Sn and atomic number 50. It is a main group metal in group 14 of the periodic table. Tin shows chemical similarity to both neighboring group 14 elements, germanium and lead and has two possible oxidation states, +2 and the slightly more stable +4...

, niobium
Niobium
Niobium or columbium , is a chemical element with the symbol Nb and atomic number 41. It's a soft, grey, ductile transition metal, which is often found in the pyrochlore mineral, the main commercial source for niobium, and columbite...

, iron
Iron
Iron is a chemical element with the symbol Fe and atomic number 26. It is a metal in the first transition series. It is the most common element forming the planet Earth as a whole, forming much of Earth's outer and inner core. It is the fourth most common element in the Earth's crust...

, chromium
Chromium
Chromium is a chemical element which has the symbol Cr and atomic number 24. It is the first element in Group 6. It is a steely-gray, lustrous, hard metal that takes a high polish and has a high melting point. It is also odorless, tasteless, and malleable...

, nickel
Nickel
Nickel is a chemical element with the chemical symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel belongs to the transition metals and is hard and ductile...

 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. Furthermore, oxidative reaction of zirconium with water releases hydrogen gas, which partly diffuses into the alloy and forms zirconium hydride
Zirconium hydride
Zirconium hydride is an inorganic chemical compound, a hydride of zirconium with the formula ZrHx. Whereas x can be as large as 4, the most common values are between 1 and 2. Zirconium hydrides form upon reaction of zirconium metal with hydrogen gas. They behave as typical metals in terms of...

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
Hydrogen embrittlement is the process by which various metals, most importantly high-strength steel, become brittle and fracture following exposure to hydrogen...

.

Production and properties

Commercial zirconium typically contains 1–5% of hafnium
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 zirconium minerals. Its existence was predicted by Dmitri Mendeleev in 1869. Hafnium was the penultimate stable...

, whose neutron absorption cross-section is 600x that of zirconium, and therefore is removed for reactor applications.

Nuclear-grade zirconium alloys contain more than 95% Zr, and therefore most of their properties are similar to those of pure zirconium
Zirconium
Zirconium is a chemical element with the symbol Zr and atomic number 40. The name of zirconium is taken from the mineral zircon. Its atomic mass is 91.224. It is a lustrous, grey-white, strong transition metal that resembles titanium...

. The absorption cross section for thermal neutrons is 0.18 barn
Barn (unit)
A barn is a unit of area. Originally used in nuclear physics for expressing the cross sectional area of nuclei and nuclear reactions, today it is used in all fields of high energy physics to express the cross sections of any scattering process, and is best understood as a measure of the...

 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.
AlloySn, %Nb, %Vendor
(country)
ComponentReactor type
Zircaloy 2 1.2–1.7 All vendors Cladding, structural components BWR
Boiling water reactor
The boiling water reactor is a type of light water nuclear reactor used for the generation of electrical power. It is the second most common type of electricity-generating nuclear reactor after the pressurized water reactor , also a type of light water nuclear reactor...

, CANDU
CANDU reactor
The CANDU reactor is a Canadian-invented, pressurized heavy water reactor. The acronym refers to its deuterium-oxide moderator and its use of uranium fuel...

Zircaloy 4 1.2–1.7 All vendors Cladding, structural components BWR
Boiling water reactor
The boiling water reactor is a type of light water nuclear reactor used for the generation of electrical power. It is the second most common type of electricity-generating nuclear reactor after the pressurized water reactor , also a type of light water nuclear reactor...

, PWR
Pressurized water reactor
Pressurized water reactors constitute a large majority of all western nuclear power plants and are one of three types of light water reactor , the other types being boiling water reactors and supercritical water reactors...

, CANDU
CANDU reactor
The CANDU reactor is a Canadian-invented, pressurized heavy water reactor. The acronym refers to its deuterium-oxide moderator and its use of uranium fuel...

ZIRLO 0.7–1 1 Westinghouse
Westinghouse Electric Company
Westinghouse Electric Company LLC is a nuclear power company, offering a wide range of nuclear products and services to utilities throughout the world, including nuclear fuel, service and maintenance, instrumentation and control and advanced nuclear plant designs...

 
Cladding PWR
Pressurized water reactor
Pressurized water reactors constitute a large majority of all western nuclear power plants and are one of three types of light water reactor , the other types being boiling water reactors and supercritical water reactors...

Zr Sponge Japan and Russia Cladding BWR
Boiling water reactor
The boiling water reactor is a type of light water nuclear reactor used for the generation of electrical power. It is the second most common type of electricity-generating nuclear reactor after the pressurized water reactor , also a type of light water nuclear reactor...

ZrSn 0.25 Westinghouse
Westinghouse Electric Company
Westinghouse Electric Company LLC is a nuclear power company, offering a wide range of nuclear products and services to utilities throughout the world, including nuclear fuel, service and maintenance, instrumentation and control and advanced nuclear plant designs...

 
Cladding BWR
Boiling water reactor
The boiling water reactor is a type of light water nuclear reactor used for the generation of electrical power. It is the second most common type of electricity-generating nuclear reactor after the pressurized water reactor , also a type of light water nuclear reactor...

Zr2.5Nb 2.4–2.8 Pressure tube CANDU
CANDU reactor
The CANDU reactor is a Canadian-invented, pressurized heavy water reactor. The acronym refers to its deuterium-oxide moderator and its use of uranium fuel...

E100 0.9–1.1 Russia Cladding RBMK
RBMK
RBMK is an initialism for the Russian reaktor bolshoy moshchnosti kanalniy which means "High Power Channel-type Reactor", and describes a class of graphite-moderated nuclear power reactor which was built in the Soviet Union. The RBMK reactor was the type involved in the Chernobyl disaster...

E125 2.5 Russia Pressure tube RBMK
E635 0.8–1.3 0.8–1 Russia Structural components RBMK
M5 0.8–1.2 Areva
Areva
AREVA is a French public multinational industrial conglomerate headquartered in the Tour Areva in Courbevoie, Paris. AREVA is mainly known for nuclear power; it also has interests in other energy projects. It was created on 3 September 2001, by the merger of Framatome , Cogema and...

 
Cladding, structural components PWR
Pressurized water reactor
Pressurized water reactors constitute a large majority of all western nuclear power plants and are one of three types of light water reactor , the other types being boiling water reactors and supercritical water reactors...



*ZIRLO stands for zirconium low oxidation.

Oxidation of zircaloy

Zirconium alloys readily react with oxygen
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...

, forming a nanometer-thin passivation
Passivation
Passivation is the process of making a material "passive", and thus less reactive with surrounding air, water, or other gases or liquids. The goal is to inhibit corrosion, whether for structural or cosmetic reasons. Passivation of metals is usually achieved by the deposition of a layer of oxide...

 layer. The corrosion resistance of the alloys may degrade significantly when some impurities (e.g. more than 300 ppm of carbon
Carbon
Carbon is the chemical element with symbol C and atomic number 6. As a member of group 14 on the periodic table, it is nonmetallic and tetravalent—making four electrons available to form covalent chemical bonds...

 or more than 40 ppm of nitrogen
Nitrogen
Nitrogen is a chemical element that has the symbol N, atomic number of 7 and atomic mass 14.00674 u. Elemental nitrogen is a colorless, odorless, tasteless, and mostly inert diatomic gas at standard conditions, constituting 78.08% by volume of Earth's atmosphere...

) are present. Corrosion resistance of zircaloys is enhanced by intentional development of thicker passivation layer of black lustrous zirconium oxide. Nitride
Nitride
In chemistry, a nitride is a compound of nitrogen where nitrogen has a formal oxidation state of −3. Nitrides are a large class of compounds with a wide range of properties and applications....

 coatings might also be used.

Whereas there is no consensus on whether zirconium and Zircaloy 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·P1/6·exp(−1.47/kBT)


The oxidation rate R is here expressed in gram/(cm2·second); P is the pressure in atmosphere
Atmosphere (unit)
The standard atmosphere is an international reference pressure defined as 101325 Pa and formerly used as unit of pressure. For practical purposes it has been replaced by the bar which is 105 Pa...

, that is the factor P1/6 = 1 at ambient pressure; the activation energy
Activation energy
In chemistry, activation energy is a term introduced in 1889 by the Swedish scientist Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occur. Activation energy may also be defined as the minimum energy required to start a chemical reaction...

 is 1.47 eV
Electronvolt
In physics, the electron volt is a unit of energy equal to approximately joule . By definition, it is equal to the amount of kinetic energy gained by a single unbound electron when it accelerates through an electric potential difference of one volt...

; kB is the Boltzmann constant (8.617 eV/K) and T is the absolute temperature in Kelvin
Kelvin
The kelvin is a unit of measurement for temperature. It is one of the seven base units in the International System of Units and is assigned the unit symbol K. The Kelvin scale is an absolute, thermodynamic temperature scale using as its null point absolute zero, the temperature at which all...

.

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 accidents (LOCA
Loca
"Loca" by Arsenium and Natalia Gordienko was the official entry for Moldova at the Eurovision Song Contest 2006. The song was performed in English and contained parts in Spanish...

) in a nuclear reactor, the Zr cladding rapidly reacts with water steam
Steam
Steam is the technical term for water vapor, the gaseous phase of water, which is formed when water boils. In common language it is often used to refer to the visible mist of water droplets formed as this water vapor condenses in the presence of cooler air...

 at high temperature. Oxidation of zirconium by water is accompanied by release of hydrogen
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...

 gas. This oxidation is accelerated at high temperatures, e.g. inside a reactor core if the fuel assemblies
Nuclear fuel
Nuclear fuel is a material that can be 'consumed' by fission or fusion to derive nuclear energy. Nuclear fuels are the most dense sources of energy available...

 are no longer completely covered by liquid water and insufficiently cooled. Metallic zirconium is then oxidized by the proton
Proton
The proton is a subatomic particle with the symbol or and a positive electric charge of 1 elementary charge. One or more protons are present in the nucleus of each atom, along with neutrons. The number of protons in each atom is its atomic number....

s of water
Water
Water is a chemical substance with the chemical formula H2O. A water molecule contains one oxygen and two hydrogen atoms connected by covalent bonds. Water is a liquid at ambient conditions, but it often co-exists on Earth with its solid state, ice, and gaseous state . Water also exists in a...

 to form hydrogen
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...

 gas according to the following redox reaction:
Zr + 2 H2O → ZrO2 + 2 H2


This exothermic reaction, although only occurring at high temperature, is similar to that of alkaline metals (such as sodium
Sodium
Sodium is a chemical element with the symbol Na and atomic number 11. It is a soft, silvery-white, highly reactive metal and is a member of the alkali metals; its only stable isotope is 23Na. It is an abundant element that exists in numerous minerals, most commonly as sodium chloride...

 or potassium
Potassium
Potassium is the chemical element with the symbol K and atomic number 19. Elemental potassium is a soft silvery-white alkali metal that oxidizes rapidly in air and is very reactive with water, generating sufficient heat to ignite the hydrogen emitted in the reaction.Potassium and sodium are...

) with water. It also closely resembles the anaerobic oxidation of iron
Iron
Iron is a chemical element with the symbol Fe and atomic number 26. It is a metal in the first transition series. It is the most common element forming the planet Earth as a whole, forming much of Earth's outer and inner core. It is the fourth most common element in the Earth's crust...

 by water (reaction used at high temperature by Antoine Lavoisier
Antoine Lavoisier
Antoine-Laurent de Lavoisier , the "father of modern chemistry", was a French nobleman prominent in the histories of chemistry and biology...

 to produce hydrogen for his experiments).

This reaction was responsible for a small hydrogen explosion accident first observed inside the reactor building of Three Mile Island
Three Mile Island accident
The Three Mile Island accident was a core meltdown in Unit 2 of the Three Mile Island Nuclear Generating Station in Dauphin County, Pennsylvania near Harrisburg, United States in 1979....

 nuclear power plant in 1979, but, the containment building was not damaged then. This same reaction occurred in the boiling water reactor
Boiling water reactor
The boiling water reactor is a type of light water nuclear reactor used for the generation of electrical power. It is the second most common type of electricity-generating nuclear reactor after the pressurized water reactor , also a type of light water nuclear reactor...

s 1, 2 and 3 of the Fukushima I Nuclear Power Plant
Fukushima I Nuclear Power Plant
The , also known as Fukushima Dai-ichi , is a disabled nuclear power plant located on a site in the towns of Okuma and Futaba in the Futaba District of Fukushima Prefecture, Japan. First commissioned in 1971, the plant consists of six boiling water reactors...

 (Japan) and in the spent fuel pool
Spent fuel pool
Spent fuel pools are storage pools for spent fuel from nuclear reactors. They are typically 40 or more feet deep, with the bottom 14 feet equipped with storage racks designed to hold fuel assemblies removed from the reactor. A reactor's pool is specially designed for the reactor in which the...

 of reactor 4 after reactors cooling was interrupted by related earthquake and tsunami
2011 Tōhoku earthquake and tsunami
The 2011 earthquake off the Pacific coast of Tohoku, also known as the 2011 Tohoku earthquake, or the Great East Japan Earthquake, was a magnitude 9.0 undersea megathrust earthquake off the coast of Japan that occurred at 14:46 JST on Friday, 11 March 2011, with the epicenter approximately east...

 events in the disaster of March 11, 2011 leading to the Fukushima I nuclear accidents. After venting of hydrogen gas into the maintenance halls of these three reactors, Zr oxidation-water reduction related explosive mixture of hydrogen with air oxygen
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...

 detonated, and resulting explosions severely damaged external installation buildings and at least one of associated containment building. To avoid explosion, many pressurized water reactor
Pressurized water reactor
Pressurized water reactors constitute a large majority of all western nuclear power plants and are one of three types of light water reactor , the other types being boiling water reactors and supercritical water reactors...

 (PWR) containment buildings, have a catalyst-based recombinator installed to rapidly convert hydrogen and oxygen into water at room temperature before explosivity limit is reached.

Formation of hydrides and hydrogen embrittlement

Also, 5–20% of hydrogen diffuses into the Zircaloy cladding forming zirconium hydride
Zirconium hydride
Zirconium hydride is an inorganic chemical compound, a hydride of zirconium with the formula ZrHx. Whereas x can be as large as 4, the most common values are between 1 and 2. Zirconium hydrides form upon reaction of zirconium metal with hydrogen gas. They behave as typical metals in terms of...

s. The hydrogen production process also mechanically weakens the rods cladding because the hydrides have lower hardness, ductility and density than zirconium or its alloys, and thus blister
Blister
A blister is a small pocket of fluid within the upper layers of the skin, typically caused by forceful rubbing , burning, freezing, chemical exposure or infection. Most blisters are filled with a clear fluid called serum or plasma...

s and cracks
Fracture
A fracture is the separation of an object or material into two, or more, pieces under the action of stress.The word fracture is often applied to bones of living creatures , or to crystals or crystalline materials, such as gemstones or metal...

 form upon hydrogen accumulation. This process is also known as hydrogen embrittlement
Hydrogen embrittlement
Hydrogen embrittlement is the process by which various metals, most importantly high-strength steel, become brittle and fracture following exposure to hydrogen...

.

In case of Loss-of-Coolant Accident (LOCA
Loca
"Loca" by Arsenium and Natalia Gordienko was the official entry for Moldova at the Eurovision Song Contest 2006. The song was performed in English and contained parts in Spanish...

) in a damaged nuclear reactor, hydrogen embrittlement accelerates the degradation of the zircaloy cladding of the fuel rods exposed to high temperature steam.

Applications

Zirconium alloys are corrosion resistant and biocompatible
Biocompatibility
Biocompatibility is related to the behavior of biomaterials in various contexts. The term may refer to specific properties of a material without specifying where or how the material is used , or to more empirical clinical success of a whole device in...

, and therefore can be used for body implants
Implant (medicine)
An implant is a medical device manufactured to replace a missing biological structure, support a damaged biological structure, or enhance an existing biological structure. Medical implants are man-made devices, in contrast to a transplant, which is a transplanted biomedical tissue...

. 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
Oxinium
Oxinium is the brand name of a material used for replacement joints manufactured by the reconstructive orthopedic surgery division of medical devices company Smith & Nephew...

 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
Cold War
The Cold War was the continuing state from roughly 1946 to 1991 of political conflict, military tension, proxy wars, and economic competition between the Communist World—primarily the Soviet Union and its satellite states and allies—and the powers of the Western world, primarily the United States...

resulted in the exotic production of household zirconium items such as the vodka jar shown on the picture.

External links

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