Names | |
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Other names zirconium tungsten oxide | |
Identifiers | |
3D model (JSmol) | |
ChemSpider | |
ECHA InfoCard | 100.037.145 |
EC Number |
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PubChem CID | |
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Properties | |
Zr(WO4)2 | |
Molar mass | 586.92 g/mol |
Appearance | white powder |
Density | 5.09 g/cm3, solid |
negligible | |
Hazards | |
GHS labelling: [1] | |
Warning | |
H315, H319, H335 | |
NFPA 704 (fire diamond) | |
Safety data sheet (SDS) | MSDS |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). |
Zirconium tungstate ( Zr W O 4) is the zirconium salt of tungstic acid and has unusual properties. The phase formed at ambient pressure by reaction of ZrO2 and WO3 is a metastable cubic phase, which has negative thermal expansion characteristics, namely it shrinks over a wide range of temperatures when heated. [2] In contrast to most other ceramics exhibiting negative CTE (coefficient of thermal expansion), the CTE of ZrW2O8 is isotropic and has a large negative magnitude (average CTE of -7.2x10−6K−1) over a wide range of temperature (-273 °C to 777 °C). [3] A number of other phases are formed at high pressures.
Cubic zirconium tungstate (alpha-ZrW2O8), one of the several known phases of zirconium tungstate (ZrW2O8) is perhaps one of the most studied materials to exhibit negative thermal expansion. It has been shown to contract continuously over a previously unprecedented temperature range of 0.3 to 1050 K (at higher temperatures the material decomposes). Since the structure is cubic, as described below, the thermal contraction is isotropic - equal in all directions. There is much ongoing research attempting to elucidate why the material exhibits such dramatic negative thermal expansion.[ citation needed ]
This phase is thermodynamically unstable at room temperature with respect to the binary oxides ZrO2 and WO3, but may be synthesised by heating stoichiometric quantities of these oxides together and then quenching the material by rapidly cooling it from approximately 900 °C to room temperature.
The structure of cubic zirconium tungstate consists of corner-sharing ZrO6 octahedral and WO4 tetrahedral structural units. Its unusual expansion properties are thought to be due to vibrational modes known as Rigid Unit Modes (RUMs), which involve the coupled rotation of the polyhedral units that make up the structure, and lead to contraction.
The arrangement of the groups in the structure of cubic ZrW2O8 is analogous to the simple NaCl structure, with ZrO6 octahedra at the Na sites, and W2O8 groups at the Cl sites. The unit cell consists of 44 atoms aligned in a primitive cubic Bravais lattice, with unit cell length 9.15462 Angstroms.
The ZrO6 octahedra are only slightly distorted from a regular conformation, and all oxygen sites in a given octahedron are related by symmetry. The W2O8 unit is made up of two crystallographically distinct WO4 tetrahedra, which are not formally bonded to each other. These two types of tetrahedra differ with respect to the W-O bond lengths and angles. The WO4 tetrahedra are distorted from a regular shape since one oxygen is unconstrained (an atom that is bonded only to the central tungsten (W) atom), and the three other oxygens are each bonded to a zirconium atom (i.e. the corner-sharing of polyhedra).
The structure has P213 space group symmetry at low temperatures. At higher temperatures, a centre of inversion is introduced by the disordering of the orientation of tungstate groups, and the space group above the phase transition temperature (~180C) is Pa.
Octahedra and tetrahedra are linked together by sharing an oxygen atom. In the image, note the corner-touching between octahedra and tetrahedra; these are the location of the shared oxygen. The vertices of the tetrahedra and octahedra represent the oxygen, which are spread about the central zirconium and tungsten. Geometrically, the two shapes can "pivot" around these corner-sharing oxygens, without a distortion of the polyhedra themselves. This pivoting is what is thought to lead to the negative thermal expansion, as in certain low frequency normal modes this leads to the contracting 'RUMs' mentioned above.
At high pressure, zirconium tungstate undergoes a series of phase transitions, first to an amorphous phase, and then to a U3O8-type phase, in which the zirconium and tungsten atoms are disordered.
Through hot-isostatically pressing (HIP) a ZrW2O8-Cu composite (system) can be realized. Work done by C. Verdon and D.C. Dunand in 1997 used similarly sized zirconium tungstate and copper powder in a low carbon steel can coated with Cu, and they were HIPed under 103MPa pressure for 3 hours at 600 °C. A control experiment was also conducted, with only a heat treatment (i.e., no pressing) for the same powder mixture also under 600 °C for 3 hours in a quartz tube gettered with titanium.
The results from X-ray diffraction (XRD) in the graph in Verdon & Dunand's paper shows expected products. (a) is from the as received zirconium tungstate powder, (b) is the result from the control experiment , and (c) is the ceramic product from the HIP process. Apparently there are new phases formed according to Spectrum (c) with no ZrW2O8 left. While for the control experiment only partial amount of ZrW2O8 was decomposed.
While complex oxides containing Cu, Zr, and W were believed to be created, selected area diffraction (SAD) of the ceramic product has proven the existence of Cu2O as precipitates after reaction. A model consisted of two concurrent processes were surmised (as presented): (b) the decomposition of the ceramic and loss of oxygen under low oxygen partial pressure at high temperature leads to Cu2O formation; (c) copper diffuses into the ceramic and forms new oxides that absorb some oxygen upon cooling.
Since only very few oxides, those of noble metals which are very expensive, are less stable than Cu2O and Cu2O was believed to be more stable than ZrW2O8, kinetic control of the reaction must be taken into account. For example, reducing reaction time and temperature helps alleviate the residual stress caused by different phases of the ceramic during reaction, which could lead to a delamination of the ceramic particles from the matrix and an increase in the CTE.
Tungsten is a chemical element with the symbol W and atomic number 74. Tungsten is a rare metal found naturally on Earth almost exclusively as compounds with other elements. It was identified as a new element in 1781 and first isolated as a metal in 1783. Its important ores include scheelite and wolframite, the latter lending the element its alternate name.
Zirconium is a chemical element with the symbol Zr and atomic number 40. The name zirconium is derived from the name of the mineral zircon, the most important source of zirconium. The word is related to Persian zargun. It is a lustrous, grey-white, strong transition metal that closely resembles hafnium and, to a lesser extent, titanium. Zirconium is mainly used as a refractory and opacifier, although small amounts are used as an alloying agent for its strong resistance to corrosion. Zirconium forms a variety of inorganic and organometallic compounds such as zirconium dioxide and zirconocene dichloride, respectively. Five isotopes occur naturally, four of which are stable. Zirconium compounds have no known biological role.
Zirconium dioxide is a white crystalline oxide of zirconium. Its most naturally occurring form, with a monoclinic crystalline structure, is the mineral baddeleyite. A dopant stabilized cubic structured zirconia, cubic zirconia, is synthesized in various colours for use as a gemstone and a diamond simulant.
Glass-ceramics are polycrystalline materials produced through controlled crystallization of base glass, producing a fine uniform dispersion of crystals throughout the bulk material. Crystallization is accomplished by subjecting suitable glasses to a carefully regulated heat treatment schedule, resulting in the nucleation and growth of crystal phases. In many cases, the crystallization process can proceed to near completion, but in a small proportion of processes, the residual glass phase often remains. Glass-ceramic materials share many properties with both glasses and ceramics. Glass-ceramics have an amorphous phase and one or more crystalline phases and are produced by a so-called "controlled crystallization" in contrast to a spontaneous crystallization, which is usually not wanted in glass manufacturing. Glass-ceramics have the fabrication advantage of glass, as well as special properties of ceramics. When used for sealing, some glass-ceramics do not require brazing but can withstand brazing temperatures up to 700 °C. Glass-ceramics usually have between 30% [m/m] and 90% [m/m] crystallinity and yield an array of materials with interesting properties like zero porosity, high strength, toughness, translucency or opacity, pigmentation, opalescence, low or even negative thermal expansion, high temperature stability, fluorescence, machinability, ferromagnetism, resorbability or high chemical durability, biocompatibility, bioactivity, ion conductivity, superconductivity, isolation capabilities, low dielectric constant and loss, corrosion resistance, high resistivity and break-down voltage. These properties can be tailored by controlling the base-glass composition and by controlled heat treatment/crystallization of base glass. In manufacturing, glass-ceramics are valued for having the strength of ceramic but the hermetic sealing properties of glass.
An oxyanion, or oxoanion, is an ion with the generic formula A
xOz−
y. Oxyanions are formed by a large majority of the chemical elements. The formulae of simple oxyanions are determined by the octet rule. The corresponding oxyacid of an oxyanion is the compound H
zA
xO
y. The structures of condensed oxyanions can be rationalized in terms of AOn polyhedral units with sharing of corners or edges between polyhedra. The oxyanions adenosine monophosphate (AMP), adenosine diphosphate (ADP) and adenosine triphosphate (ATP) are important in biology.
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 to deal with a LOCA.
Tungsten(VI) oxide, also known as tungsten trioxide is a chemical compound of oxygen and the transition metal tungsten, with formula WO3. The compound is also called tungstic anhydride, reflecting its relation to tungstic acid H2WO4. It is a light yellow crystalline solid.
Negative thermal expansion (NTE) is an unusual physicochemical process in which some materials contract upon heating, rather than expand as most other materials do. The most well-known material with NTE is water at 0 to 3.98 °C. Also, the density of water ice is smaller than the density of liquid water. Water's NTE is the reason why water ice floats, rather than sinks, in liquid water. Materials which undergo NTE have a range of potential engineering, photonic, electronic, and structural applications. For example, if one were to mix a negative thermal expansion material with a "normal" material which expands on heating, it could be possible to use it as a thermal expansion compensator that might allow for forming composites with tailored or even close to zero thermal expansion.
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 the form of its presence in the zirconium hydride controls qualities such as the hardness, ductility, and tensile strength of the resulting zirconium hydride. Zirconium hydride with increased hydrogen content can be made harder and stronger than zirconium, but such zirconium hydride is also less ductile than zirconium.
Zirconium carbide (ZrC) is an extremely hard refractory ceramic material, commercially used in tool bits for cutting tools. It is usually processed by sintering.
Rigid unit modes (RUMs) represent a class of lattice vibrations or phonons that exist in network materials such as quartz, cristobalite or zirconium tungstate. Network materials can be described as three-dimensional networks of polyhedral groups of atoms such as SiO4 tetrahedra or TiO6 octahedra. A RUM is a lattice vibration in which the polyhedra are able to move, by translation and/or rotation, without distorting. RUMs in crystalline materials are the counterparts of floppy modes in glasses, as introduced by Jim Phillips and Mike Thorpe.
Glass-to-metal seals are a type of mechanical seal which joins glass and metal surfaces. They are very important elements in the construction of vacuum tubes, electric discharge tubes, incandescent light bulbs, glass-encapsulated semiconductor diodes, reed switches, glass windows in metal cases, and metal or ceramic packages of electronic components.
Yttria-stabilized zirconia (YSZ) is a ceramic in which the cubic crystal structure of zirconium dioxide is made stable at room temperature by an addition of yttrium oxide. These oxides are commonly called "zirconia" (ZrO2) and "yttria" (Y2O3), hence the name.
Zirconium diboride (ZrB2) is a highly covalent refractory ceramic material with a hexagonal crystal structure. ZrB2 is an ultra-high temperature ceramic (UHTC) with a melting point of 3246 °C. This along with its relatively low density of ~6.09 g/cm3 (measured density may be higher due to hafnium impurities) and good high temperature strength makes it a candidate for high temperature aerospace applications such as hypersonic flight or rocket propulsion systems. It is an unusual ceramic, having relatively high thermal and electrical conductivities, properties it shares with isostructural titanium diboride and hafnium diboride.
Corium, also called fuel-containing material (FCM) or lava-like fuel-containing material (LFCM), is a material that is created in a nuclear reactor core during a nuclear meltdown accident. Resembling lava in consistency, it consists of a mixture of nuclear fuel, fission products, control rods, structural materials from the affected parts of the reactor, products of their chemical reaction with air, water, steam, and, in the event that the reactor vessel is breached, molten concrete from the floor of the reactor room.
Ultra-high-temperature ceramics (UHTCs) are a type of refractory ceramics that that can withstand extremely high temperatures without degrading, often above 2,000 °C. They also often have high thermal conductivities and are highly resistant to thermal shock, meaning they can withstand sudden and extreme changes in temperature without cracking or breaking. Chemically, they are usually borides, carbides, nitrides, and oxides of early transition metals.
NASICON is an acronym for sodium (Na) Super Ionic CONductor, which usually refers to a family of solids with the chemical formula Na1+xZr2SixP3−xO12, 0 < x < 3. In a broader sense, it is also used for similar compounds where Na, Zr and/or Si are replaced by isovalent elements. NASICON compounds have high ionic conductivities, on the order of 10−3 S/cm, which rival those of liquid electrolytes. They are caused by hopping of Na ions among interstitial sites of the NASICON crystal lattice.
Ceria-zirconia is a solid solution of cerium(IV) oxide (CeO2, also known as ceria) and zirconium oxide (ZrO2, also known as zirconia).
Lanthanum ytterbium oxide is a solid inorganic compound of lanthanum, ytterbium and oxygen with the chemical formula of LaYbO3. This compound adopts the Perovskite structure.
Nickel tungstate is an inorganic compound of nickel, tungsten and oxygen, with the chemical formula of NiWO4.