Zirconium dioxide

Last updated
Zirconium dioxide
ZrO2powder.jpg
Kristallstruktur Zirconium(IV)-oxid.png
Names
IUPAC names
Zirconium dioxide
Zirconium(IV) oxide
Other names
Zirconia
Baddeleyite
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.013.844 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 215-227-2
PubChem CID
UNII
  • InChI=1S/2O.Zr
    Key: MCMNRKCIXSYSNV-UHFFFAOYSA-N
  • O=[Zr]=O
Properties
ZrO
2
Molar mass 123.218 g/mol
Appearancewhite powder
Density 5.68 g/cm3
Melting point 2,715 °C (4,919 °F; 2,988 K)
Boiling point 4,300 °C (7,770 °F; 4,570 K)
negligible
Solubility soluble in HF, and hot H2SO4
2.13
Thermochemistry
Std molar
entropy
(S298)
50.3 JK−1mol−1
–1080 kJ/mol
Hazards
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H315, H319, H335
P261, P264, P271, P280, P302+P352, P304+P340, P305+P351+P338, P312, P321, P332+P313, P337+P313, P362, P403+P233, P405, P501
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
> 8.8 g/kg (oral, rat)
Safety data sheet (SDS) MSDS
Related compounds
Other anions
Zirconium disulfide
Other cations
Titanium dioxide
Hafnium dioxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Zirconium dioxide (ZrO
2
), sometimes known as zirconia (not to be confused with zirconium silicate or zircon), is a white crystalline oxide of zirconium. Its most naturally occurring form, with a monoclinic crystalline structure, is the mineral baddeleyite. A dopant[ clarification needed ] stabilized cubic structured zirconia, cubic zirconia, is synthesized in various colours for use as a gemstone and a diamond simulant. [1]

Contents

Production, chemical properties, occurrence

Zirconia is produced by calcining zirconium compounds, exploiting its high thermostability. [2]

Structure

Three phases are known: monoclinic below 1170 °C, tetragonal between 1170 °C and 2370 °C, and cubic above 2370 °C. [3] The trend is for higher symmetry at higher temperatures, as is usually the case. A small percentage of the oxides of calcium or yttrium stabilize in the cubic phase. [2] The very rare mineral tazheranite, (Zr,Ti,Ca)O2, is cubic. Unlike TiO2, which features six-coordinated titanium in all phases, monoclinic zirconia consists of seven-coordinated zirconium centres. This difference is attributed to the larger size of the zirconium atom relative to the titanium atom. [4]

Chemical reactions

Zirconia is chemically unreactive. It is slowly attacked by concentrated hydrofluoric acid and sulfuric acid. When heated with carbon, it converts to zirconium carbide. When heated with carbon in the presence of chlorine, it converts to zirconium(IV) chloride. This conversion is the basis for the purification of zirconium metal and is analogous to the Kroll process.

Engineering properties

Bearing balls Zirconium dioxide ZrO2 bearing balls.jpg
Bearing balls

Zirconium dioxide is one of the most studied ceramic materials. ZrO2 adopts a monoclinic crystal structure at room temperature and transitions to tetragonal and cubic at higher temperatures. The change of volume caused by the structure transitions from tetragonal to monoclinic to cubic induces large stresses, causing it to crack upon cooling from high temperatures. [5] When the zirconia is blended with some other oxides, the tetragonal and/or cubic phases are stabilized. Effective dopants include magnesium oxide (MgO), yttrium oxide (Y2O3, yttria), calcium oxide (CaO), and cerium(III) oxide (Ce2O3). [6]

Zirconia is often more useful in its phase 'stabilized' state. Upon heating, zirconia undergoes disruptive phase changes. By adding small percentages of yttria, these phase changes are eliminated, and the resulting material has superior thermal, mechanical, and electrical properties. In some cases, the tetragonal phase can be metastable. If sufficient quantities of the metastable tetragonal phase is present, then an applied stress, magnified by the stress concentration at a crack tip, can cause the tetragonal phase to convert to monoclinic, with the associated volume expansion. This phase transformation can then put the crack into compression, retarding its growth, and enhancing the fracture toughness. This mechanism, known as transformation toughening, significantly extends the reliability and lifetime of products made with stabilized zirconia. [6] [7]

The ZrO2 band gap is dependent on the phase (cubic, tetragonal, monoclinic, or amorphous) and preparation methods, with typical estimates from 5–7 eV. [8]

A special case of zirconia is that of tetragonal zirconia polycrystal, or TZP, which is indicative of polycrystalline zirconia composed of only the metastable tetragonal phase.

Uses

The main use of zirconia is in the production of hard ceramics, such as in dentistry, [9] with other uses including as a protective coating on particles of titanium dioxide pigments, [2] as a refractory material, in insulation, abrasives, and enamels.

Stabilized zirconia is used in oxygen sensors and fuel cell membranes because it has the ability to allow oxygen ions to move freely through the crystal structure at high temperatures. This high ionic conductivity (and a low electronic conductivity) makes it one of the most useful electroceramics. [2] Zirconium dioxide is also used as the solid electrolyte in electrochromic devices.

Zirconia is a precursor to the electroceramic lead zirconate titanate (PZT), which is a high-κ dielectric, which is found in myriad components.

Niche uses

The very low thermal conductivity of cubic phase of zirconia also has led to its use as a thermal barrier coating, or TBC, in jet and diesel engines to allow operation at higher temperatures. [10] Thermodynamically, the higher the operation temperature of an engine, the greater the possible efficiency. Another low-thermal-conductivity use is as a ceramic fiber insulation for crystal growth furnaces, fuel-cell stacks, and infrared heating systems.

This material is also used in dentistry in the manufacture of subframes for the construction of dental restorations such as crowns and bridges, which are then veneered with a conventional feldspathic porcelain for aesthetic reasons, or of strong, extremely durable dental prostheses constructed entirely from monolithic zirconia, with limited but constantly improving aesthetics. [11] [12] Zirconia stabilized with yttria (yttrium oxide), known as yttria-stabilized zirconia, can be used as a strong base material in some full ceramic crown restorations. [12] [13]

Transformation-toughened zirconia is used to make ceramic knives. [14] Because of the hardness, ceramic-edged cutlery stays sharp longer than steel edged products. [15]

Due to its infusibility and brilliant luminosity when incandescent, it was used as an ingredient of sticks for limelight.[ citation needed ]

Zirconia has been proposed to electrolyze carbon monoxide and oxygen from the atmosphere of Mars to provide both fuel and oxidizer that could be used as a store of chemical energy for use with surface transportation on Mars. Carbon monoxide/oxygen engines have been suggested for early surface transportation use, as both carbon monoxide and oxygen can be straightforwardly produced by zirconia electrolysis without requiring use of any of the Martian water resources to obtain hydrogen, which would be needed for the production of methane or any hydrogen-based fuels. [16]

Zirconia can be used as photocatalyst [17] since its high band gap (~ 5 eV) [18] allows the generation of high-energy electrons and holes. Some studies demonstrated the activity of doped zirconia (in order to increase visible light absorption) in degrading organic compounds [19] [20] and reducing Cr(VI) from wastewaters. [21]

Zirconia is also a potential high-κ dielectric material with potential applications as an insulator in transistors.

Zirconia is also employed in the deposition of optical coatings; it is a high-index material usable from the near-UV to the mid-IR, due to its low absorption in this spectral region. In such applications, it is typically deposited by PVD. [22]

In jewelry making, some watch cases are advertised as being "black zirconium oxide". [23] In 2015 Omega released a fully ZrO2 watch named "The Dark Side of The Moon" [24] with ceramic case, bezel, pushers, and clasp, advertising it as four times harder than stainless steel and therefore much more resistant to scratches during everyday use.

In gas tungsten arc welding, tungsten electrodes containing 1% zirconium oxide (a.k.a. zirconia) instead of 2% thorium have good arc starting and current capacity, and are not radioactive. [25]

Diamond simulant

Brilliant-cut cubic zirconia CZ brilliant.jpg
Brilliant-cut cubic zirconia

Single crystals of the cubic phase of zirconia are commonly used as diamond simulant in jewellery. Like diamond, cubic zirconia has a cubic crystal structure and a high index of refraction. Visually discerning a good quality cubic zirconia gem from a diamond is difficult, and most jewellers will have a thermal conductivity tester to identify cubic zirconia by its low thermal conductivity (diamond is a very good thermal conductor). This state of zirconia is commonly called cubic zirconia, CZ, or zircon by jewellers, but the last name is not chemically accurate. Zircon is actually the mineral name for naturally occurring zirconium(IV) silicate (ZrSiO4).

See also

Related Research Articles

<span class="mw-page-title-main">Zirconium</span> Chemical element with atomic number 40 (Zr)

Zirconium is a chemical element; it has symbol Zr and atomic number 40. First identified in 1789, isolated in impure form in 1824, and manufactured at scale by 1925, pure zirconium is a lustrous transition metal with a greyish-white color that closely resembles hafnium and, to a lesser extent, titanium. It is solid at room temperature, ductile, malleable and corrosion-resistant. 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. Besides zircon, zirconium occurs in over 140 other minerals, including baddeleyite and eudialyte; most zirconium is produced as a byproduct of minerals mined for titanium and tin.

<span class="mw-page-title-main">Cubic zirconia</span> The cubic crystalline form of zirconium dioxide

Cubic zirconia (abbreviated CZ) is the cubic crystalline form of zirconium dioxide (ZrO2). The synthesized material is hard and usually colorless, but may be made in a variety of different colors. It should not be confused with zircon, which is a zirconium silicate (ZrSiO4). It is sometimes erroneously called cubic zirconium.

<span class="mw-page-title-main">Thorium dioxide</span> Chemical compound

Thorium dioxide (ThO2), also called thorium(IV) oxide, is a crystalline solid, often white or yellow in colour. Also known as thoria, it is mainly a by-product of lanthanide and uranium production. Thorianite is the name of the mineralogical form of thorium dioxide. It is moderately rare and crystallizes in an isometric system. The melting point of thorium oxide is 3300 °C – the highest of all known oxides. Only a few elements (including tungsten and carbon) and a few compounds (including tantalum carbide) have higher melting points. All thorium compounds, including the dioxide, are radioactive because there are no stable isotopes of thorium.

<span class="mw-page-title-main">Refractory</span> Materials resistant to decomposition under high temperatures

In materials science, a refractory is a material that is resistant to decomposition by heat or chemical attack and that retains its strength and rigidity at high temperatures. They are inorganic, non-metallic compounds that may be porous or non-porous, and their crystallinity varies widely: they may be crystalline, polycrystalline, amorphous, or composite. They are typically composed of oxides, carbides or nitrides of the following elements: silicon, aluminium, magnesium, calcium, boron, chromium and zirconium. Many refractories are ceramics, but some such as graphite are not, and some ceramics such as clay pottery are not considered refractory. Refractories are distinguished from the refractory metals, which are elemental metals and their alloys that have high melting temperatures.

<span class="mw-page-title-main">Zirconium tungstate</span> Chemical compound

Zirconium tungstate is the zirconium salt of tungstic acid with the formula Zr(WO4)2. 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. 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). A number of other phases are formed at high pressures.

<span class="mw-page-title-main">Yttrium(III) oxide</span> Chemical compound

Yttrium oxide, also known as yttria, is Y2O3. It is an air-stable, white solid substance.

<span class="mw-page-title-main">Bismuth(III) oxide</span> Chemical compound

Bismuth(III) oxide is a compound of bismuth, and a common starting point for bismuth chemistry. It is found naturally as the mineral bismite (monoclinic) and sphaerobismoite, but it is usually obtained as a by-product of the smelting of copper and lead ores. Dibismuth trioxide is commonly used to produce the "Dragon's eggs" effect in fireworks, as a replacement of red lead.

<span class="mw-page-title-main">Zirconium carbide</span> Chemical compound

Zirconium carbide (ZrC) is an extremely hard refractory ceramic material, commercially used in tool bits for cutting tools. It is usually processed by sintering.

<span class="mw-page-title-main">Ceramic knife</span> Knife with a blade made out of non-metallic material

A ceramic knife is a knife with a ceramic blade typically made from zirconium dioxide (ZrO2; also known as zirconia), rather than the steel used for most knives. Ceramic knife blades are usually produced through the dry-pressing and firing of powdered zirconia using solid-state sintering. The blades typically score 8.5 on the Mohs scale of mineral hardness, compared to 4.5 for normal steel and 7.5 to 8 for hardened steel and 10 for diamond. The resultant blade has a hard edge that stays sharp for much longer than conventional steel blades. However, the blade is brittle, subject to chipping, and will break rather than flex if twisted. The ceramic blade is sharpened by grinding the edges with a diamond-dust-coated grinding wheel.

<span class="mw-page-title-main">Ceramic engineering</span> Science and technology of creating objects from inorganic, non-metallic materials

Ceramic engineering is the science and technology of creating objects from inorganic, non-metallic materials. This is done either by the action of heat, or at lower temperatures using precipitation reactions from high-purity chemical solutions. The term includes the purification of raw materials, the study and production of the chemical compounds concerned, their formation into components and the study of their structure, composition and properties.

<span class="mw-page-title-main">Hafnium(IV) oxide</span> Chemical compound

Hafnium(IV) oxide is the inorganic compound with the formula HfO
2
. Also known as hafnium dioxide or hafnia, this colourless solid is one of the most common and stable compounds of hafnium. It is an electrical insulator with a band gap of 5.3~5.7 eV. Hafnium dioxide is an intermediate in some processes that give hafnium metal.

<span class="mw-page-title-main">Thermal barrier coating</span> Form of exhaust heat management

Thermal barrier coatings (TBCs) are advanced materials systems usually applied to metallic surfaces on parts operating at elevated temperatures, such as gas turbine combustors and turbines, and in automotive exhaust heat management. These 100 μm to 2 mm thick coatings of thermally insulating materials serve to insulate components from large and prolonged heat loads and can sustain an appreciable temperature difference between the load-bearing alloys and the coating surface. In doing so, these coatings can allow for higher operating temperatures while limiting the thermal exposure of structural components, extending part life by reducing oxidation and thermal fatigue. In conjunction with active film cooling, TBCs permit working fluid temperatures higher than the melting point of the metal airfoil in some turbine applications. Due to increasing demand for more efficient engines running at higher temperatures with better durability/lifetime and thinner coatings to reduce parasitic mass for rotating/moving components, there is significant motivation to develop new and advanced TBCs. The material requirements of TBCs are similar to those of heat shields, although in the latter application emissivity tends to be of greater importance.

Zirconia toughened alumina is a ceramic material comprising alumina and zirconia. It is a composite ceramic material with zirconia grains in the alumina matrix.

<span class="mw-page-title-main">Yttria-stabilized zirconia</span> Ceramic with room temperature stable cubic crystal structure

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.

Ultra-high-temperature ceramics (UHTCs) are a type of refractory ceramics 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.

<span class="mw-page-title-main">Ceria-zirconia</span>

Ceria-zirconia is a solid solution of cerium(IV) oxide (CeO2, also known as ceria) and zirconium oxide (ZrO2, also known as zirconia).

<span class="mw-page-title-main">Yttralox</span>

Yttralox is a transparent ceramic consisting of yttria (Y2O3) containing approximately 10% thorium dioxide (ThO2). It was one of the first transparent ceramics produced, and was invented in 1966 by Richard C. Anderson at the General Electric Research Laboratory while sintering mixtures of rare earth minerals.

<span class="mw-page-title-main">George Gogotsi</span>

Geо́rge Antо́novych Gogо́tsi is a soviet Ukrainian scientist, professor of solid mechanics, doctor of science, and leading researcher of the Pisarenko Institute for Problems of Strength of the National Academy of Sciences of Ukraine.

<span class="mw-page-title-main">Katherine Faber</span> American materials scientist

Katherine T. Faber is an American materials scientist and one of the world's foremost experts in ceramic engineering, material strengthening, and ultra-high temperature materials. Faber is the Simon Ramo Professor of Materials Science at the California Institute of Technology (Caltech). She was previously the Walter P. Murphy Professor and department chair of Materials Science and Engineering at the McCormick School of Engineering and Applied Science at Northwestern University.

Hafnium compounds are compounds containing the element hafnium (Hf). Due to the lanthanide contraction, the ionic radius of hafnium(IV) (0.78 ångström) is almost the same as that of zirconium(IV) (0.79 angstroms). Consequently, compounds of hafnium(IV) and zirconium(IV) have very similar chemical and physical properties. Hafnium and zirconium tend to occur together in nature and the similarity of their ionic radii makes their chemical separation rather difficult. Hafnium tends to form inorganic compounds in the oxidation state of +4. Halogens react with it to form hafnium tetrahalides. At higher temperatures, hafnium reacts with oxygen, nitrogen, carbon, boron, sulfur, and silicon. Some compounds of hafnium in lower oxidation states are known.

References

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Further reading