STRUCTURAL

CERAMIC MATERIALS

ZIRCONIA – Structure, Properties, Applications

ZrO2

Zirconium dioxide (ZrO2), popularly known as zirconia, which is a white crystalline oxide
of zirconium. Its most naturally occurring form, with a monoclinic crystalline structure, is
the mineral baddeleyite.
ZrO2 – Zirconia Phase Transformation

There are three known phases for Zirconia: monoclinic below 1170 °C, tetragonal between
1170 °C and 2370 °C, and cubic above 2370 °C. 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. The tetragonal to monoclinic transformation is of great
technological significance, due to the martensitic nature of the reaction and the
accompanying 3-5% volume expansion.
Partially Stabilized / Stabilized Zirconia

monoclinic (1173 °C) tetragonal (2370 °C) cubic (2690 °C) melt

Obtaining stable sintered zirconia ceramic products is difficult because of the large volume
change accompanying the transition from tetragonal to monoclinic (about 5%). Stabilization
of the cubic polymorph of zirconia over wider range of temperatures is accomplished by
substitution of some of the Zr4+ ions (ionic radius of 0.82 Å, too small for ideal lattice of
fluorite characteristic for the cubic zirconia) in the crystal lattice with slightly larger ions,
e.g., those of Y3+ (ionic radius of 0.96 Å). The resulting doped zirconia materials are termed
stabilized zirconia.
Partially Stabilized / Stabilized Zirconia

Materials related to YSZ include calcia-, magnesia-, ceria- or alumina-stabilized zirconias,

or partially stabilized zirconias (PSZ). Hafnia stabilized Zirconia is also known.

Although 8-9 mol% YSZ is known to not be completely stabilized in the pure cubic YSZ
phase up to temperatures above 1000 °C

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.
ZrO2 – Zirconia Properties

Zirconia is chemically unreactive. It is slowly attacked by concentrated hydrofluoric acid

and sulfuric acid.

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.

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). Zirconia is often more useful in its
phase 'stabilized' state.

Stabilized Zirconia has superior thermal, mechanical, and electrical properties.

ZrO2 – Zirconia Properties

Zirconia has excellent resistance to chemicals and corrosion without the typical brittleness
common in technical ceramics.

When compared to other advanced ceramic materials, zirconia has exceptional strength at
room temperature.

Other principal properties of this material include high fracture toughness, high density,
high hardness and wear resistance, good frictional behavior, high temperature capability up
to 2,400ºC, non-magnetic, low thermal conductivity, electrical insulation, coefficient of
thermal expansion similar to iron, and modulus of elasticity similar to steel. Over the years,
a new name was coined for zirconia called ‘ceramic steel’.
ZrO2 – Zirconia Properties
Properties Yttria-Stabilized ZrO2
Zirconia
Content (%) ≥ 93.2% + yttria –

Density (g/m3) 6.0 6.1

Average grain size (μm) ≤ 0.6

Vickers hardness (GPa) 1200 12

Compressive strength (MPa) 1200 1074

Flexural strength (MPa) 800 –

Elastic modulus (GPa) 200 201

Fracture toughness (K1c) MPa 15 6–15

ZrO2 – Zirconia Properties
ZrO2 – Zirconia Applications

Zirconia is used in a wide range of applications, such as precision ball valve (seats and
balls), valves and impellors, pump seals, oxygen sensors, high density grinding media, fuel
cell membranes, thread guides, medical prostheses, cutting blades, gears, metal forming,
radio frequency heating susceptors, metrology components, bearings, bushes and drive
shafts.

Zirconia (ZrO2) bioceramics have been an outstanding biocompatible biomaterial. Due to

its good tribological properties, this material is used for fabricating hip prostheses as the
articulating ball.
ZrO2 – Zirconia Applications

Advanced Technical Ceramics

Advanced technical ceramic parts are used in harsh environments in which resistance to
wear and corrosion and high mechanical performance are of primary importance. Zirconia-
based materials are the best solution for these types of applications due to their excellent
bending strength and toughness, superior hardness and resistance to corrosive
environments.

Optical Fiber Connectors

Optical fiber connectors are devices that enable two optical fibers or an optical fiber and a
terminal to connect. Ferrules and sleeves are the key components of connectors, which
ensure perfect alignment of the fiber after connection to prevent signal loss.
ZrO2 – Zirconia Applications

Thermal Barrier Coatings

Modern diesel, gas and turbine engines are being operated at increasingly higher
temperatures in order to improve combustion performance, lower operating costs and
reduce environmental impact. This is particularly the case in the aerospace and land-based
power turbine industries.

Pigments for Ceramic Tile Decoration

The ceramic tile, porcelain and tableware industries are constantly seeking new decoration
solutions through colors that offer improved aesthetics and longer life. Zirconium silicate-
based synthetic pigments are extensively used in these applications.
ZrO2 – Zirconia Applications

PZT – Lead Zirconate Titanate

A piezoelectric material has the ability to change shape when subjected to an electric
charge. Conversely, a piezoelectric material is able to generate a charge when it is
deformed. Piezoelectric materials are used in applications such as industrial equipment
(flow meter, non-destructive testing), automotive (parking sensor, diesel injector), medical
(ultrasonography, surgical tool), consumer goods (ink jet printing heads, hard drive) and
military (sonobuoy, guidance system).

Brake Pads

Brake pad specifications go far beyond the simple stopping of a vehicle in motion. Other
important requirements include low noise emission during braking, low dust generation,
respect for environmental regulations and maintaining pad physical integrity while braking.
ZrO2 – Zirconia Applications
Refractories for Foundry

the development of performance-enhanced refractories with higher resistance to thermal

shock, corrosion, erosion and wear.

Conductive Ceramics

Although ceramics typically are resistive materials, some ceramic materials — like doped-
zirconia — exhibit outstanding electric conduction properties. Doped-zirconia ceramics
frequently are used as electrolyte in oxygen sensors (lambda probe) or for solid oxide fuel
cell (SOFC) applications due to their high oxygen ion conduction at elevated temperatures
(>300°C). Doped-zirconium dioxide-based electrolyte also exhibits high mechanical
properties, gas tightness, low electronic conduction and chemical stability in both oxidant
and reductive atmospheres