Alumina (Aluminium Oxide) - The Different Types of

Commercially Available Grades

Background
Alumina is the most widely used oxide ceramic material. Its applications are
widespread, and include spark plugs, tap washers, pump seals, electronic
substrates, grinding media, abrasion resistant tiles, cutting tools, bioceramics,
(hip-joints), body armour, laboratory ware and wear parts for the textile and
paper industries. Very large tonnages are also used in the manufacture of
monolithic and brick refractories. It is also used mixed with other materials
such as flake graphite where even more severe applications are envisaged,
such as pouring spouts and sliding gate valves.
Key Properties
The characteristics which alumina has and which are important for these
applications are shown below.
High compression strength
High hardness
Resistant to abrasion
Resistant to chemical attack by a wide range of chemicals even at
elevated temperatures
High thermal conductivity
Resistant to thermal shock
High degree of refractoriness
High dielectric strength
High electrical resistivity even at elevated temperatures
Transparent to microwave radio frequencies
Low neutron cross section capture area
Raw material readily available and price not subject to violent
fluctuation
Annual Production
Annual production of alumina is some 45 million tonnes, of which 90% is used
in the manufacture of aluminium metal by electrolysis.
Where Does Alumina Come From?
Most of the aluminium oxide produced commercially is obtained by the
calcination of aluminium hydroxide (frequently termed alumina trihydrate or
ATH). The aluminium hydroxide is virtually all made by the Bayer Process. This
involves the digestion of bauxite in caustic soda and the subsequent
precipitation of aluminium hydroxide by the addition of fine seed crystals of
aluminium hydroxide.
Phases of Alumina
Aluminium oxide exists in many forms, o, _, q, o, k, u, , ; these arise during the
heat treatment of aluminium hydroxide or aluminium oxy hydroxide. The most
thermodynamically stable form is a-aluminium oxide.
Aluminium Hydroxides
Aluminium forms a range of hydroxides; some of these are well characterised
crystalline compounds, whilst others are ill-defined amorphous compounds.
The most common trihydroxides are gibbsite, bayerite and nordstrandite,
whilst the more common oxide hydroxide forms are boehmite and diaspore.
Commercially the most important form is gibbsite, although bayerite and
boehmite are also manufactured on an industrial scale.
Aluminium hydroxide has a wide range of uses, such as flame retardants in
plastics and rubber, paper fillers and extenders, toothpaste filler, antacids,
titania coating and as a feedstock for the manufacture of aluminium chemicals,
e.g. aluminium sulfate, aluminium chlorides, poly aluminium chloride,
aluminium nitrate.


Commercial Grades of Alumina
Smelter Grade Alumina
Smelter or metallurgical grade alumina is the name given to alumina utilised in
the manufacture of aluminium metal. Historically it was manufactured from
aluminium hydroxide using rotary kilns but is now generally produced in fluid
bed or fluid flash calciners. In the fluid flash processes the aluminium
hydroxide is fed into a counter-current stream of hot air obtained by burning
fuel oil or gas. The first effect is that of removing the free water and this is
followed by removal of the chemically combined water; this occurs over a
range of temperatures between 180-600C. The dehydrated alumina is
principally in the form of activated alumina and the surface area gradually
decreases as the temperature rises towards 1000C. Further calcination at
temperatures > 1000C converts this to the more stable a-form. The
conversion to the a-form is typically of the order of 25% and the specific
surface area is relatively high at >50m/g due to the presence of transition
aluminas.
Calcined Alumina
If aluminium hydroxide is heated to a temperature in excess of 1100C, then it
passes through the transition phases of alumina referred to above.
The final product, if a high enough temperature is used, is a-alumina. The
manufacturing process is commercially undertaken in long rotary kilns.
Mineralisers are frequently added to catalyse the reaction and bring down the
temperature at which the a-alumina phase forms; fluoride salts are the most
commonly used mineralisers.
These calcined alumina products are used in a wide range of ceramic and
refractory applications. The main impurity present is sodium oxide. Various
grades are produced which differ in crystallite size, morphology and chemical
impurities.
The calcined grades are often sub-divided into ordinary soda, medium soda
(soda level 0.15-0.25% wt%) and low soda alumina.

Low Soda Alumina
Many applications, particularly in the electrical/electronic areas, require a low
level of soda to be present in the alumina. A low soda alumina is generally
defined as an alumina with soda content of <0.1% by weight. This can be
manufactured by many different routes including acid washing, chlorine
addition, boron addition, and utilisation of soda adsorbing compounds.
Reactive Alumina
Reactive alumina is the terms normally given to a relatively high purity and
small crystal size (<1 m) alumina which sinters to a fully dense body at lower
temperatures than low soda, medium-soda or ordinary-soda aluminas. These
powders are normally supplied after intensive ball-milling which breaks up the
agglomerates produced after calcination. They are utilised where exceptional
strength, wear resistance, temperature resistance, surface finish or chemical
inertness are required.
Tabular Alumina
Tabular alumina is recrystallised or sintered o-alumina, so called because its morphology
consists of large, 50-500 m, flat tablet-shaped crystals of corundum. It is produced by
pelletising, extruding, or pressing calcined alumina into shapes and then heating these shapes
to a temperature just under their fusion point, 1700-1850C in shaft kilns.
After calcination, the spheres of shapes of sintered alumina can be used as they are for some
applications, e.g. catalyst beds, or they can be crushed, screened and ground to produce a
wide range of sizes. As the material has been sintered it has an especially low porosity, high
density, low permeability, good chemical inertness, high refractoriness and is especially
suitable for refractory applications.
Fused Alumina
Fused alumina is made in electric arc furnaces by passing a current between vertical carbon
electrodes. The heat generated melts the alumina. The furnace consists of a water cooled
steel shell and 3-20 tonne batches of material are fused at any one time. The fused alumina
has a high density, low porosity, low permeability and high refractoriness. As a result these
characteristics, it is used in the manufacture of abrasives and refractories.
High Purity Aluminas
High purity aluminas are normally classified as those with a purity of 99.99% and can be
manufactured by routes starting from Bayer hydrate using successive activations and
washings, or via a chloride to achieve the necessary degree of purity. Even higher purities
are manufactured by calcining ammonium aluminium sulfate or from aluminium metal. In
the case of the route via ammonium aluminium sulfate, the necessary degree of purity is
obtained by successive recrystallisations. Especially high purities can be made from
aluminium by reacting the metal with an alcohol, purifying the aluminium alkoxide by
distillation, hydrolysing and the calcination. A minor route involves subjecting super purity
aluminium metal pellets under distilled water to a spark discharge.
Applications include the manufacture of synthetic gem stones such as rubies and yttrium
aluminium garnets for lasers, and sapphires for instrument windows and lasers.
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