POWDER PREPARATION ^ MIXING AND GRINDING 97

However, it is usually quite easy to determine as a loss in weight after heating to a suitable
temperature.

Chemical composition is only one aspect of the specication of a raw material. Particle size and
degree of aggregation are often important, and are more dicult to specify and to agree on with
a supplier. It is even more dicult to specify the reactivity of a material but it can be of
primary importance. Reactivity depends on particle size and the perfection of the crystals
comprising the particles. Many raw materials are subjected to heat treatment during their
preparation, and variations in the temperature and duration of this may aect reactivity. These
raw material parameters are modied by the subsequent processing so that corrections can be
made for some variations in them provided that the magnitude of the variations is known. The
more detailed is the specication the more expensive is the material, so that a balance has to be
kept between the elaboration of the specication and the cost of testing and correcting for
variations during processing.

The ultimate test for a starting material is that when it is put through a standard process it yields
a product with specied properties. The assumption is often made that the process used in
production is suciently standard to be used as a basis for raw material testing. This assumption
needs careful conrmation since wear and tear causes changes in the behaviour of plant and
machinery. Frequently a model production line is set up in the laboratory with a closely
controlled and consistent performance and bearing a well-established relation- ship to the large-
scale production line. This can serve as a check on the production process. Such a line is a
necessity when introducing a new process but may be expensive to maintain. Most commercial
operations employ a mixture of analytical and physical tests coupled with laboratory and
manufacturing trials in an endeavour to achieve an economical compromise. The dicult factor
to estimate is the possible cost of a breakdown in production leading to a high scrap level or a
loss of orders.

The storage of materials is important. The cheapest method is a heap in the open, which may be
adequate for coal for a furnace. The most expensive is a room in which the humidity and
temperature are controlled. The importance of controlling moisture content is the most relevant
factor determining the amount spent on storage space. The quantity of material kept in store has
signicant economic consequences. On the one hand it represents idle capital; on the other each
of a succession of small batches needs handling and testing, both involving expense. It may seem
superuous to mention that every batch of every material should be clearly identied and
accessible, but such details can lead to much trouble if neglected.
3.4 Powder Preparation ^ Mixing and Grinding

The rst step is to weigh out the raw material with due allowance for impurity and moisture
content. Many modern weighing machines record each weighing; otherwise the only safeguard
against normal human fallibility is to have every weighing checked by a second person.

The next step is mixing, eliminating aggregates and/or reducing the particle size. If compound
formation is to occur during calcining or ring, the matter of neighbouring particles must
interdiuse and the time taken to complete the process will be proportional to the square of the
particle size. The process will clearly be considerably slower if the particles consist of aggregates
of crystals rather than individual crystals. Even where there is only a single component,
aggregates that are present during sintering usually densify more rapidly internally than with
neighbouring aggregates, with a resulting residue of pores in the spaces originally between the
aggregates. Apart from breaking up agglomerates and forming an intimate mixture of the
constituents, a milling process introduces defects into the crystals which may enhance diusion
and accelerate sintering.

The most commonly used method of initial mixing is wet ball-milling. A ball- mill is a barrel
(usually of ceramic material) that rotates on its axis and is partially lled with a grinding medium
in the form of spheres, cylinders or rods. The grinding medium is in such quantity that the
rotation of the mill causes it to cascade, rather like the breaking of a wave on the shore, so that
both a shearing and a crushing action is applied to any material lying between the milling
elements. For ecient action the real volume of material to be milled should be about a third of
that of the milling media. The volume of liquid must be sucient to form a freely owing cream,
usually between 100 and 200% of the volume of the powder. The addition of surface-active
agents reduces the amount of water needed for a given uidity and assists in the dispersion of the
softer aggregates. The ball charge normally contains a range of sizes with the largest diameter
being of the order of a tenth of the diameter of the barrel. The optimum quantity of balls, their
sizes and composition, the quantity of slip and the rate of rotation are normally dened by the
supplier of the plant but require adjustment for particular applications. Ball-mills are slow but
mechanically simple and robust. They mix and eliminate aggregates and can reduce the particle
size to around 10 m m.

The milling media are inevitably abraded by the charge and therefore contaminate it.
Contamination is minimized by adhering to well-established practice which will optimize the
time of milling, by using hard materials for the grinding media, e.g. int, alumina or tungsten
carbide, or by using materials of the same composition as one of the constituents of the charge,
e.g. alumina for aluminous porcelains or steel for ferrites. The contamination may be less than
0.1% but can rise to 1 or 2% under adverse conditions. It is important that the media are
inspected periodically and undersized pieces discarded since they will eventually be smashed by
impact with larger pieces and contribute excessive contamination. The barrel is normally made
of aluminous porcelain and will also be abraded. It can be coated internally with an abrasion-
resistant polymer or formed entirely of a polymer, and any contamination from this will be
burned away in subsequent ring stages; however, larger pieces of polymer that survive up to the
nal sintering may result in large pores.

Wet ball-milling is faster than dry-milling and facilitates the separation of the milling media
from the charge. Its disadvantage is that the liquid must be removed, which is most economically
achieved by ltration, but any soluble constituent will be removed with the liquid. If this is
undesirable the alternative is to evaporate the liquid which can be eected by spray-drying if the
liquid is water. Evaporation can also take place in shallow trays in ovens; in this case soluble
material may appear as a skin on the surface and heavy coarse particles may settle out.

The liquid used is usually water since it is available with adequate purity at low cost and is non-
ammable and non-toxic. However, because it results in a powder with a very thoroughly
hydrated surface which may have a signicantly reduced reactivity during the sintering process,
dry-milling is sometimes preferred. In this case it is usually necessary to add a surface-active
material such as a stearate containing an inorganic cation to prevent the powder forming a cake
on the mill walls. Dry-milling can be combined with the continuous removal of ne particles by
forcing air over the surface of the rotating charge and ltering out the entrained material.

Alternatives to ball-mills include vessels with rotating paddles and rotating barrels that contain
baes that ensure that the powder is tossed about. These have no grinding action so that the
particle size is unaltered. They also have little eect on aggregates.

So-called vibro-energy mills are machines for vibrating vessels lled with grinding media at
amplitudes up to approximately 5 cm. The interstices are lled with a slip containing the material
to be ground. Size reduction is far more rapid than in ball-mills and the particle size can be
regulated to some extent by the size of the media elements; 3-mm alumina balls give a size range
of 13 m m. Similar results are obtained by having a paddle rotating through the grinding media
in a stationary vessel the attritor mill. In this case the heat generated must be removed by
water cooling. Such methods can yield powders in which a high proportion of particles have
sizes below 1 m m.

Contamination by the milling media can be largely avoided by the use of uid energy mills. In
these the powder is entrained in two streams of high-velocity air which are made to impinge on
one another so that the particles are broken up by impact. The feedstock must already be ground
to within a factor of 10 of the nal size required and adjustments are necessary to suit particular
materials. Very good mixing on an atomic scale can be achieved by chemical methods [5], and in
the context of electroceramics the production of high purity, sub-micron barium titanate-based
powders for the manufacture of multilayer capacitors (see Section 5.4.3) is of paramount
importance. Tight control over powder chemistry has a direct and signicant inuence over
capacitor failure rates. Also, the strong interest in ferroelectric random access memories
(FeRAMs) and in new ceramics for dynamic random access memories DRAMS (see Section
5.7.5) has stimulated demand for precursors for the fabrication of thin lms that can be
incorporated into integrated circuits.

If the cations of interest, Ba 2+ and Ti 4+ in the case of barium titanate, can be obtained in
solution in the correct ratio then precursors to the nal required product can be formed.
Subsequent heating of the precursors leads to the formation of BaTiO 3 (BT) involving the
minimum of ion diusion distances.

Because of this the oxides can be formed at relatively low temperatures, for example $ 500 8 C
rather than the usual 4 1000 8 C necessary to eect the solid state reaction between mixed
oxides.

An example of this approach is the co-precipitation of mixed oxides, hydroxides and carbonates
from aqueous solution. Another approach is for the cations of interest to be complexed to form
an organometallic compound, an alkoxide, for example. Subsequent hydrolysis and heat
treatment of the precursors yields the required oxide. Cations can also often be incorporated into
sols and gels and the mixed oxides produced by dehydration. There are four principal routes to
producing barium titanate powders.

3.4.1 The mixed oxide or solid state route

This route is the solid state reaction at temperatures above $ 1100 8 C of a mixture of BaCO 3
and TiO 2 together with modiers. The calcination is followed by comminution to reduce the
particle size to approximately 1 mm.

Although the route is still widely used for commercial scale production, as the demands for
modied powders having precisely controlled physical and chemical characteristics intensies,
so there will be a progressive move away from the mixed oxide toward the chemical routes.