SYNTHESIS OF SOLIDS

INTRODUCTION
Interest in the properties of solids and in the development of new materials has given rise to the
development of a huge variety of methods for preparing them. The method chosen for any solid will
depend not only on the composition of the solid but also on the form it is required in for its proposed
use. For example, silica glass used for fibre optics needs to be much freer of impurities than silica
glass used for manufacturing laboratory equipment. Some methods may be chosen because they
favour the formation of unusual oxidation states, for example, the preparation of chromium dioxide by
hydrothermal method, or because they promote the production of fine powders or, by contrast, large
single crystals. For industrial use, a method that does not employ high temperatures could be
favoured because of the ensuing energy savings.
In the preparation of solids, usually, care has to be taken to use stoichiometric quantities, pure
starting materials and to ensure that the reaction has been completed, because it is usually not
possible to purify a solid once it has formed.
We do not have space here to discuss all the ingenious syntheses that have been employed over the
past few years, so well shall concentrate on those that are commonly used, with a few examples of
the techniques used for solids with particularly interesting properties. The preparation of organic solid-
sate compounds and polymers is not covered as, generally, it involves organic synthesis techniques,
which is a whole field in itself, and is covered in many organic textbooks.
It is difficult to impose a logical order on such a diverse subject. The chapter starts by considering the
most basic and most commonly used method of preparing solids, the ceramic method: this grand title
disguises the fact that it simply means grinding up the reactant solids and heating them hard until
they react! We then go on to look at refinements of this method and ways of improving the uniformity
of the reaction and reducing the reaction temperature. The following sections on microwave heating
and combustion synthesis show alternative methods of inducing solid-state reactions. Later sections
concentrate on less well-known methods of preparing inorganic solids, such as using high pressures
and gas-phase reactions. We also consider some methods used for the production of particularly
pure solids, which are important in the semiconductor industry, for the preparation of single crystals
and for the preparation of nanostructured solids.

HIGH-TEMPERATURE CERAMIC METHODS

DIRECT HEATING OF SOLIDS
CERAMIC METHOD: the simplest and most common way of preparing solids is the ceramic method,
which consists of heating together two nonvolatile solids, which react to form the required product.
This method is widely used both industrially and in the laboratory and can be used to synthesise a
whole range of materials, such as mixed metal oxides, sulfides, nitrides, aluminosilicates and many
others- the first high- temperature superconductors were made by a ceramic method. To take a
simple example, we can consider the formation of zircon, which is used in the ceramics industry as
the basis of high- temperature pigments to colour the glazes on bathroom porcelain. It is made by the
direct reaction of zirconia and silica at 1300°C
The procedure is to take accurately weighed, stoichiometric amounts of the binary oxides, using the
purest of solids, grind them in a pestle and mortar to give a uniform small particle size and then heat
in a furnace for several hours in an alumina crucible.
Despite its widespread use, the simple ceramic method has several disadvantages. High
temperatures are generally required, typically between 500°C and 2000° C and this requires a large
input of energy. This is because the coordination numbers in these ionic binary compounds are high,
verying from 4 to 12, depending on the size and charge of the ion, and it takes a lot of energy to
overcome the lattice energy so that a cation can leave is position in the lattice and diffuse to a
different site. In addition, the phase or compound desired may be unstable or decompose at such
high temperatures. Reactions such as this can be very slow; increasing the temperature speeds up
the reaction as it increases the diffusion rate of the ions. In general, the solids are not raised to their
melting temperatures, so the reaction occurs in the solid state. Solid-state reactions can only take
place at the interface of two solids, and once the surface layer has reacted, the reaction continues as
the reactants diffuse from the bulk to the interface. Raising the temperature enables the reaction at
the interface and the diffusion through the solid to be faster than at room temperatures, a rule of
thumb suggests that a temperature of about two- thirds of the melting temperature of the solids gives
a reasonable reaction time. Even so, diffusion is often the limiting step. Because of this, it is important
that the starting materials are ground to give a small particle size and are very well mixed to maximize
the surface contact area and minimize the distance that the reactants have to diffuse.
To achieve a homogeneous mix of small particles, it is necessary to be very thorough on grinding the
reactants. The number of crystallite faces in direct contact with one another can also be improved by
pelletising the mixed powders in a hydraulic press. Commonly, the reaction mixture is removed during
the heating process and is reground to bring fresh surfaces in contact, thereby speeding up the
reaction. Nevertheless, the reaction time is measured in hours; the preparation of the ternary oxide
CuFe2O4 from CuO and Fe2O3 for example 23 h.
The product is often not homogeneous in composition because as the reaction proceeds, a layer of
the ternary oxide is produced at the interface of the two crystals, so ions now need to diffuse through
this before they react. It is usual to take the initial product, grind it again and reheat several times
before a phasepure product is obtained. Usually trial and error has to be used to find out the best
reaction conditions, with samples tested by powder X- ray diffraction to determine the phase purity.
Solid-state reactions up 2000°C are usually carried out in furnaces that use resistance heating: the
resistance of a metal element results in electrical energy being converted to heat, as in an electric
fire. This is a common method of heating up to 2000°C however, above this temperature; other
methods have to be employed. Higher temperatures in samples can be achieved by directing an
electric arc at the reaction mixture and for very high temperatures; a carbon dioxide laser can give
temperatures up to 4000°C.
Containers must be used for the reactions that can withstand both high temperatures and are also
sufficiently inert not to react themselves; suitable crucibles are commonly made of silica, alumina,
zirconia or magnesia, but metals such as platinum and tantalum and graphite linings are used for
some reactions.
If any of the reactant oxides are nonstoichiometric, volatile, hygroscopic or air-sensitive, then it may
be possible to use carbonates instead. If this simple method of heating in the open atmosphere is no
longer appropriate, a sealed tube method will be needed.
SEALED TUBE METHODS: Evacuated tubes are used when the products or reactants are sensitive
to air or water or are volatile. An example of the use of this method is the preparation of samarium
sulfide. In this case, sulfur has a low boiling temperature and an evacuated tube is necessary to
prevent it from boilinf off and being lost from the reaction vessel.
The preparation of samarium sulfide is of interest because it contains samarium in an unusual
oxidation state of +2 rather than the more common state +3. Samarium metal in powder form and
powdered sulfur are mixed together in stoichiometric proportions and heated to around 730°C in an
evacuated silica tube. The product from the initial heating is then homogenized and heated again, this
time to around 2000°C in a tantalum tube by passing an electric current through the tube, the
resistance of the tantalum providing the heating.
A high pressure of oxygen may be used to prepare an oxide of high- oxidation state or hydrogen for a
reduction reaction. An inert atmosphere may be used to prevent oxidation or decomposition.
The pressures obtained in sealed reaction tubes can be very high, and it is not unknown for tubes to
explode, however carefully they are made; it is thus very important to seal them carefully and to take
safety precautions such as surrounding the tube with a protective metal container and using safety
screens.
SPECIAL ATMOSPHERES: The preparation of some compounds must be carried out under a
special atmosphere, but not necessarily at high pressures: an inert gas such as argon may be used to
prevent oxidation to a higher- oxidation state; or, conversely, a hydrogen atmosphere can be used to
produce a low- oxidation state. Experiments of this type are usually carried out with the reactant
solids in a small boat placed in a tube in a horizontal tube furnace. The gas is passed over the
reactants for a time to expel all the air from the apparatus, and then it flows over the reactants during
the heating and cooling cycles, exiting through a bubbler to maintain a positive pressure and prevent
the ingress of air by back diffusion. To obtain more homogeneous products and better reaction rates,
methods involving particles smaller than those that can be obtained by grinding have been
introduced, and these methods are described in the next section.