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Production of High Silicon Alloys

Article · January 1998

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Halvard Tveit
Norwegian University of Science and Technology
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Chapter 1

Introduction
Silicon is the second-most abundant element in the earth’s crust after oxygen. In natural form
it is almost exclusively combined with oxygen as fairly pure silicon dioxide and silicates.
Silicon dioxide as flint was a main tool for man in the Stone Age, and later silicates have been
essential in materials such as ceramics and glass. Silicon was recognized as an element in the
early nineteenth century and produced on industrial scale as element or in alloys from the end
of the century. Around 1950, extremely pure silicon was produced and used in the silicon
chip, the key unit in calculators, computers and other electronic devices. Elementary silicon
has a semi-metallic shiny look. It is hard, but rather fragile and not suited for the making of
consumer goods. Therefore silicon and its alloys were rather unknown to the general public
before the computer industry made it famous and the Silicon Valley became a symbol for the
modern world.
This chapter gives a short survey of the production and use of high silicon alloys. At last the
availability of raw materials is discussed.

1.1. Metallurgical production of high silicon alloys

Silicon is produced industrially by reduction of silicon dioxide with carbon in arc furnaces by
a reaction that in an idealized form can be written as:
SiO2 + 2 C = Si + 2 CO [1.1]
We will see later that the real reaction is more complex. In industry the available raw
materials are not pure, and the product will contain other elements. With pure operation and
pure raw materials and electrodes it is possible to obtain silicon with less than 1 - 2 per cent
of other elements. This product is traditionally called silicon metal even though solid silicon
is not a metal. The furnace behaviour during the production of silicon metal has several
features that are markedly different from the corresponding behaviour during production of
most metals. These features will be discussed in detail later; here it suffices to state a few
characteristic features of the silicon process:
1. The gas in the hottest zone of the furnace has a high content of a silicon-containing gas
that must be recovered in the outer charge layers if the silicon recovery is to be high.
2. The silicon-recovering reactions in the outer charge layers heat the charge to a very high
temperature and create a sticky charge that does not flow easily into the hottest zone.
3. The gas from the furnace contains significant amounts of a dust consisting of SiO2.
This characteristic behaviour of furnaces for silicon metal will be found also if we add a
limited amount of metals to the charge. The most common alloying element is iron. Silicon
content is given by numbers. For example, FeSi75 means an iron-silicon alloy with 75 weight
% silicon. In practice there may be up to several per cent of other elements than silicon and
iron. In this book, the term high silicon alloys includes all the silicon-containing alloys
where the silicon dominates the behaviour in the furnace. We also include alloys that can be
produced by metallurgical refining of high silicon alloys from the arc furnace. Such
metallurgical refining may be done by slag treatment, gas purging or crystallization. This
definition includes the purest silicon that can be made by metallurgical means, but not
semiconductor silicon made through distillation and decomposition of compounds containing
silicon.
The production of high silicon alloys is presently based on the carbothermal reaction that is
idealized in Reaction [1.1]. In practical operation there is always some silicon loss in the gas.
This is mainly due to a loss of the gas species SiO. The SiO burns together with CO in excess
air above the charge. A more accurate description of the process must necessarily be more
complex:
(1+x) SiO2 + (2+x) C = Si + x SiO + (2+x) CO [1.2]
(1+x) SiO2 + (2+x) C + (1+x) O2 = Si + x SiO2(silica fume) + (2+x) CO2 + heat [1.3]

Equation [1.2] describes the process seen inside the furnace; Equation [1.3] also includes the
reactions that take place after the furnace.
A silicon metal plant that is designed and based on this reaction is shown in Figure 1.1.

Figure 1.1 A typical plant for the production of silicon metal.

The core of the plant is the arc furnace. A typical furnace has a pot with a diameter around 10
metres. The pot is filled with charge materials. Three electrodes submerged into the charge
supply a three-phase current that passes through the content of the furnace. The current heats
part of the charge to about 2000 °C in the hottest part. At this high temperature the silicon
dioxide is reduced to molten silicon. The silicon is tapped from the furnace through a taphole
at the bottom and refined by slag treatment or gas purging. During the refining, particles of
oxide and carbide are removed, and the composition is adjusted to the specified value. After
refining, the molten alloy is allowed to cool in a suitable mould and then crushed to the
specified size. The consumption of electric energy is 11 - 13 MWh per metric ton of silicon
metal in most plants.
The gas from the furnace burns above the surface of the charge. It has a heat content of the
same order of magnitude as the electric energy added to the furnace. This heat can be used in
a heat recovery station for heating or to produce electricity in a power plant. The filtered gas
still has some impurities, mainly sulphur dioxide. The dust in the filter consists mainly of
amorphous SiO2 with a particle size around 0.1 µm and is sometimes named condensed silica
fume (CSF). The silica fume has a specific surface around 20 m2 per gram. It can be used as
an addition or filler to concrete, ceramics, refractory, rubber etc1. A furnace produces 0.2 - 0.4
tons of silica per ton of silicon metal.
The products of the process are:
1. High silicon alloy.
2. Condensed silica fume.
3. Recoverable heat energy.
The most important high silicon alloys are silicon metal and ferrosilicon with 65, 75 or 90 per
cent silicon. Any composition in the Fe-Si system can be produced, and small amounts of
alloys of other compositions are produced. Special compositions are most common in
connection with small amounts of additional elements such as magnesium, calcium and rare
earth’s. A high silicon Al-Si can be produced in the arc furnace, but it has yet not found a
large market.
The world production of the main high silicon alloys is shown in Figures 1.2a and 1.2b. The
total production is approximately 980 000 tonnes of silicon and 2 600 000 tonnes of silicon
contained in ferrosilicon.

Others
Norway 25%
12%

Brazil USA
14% 19%
China CIS
24% 6%

1 ®
Elkem sells silica fume under the trade name Microsilica
 USA CIS
8% 19%

Others
China
24%
31%
Norway Brazil
12% 6%

Figure 1.2a Major silicon producers. The World production of silicon in 1997 was about 980 000
tonnes. [CRU Intenational 1998].

Figure 1.2b Major ferrosilicon producers. The World production of ferrosilicon in 1997 is about 2
600 000 tonnes of silicon contained in ferrosilicon. [CRU Intenational 1998].

1.2. Silicon applications

The main applications for silicon are:
1. Desoxidation and alloying of steel and cast iron (mainly ferrosilicon)
2. Alloying of other metals, especially aluminium (mainly silicon metal)
3. Raw material in the chemical industry (mainly silicon metal, some high silicon
ferrosilicon)
4. Raw material for the semiconductor industry
- Electronic devices (silicon with impurities in the ppb range)
- Photovoltaic cells (silicon with impurities in the ppm range)

1.2.1. Ferrosilicon alloys

The largest application is ferrosilicon in steel and cast iron. The desoxidation task is to bind
and remove oxygen and oxides in steel. One example is the use of ferrosilicon in stainless
steel production where the ferrosilicon reduces the Cr-rich slag and consequently most of the
valuable elements in the slag, such as chromium and manganese, are recovered.
As an alloying element, silicon is used to increase the elasticity and the tensile yield as well as
annealing resistance for different steel qualities.
In cast iron applications ferrosilicon is used as a base for inoculant materials. Inoculation of
liquid iron is the practice of adding small quantities of alloys, which induce graphite
nucleation and thereby realize the graphitization potential of the liquid.
This use of silicon for the application mentioned above is not expected to grow rapidly, since
the iron and steel industry grows slowly, and the consumption of silicon per tonne of product
decreases.

• Automotive
• Steel • Buildings
FERRO- • Industriel
SILICON equipment
• Foundry • Farming

SOME SILICON AND FERROSILICON USAGES

• Aluminum • Automotive
• Aeroplanes
SILICON-
• Silicones
METAL • •CChemical
elektronikk • Computers
• Solar Cells
• Electronic

Figure 1.3 Examples of usage of silicon and ferrosilicon alloys.

1.2.2. Silicon as an alloying element

Alloying of other metals consumes about a half of the production of silicon metal. The use of
silicon as an alloying element for aluminium is parallel to ferrosilicon for steel. The main
difference is that iron is normally a contamination in aluminium. The need to achieve low
iron content in silicon induces several process parameters such as the choice of raw material
and the use of special iron-free electrodes for silicon production.

1.2.3. Silicon for chemical use

Some silicon metal or high silicon ferrosilicon is converted to SiCl4 following reaction with
HCl. The SiCl4 is later reacted with water to an SiO2 with an extremely high specific surface.
The product is used as filler in a series of products. The production process can be varied and
gives a set of product types with a strong variation in price.
The main product from the chemical industry is the silicones, which are silico-organic
polymers. They consist of long chains -O-Si-O- where the two other bonding positions are
taken by organic groups, usually the methyl -CH3 or phenyl -C6H5 groups. The properties
vary over a wide range of liquid oils, greases, rubbers and solid resins. The silicones are
chemically inert, water-repellent and stable up to about 400 °C. They are used as lubricants,
hydraulic fluids, protective coatings, electric insulators and artificial body parts. The silicon
producer may influence the production process for silicones by controlling the content of
tramp elements in silicon and by the casting technique.
1.2.4. Silicon for electronic use
Another important application of silicon is the use in semiconductors in everyday electronic
devices such as calculators and computers. This use is well known even if it stands for a
rather small percentage of the total silicon consumption. Silicon for semiconductors must be
extremely pure with an overall content of other elements in the low ppb range. This purity is
obtained by a complex chemical purification of standard silicon metal. Several processes are
possible, but at present the so-called Siemens process is the most important. There the silicon
is transformed to a silicon-containing gas:
300 ° C
Si + 3 HCl(g) 
→ HSiCl 3 (g) + H 2 (g) [1.4]
The gas is purified by distillation and reduced to silicon by hydrogen.
1100 °C
4 HSiCl 3 (g) + 2 H 2 (g) → 3 Si + SiCl 4 (g) + 8 HCl(g) [1.5]
The real process is more complicated than shown here, and the yield of silicon is rather low
for most producers. The product is deposited on silicon rods in bell jars of very pure silica
glass. The deposition is a slow process, and much energy has to be spent to keep the interior
of the bell jar hot. Therefore the energy consumption of the purification process is very high,
maybe 100 MWh per metric ton.
A new and interesting electronic application of silicon is photovoltaics. Photovoltaic cells
convert energy in light directly to electricity. The cells can be made from many materials, but
silicon is very promising as the main material since it is available in virtually unlimited
quantities, is non-poisonous and only moderately expensive. The specification for solar
silicon will be less strict than the specification for semiconductor silicon.
The photovoltaic energy has a long way to go before it is competitive in cost with fossil fuels.
The cost of sufficiently pure silicon is presently a relatively small fraction of the total cost.
Therefore low-cost silicon will not in itself cause a breakthrough in the cost of photovoltaic
electricity, but it is necessary to have silicon available at a moderate cost if the production of
silicon solar cells is to develop further. Up to this time, offgrade from the semiconductor
industry has covered the need, but in the future a new source of cheap photovoltaic silicon is
necessary.

3. Availability of raw materials

The earth’s crust is estimated to contain about 28 per cent silicon bound as SiO2 and silicates.
A fairly large fraction of this exists as relatively pure SiO2 in huge deposits of quartzite or
quartz sand. In addition many rock species contain quartz crystals. As long as pure SiO2 is
available, it will be the favoured source of silicon. SiO2 can be upgraded from quartz-
containing rock species and even extraction from silicates is possible without increasing the
energy cost of silicon drastically. Therefore it can safely be concluded that the resources of
silicon such as quartz and silicates are virtually unlimited.
The resources of reduction materials are more limited. The main source is coal that can be
used either directly or as a char after heating. The specification of the product composition
limits the number of coal types that can be used. The process requires a certain reactivity of
the carbon material, which further reduces the number of available types of coal. Petroleum
coke from the oil industry is normally very pure, but the reactivity is too low for the
application of more than a small percentage. However, renewable materials, such as charcoal
can replace fossil carbon. This is more expensive and hardly competitive today as the only
carbon sources in the industrial countries, but it is a potential long term solution to the
problem.
 Silicon production is dependent on electric energy. A change in the global energy use or the
energy price may effect silicon production. In recent years there has been a change in silicon
production away from countries such as Japan and United Kingdom to countries with lower
electric power costs.

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