ZONE

REFINING
 INTRODUCTION

• Zone melting is a technique for purification by melt

crystallization developed in the early 1950s at

Bell Telephone
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INTRODUCTION

Zone melting also known as Zone refining can

purification
be appliedtoofthe
almost every type of substance that can be
melted and solidified, eg, elements, organic compounds, and
inorganic compounds. Because the solid–liquid phase
equilibria are not favorable for all impurities, zone refining
often is combined with other techniques to achieve ultrahigh
The high cost of zone refining has thus far limited its
purity.
application to laboratory reagents and valuable chemicals
such as electronic materials. The cost arises primarily from
the low processing rates, handling, and high energy
consumption owing to the large temperature gradients needed.
Zone refining is the most important of the zone-melting
techniques. In zone refining, a solid is refined by passing a
number of molten zones through it in one direction.
Each zone carries a fraction of the impurities to the end of the
solid charge, thereby purifying the remainder.
ZONE MELTING
Zone refining refers to the method of purifying a crystal wherein a thin
region of the crystal undergoes melting. This ‘molten zone’ is now moved
across the crystal.
The impurities in the metal are melted at the forward edge by the molten
zone and move through the block of metal, leaving the solidified pure
element behind.
As they move through the block of metal, the impurities in the metal are
concentrated in the melt and are transported to one end of the metal
block. 
 PRINCIPLE

• The principle of zone refining is that the impurities in an

ingot or ore of metal are more soluble in the melt state
when compared to the corresponding solid state of the
impurities.
• In the zone refining process, the impurities are
concentrated at one end of the block of metal so that
the rest of the block is purified. It can be noted that the
segregation coefficient (which is defined as the ratio of
impurity in the solid state to the impurity in the liquid or
melt state) is generally less than 1.
• This implies that when the conditions are set at the solid-
liquid boundary, the atoms of the impurity tend to
diffuse into the liquid region.
 PROCESS

• In the zone refining process, a circular mobile heater is fixed at

one end of the metal rod which is made up of the impure metal.
Now, the circular mobile heater is moved slowly across the metal
rod.
• The metallic impurities melt at the temporary position of this heater.
The melt containing the impurities moves forward along with the
heater through the entirety of the metal rod. The pure metal is left
to solidify as the heater moves along the rod.
• As the heater moves forward, the concentration of the impurities
in the melt increases. This is because the impurities are more
soluble in their corresponding melt state. Finally, the impurities are
accumulated at one end of the metal rod.
• The process described above is repeated many times in the same
direction. The end of the rod in which the impurities have now
accumulated in is cut off, leaving behind the pure metal.
 ZONE MELTING
• With subsequent zone passes, becom increasin
back-mixing significant. es gly

• The number of zone passes required to approach the ultimate

distribution is about twice the number of zone masses in the
rod for small effective distribution coefficients. Thus, longer
zones permit the attainment of the ultimate distribution
sooner. On the other hand, the attainable separation increases
as the zone size becomes smaller (permitting less back-mixing).
 ZONE MELTING
• As the zone-travel rate is increased,
a breakdown of the freezing
interface from smooth to dendritic
is eventually observed. Dendrites
are treelike structures that trap
melt and dramatically reduce
separation. The onset of interface
breakdown is predicted by the
elementary theory of
• constitutional supercooling.
k< 1 causes impurity to accumulate
in the melt at the freezing interface,
thereby lowering the freezing
actual temperature
point. Thus, the may be
melting
below point
the for some distance
into the melt, even though the two
are identical at the freezing
interface. This is known as
constitutional supercooling
because it is brought about by a Constitutional supercooling. (a) impurity
change in constitution or concentration profile during solidification; (b)
actual temperature T and equilibrium freezing
composition
 FLOAT ZONE MELTING
• Zone refining with electrical heating
coils did not work for substance like
silicon which melts at high
temperature (1415°C).

• Beginning in 1952, Bell Labs chemist

Henry Theurer developed a
variation on this technique called
float-zone refining in which a rod of
silicon clamped at both ends passes
vertically through a heating coil.
The small molten segment remains
fixed in place between the solid
portions of the rod due to surface
tension. Using steam refining to
remove the most stubborn
impurities, such as boron, he
produced silicon with impurity
levels below one part per billion in
early 1955. The process was
developed independently at two
other laboratories; by
P. H. Keck and M. J. E. Golay, at the U.
 STIRRING
• For maximum purification, the zone should move as slowly as
possible, the sample should be many zone lengths long, the melt
should be stirred, and more zone passes should be made than several
times the number.

• Stirring is essential to maximize the rate of purification, and the

travel rate V should be adjusted in such a way that δV/D ≈ 1

• Stirring increases optimal zone travel rate by lowering film thickness

and aids significantly in removal of foreign particles.

• Stirring can be done by rotating the tube along its axis. Vigorous
stirring can be provided when the crucible is spun rapidly, suddenly
stopped, spun rapidly, etc

• Induction heating also causes vigorous convection because of the

spatially varying average force field imposed along the melt surface.

• transverse rotating magnetic field or passage of electric current

 CONTAINERS
• Ideal containers for zone melting should not contaminate the melt nor be
• damaged by the melt. Containers for different substances:-
• For organic materials: borosilicate glasses, metals, fluorocarbon, and other
polymers.
• For metals and semiconductors: fused silica is ideal.
• sometimes the substance sticks to glass and causes break. This is prevented
by coating the inside of vessel with film of carbon, deposited by passing
acetone vapor through glass tube at 700 C. but at high temperature such
coating may result in contamination with carbon or silicon.

• For metals like Al with high free energy oxidation: it reacts with silica glass, so
use oxide container of higher free energy of formation like alumina, zirconia
and boron nitride.
• high melting inorganic salts: treated in noble metal containers like platinum,
rhodium, and irridium. Also refractory containers like graphite, molybdenum,
tungsten have been used.
• Low melting salts: fused
silica.
• Container shape: tube, horizontal boat, horizontal boat with a tilt.
• horizontal boat with tilt reduces back mixing in subsequent passes and is
not feasible if substance is volatile.