Energy Conversion and Management 43 (2002) 1773–1789

www.elsevier.com/locate/enconman

Freezing phenomena in ice–water systems

M. Akyurt a,b,*, G. Zaki a,b, B. Habeebullah a,b
a
Fakieh Center for Applied Research, P.O. Box 6297, Makkah Al-Mukarramah, Saudi Arabia
b
Department of Mechanical Engineering, College of Engineering, King Abdulaziz University, P.O. Box 80204,
Jeddah 21589, Saudi Arabia
Received 20 March 2001; accepted 6 July 2001

Abstract
The characteristics of solidification and melting are reviewed. The properties of water and ice and the
phase diagram of water are discussed with special emphasis on ice density. A concise account of the freezing
process and the Stefan problem is presented. To this end, the four stages of freezing are identified, su-
percooling, nucleation and the formation of dendritic ice, the growth of concentric rings of solid ice at 0 °C
and the final cooling of the solid ice are treated in some detail. The subject of bursting of pipes is given
particular emphasis. Attention is drawn to a common misconception on pipe bursting and to misleading
relationships for the computation of freezing time for ice blockage. Several current applications of melting
and freezing systems are outlined. Ó 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Blockage; Bursting; Dendrite; Density; Freezing; Ice; Supercooling; Water

1. Introduction

Problems involving the solidification or melting of materials are of considerable importance in

many technical fields. Typical examples are the making of ice, the freezing of foods and the so-
lidification and melting of metals in casting processes. In geology, the solidification rate of the
earth has been used to estimate the age of our planet [24]. Whatever the field of application, the
problem of central interest is the rate at which solidification or melting occurs.
Ice, the frozen form of liquid water, is abundant on the earth’s surface. If all the ice presently
existing on earth melted, the sea level would rise about 70 m [13]. The subject of the freezing

*
Corresponding author. Address: Department of Mechanical Engineering, College of Engineering, King Abdulaziz
University, P.O. Box 80204, Jeddah 21589, Saudi Arabia. Fax: +966-2-695-2193.
E-mail address: akyurt99@hotmail.com (M. Akyurt).

0196-8904/02/$ - see front matter Ó 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 9 6 - 8 9 0 4 ( 0 1 ) 0 0 1 2 9 - 7
1774 M. Akyurt et al. / Energy Conversion and Management 43 (2002) 1773–1789

phenomena in ice–water systems is of considerable interest to industry. These include activities

relating to the development of natural resources in arctic regions, ice formation in industrial
plants, technologies involving the manufacture of crystals in space for semiconductors and
computer chips, atmospheric physics and geophysics [8]. Other practical situations that involve
the formation of ice may be cited as the formation and accumulation of ice on wings of aircraft,
melting of snow and frost formation, solidification and melting of solutions, frazzle ice, ground
freezing and frost heave and atmospheric and marine icing of structures.

2. The phase diagram of ice

A complex interplay of molecular forces causes water to behave in a curious way when it is
frozen into ice. Most substances become more dense as they are cooled, and they are more dense
in the frozen state than when liquid. However, when water is cooled below þ4 °C, it begins to
expand, such that when water freezes, it becomes less dense than water. This is why ice floats. This
phenomenon is particularly fortunate for us on this planet, for if ice did not float in liquid water,
then the icebergs in the arctic and antarctic regions would sink to the bottom and would never
melt. They would simply freeze over and keep expanding until the oceans became solid ice [10,26].
Ice crystals may have a number of structures. All of the natural ice on earth is in the form of
hexagonal ice, called ice Ih, as manifested in six cornered snow flakes. At lower temperatures and
at pressures above 2 kbar, many other ice structures may exist. Fig. 1(a) [13,20] shows a phase
(equilibrium) diagram for water. The vertical axis in this diagram shows the temperature in °C,

Fig. 1. The phase diagram of (a) ice and (b) water.

 M. Akyurt et al. / Energy Conversion and Management 43 (2002) 1773–1789 1775

and the horizontal axis is pressure, expressed in GPa. Noting that 1 GPa ¼ 10,000 bars, it is
realized that the pressures shown in Fig. 1(a) are enormous by common engineering standards.
No other known substance exhibits such a variety of forms, as depicted in Fig. 1(a) to exist for
ice. The phase diagram of ice shows the conditions of stability for the ice phases. The equilibrium
line between water and ice Ih has a negative slope, which is a consequence of the solid having a
lower density than the liquid, unlike most other substances and the higher pressure ice phases. The
equilibrium lines extend as metastable phase boundaries into the area of stability of other ice
phases. It is noteworthy to mention that although there are 11 crystalline forms of ice, most of
which are shown in Fig. 1(a), only the hexagonal form, known as ice Ih, is found naturally on
earth.
With reference to Fig. 1(a), it is observed that the first tick mark on the horizontal axis cor-
responds to 2000 bars. The implication then is that only a thin slice of the diagram, shown en-
larged in Fig. 1(b), is of practical importance. Referring now to Fig. 1(b), liquid water at zero
gauge pressure will turn into ice Ih at about 0 °C. If the pressure is increased to about 600 bars,
which would normally be referred to as ‘‘high pressure’’, ice would not form at 0 °C, instead the
water needs to be cooled to about 4 °C before Ih can be obtained.

3. Other properties of ice

Ice is transparent to visible light. It has the lowest index of refraction for the sodium D line of
any known crystalline material. Ice is also a viscoelastic material with a nonlinear flow law. When
shear stress is applied to a single crystal of ice, it undergoes plastic shear strain easily, parallel to
the basal plane. In other directions, the stress needed to produce plastic shear deformation is
much higher. When polycrystalline ice is subjected to stress, it immediately deforms elastically,
followed by transient creep, and finally steady viscous flow, called secondary creep, is reached
[22,34].
The surface of ice Ih shows unique properties. Near the melting point, the surface contains
many dangling broken bonds that promote the existence of a liquid-like layer. Consequences of
the surface properties are sintering of snow to cohesive snowballs, re-crystallization of snow to
firn and its transformation to glacier ice and the low friction of many materials on ice, which is
useful for sled riding, skiing and skating. Regelation is a unique ice property: melting of ice under
pressure, coupled with adjacent refreezing of melt water at lower pressure, is the mechanism by
which a loop of wire can be pulled slowly through an ice block without cutting the block in two
[29].
The density of ice Ih is 0.917 Mg/m3 at 0 °C. Ice density increases in other phases of ice, as
outlined in Table 1 [22] for a temperature of 110 K. The latter phases occur under much higher
pressures. Some other relevant physical properties of ice Ih, also reported by Kamb [22], are
summarized in Table 2. Of these, it may be pointed out as particularly pertinent, that the thermal
conductivity of ice is 2.2 W m1 K1 . When compared with the thermal conductivities of mild steel
(45.5), aluminum (201) and glass wool (0.05), all in W m1 K1 [24], it may be concluded that
perhaps it would be more correct to classify ice as an insulator than a conductor.
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Table 1
Variation of density of ice with phase at 110 K [22]
Phase of ice Density (Mg/m3 )
Ih 0.93
II 1.18
III 1.15
IV 1.27
V 1.24
VI 1.33
VII 1.56
VIII 1.56
IX 1.16
X 2.51

Table 2
Physical properties of ice Ih at 0 °C [22]
Density 0.917 Mg/m3
Adiabatic compressibility 0.119 GPa1
Isothermal compressibility 0.33 GPa1
Melting point 273.15 K
Melting point depression 74 K/GPa
Specific heat 2.01 kJ kg1 K1
Heat of melting 334 kJ/kg
Thermal conductivity 2.2 W m1 K1
Linear expansion coefficient 106 /K
Cubical expansion coefficient 106 /K
Vapor pressure 610.7 Pa

Ice can be considered to be brittle, since it fractures with rapid application of stress, as when
impacted by an ice pick. It fails by brittle fracture, starting with the formation of voids between
crystals.

4. The freezing process

To briefly review the physico-chemical processes that occur during a freezing process, reference
is made to Fig. 2 [2], which shows the time–temperature relationship for freezing of pure water
(ABCDE) and aqueous solutions (AB0 C0 D0 E0 ). The first thermal event that can be seen from the
figure is undercooling, also called supercooling, below the freezing point Tf , which is equal to the
melting point Tm , before the induction of crystallization, from A to B or B0 . This is a nonequi-
librium, metastable state, which is analogous to an activation energy necessary for the nucleation
process. Pure water can be undercooled by several degrees before the nucleation phenomenon
begins.
Once the critical mass of nuclei is reached, the system nucleates at point B or B0 in the figure and
releases its latent heat faster than the heat that is being removed from the system. In aqueous
 M. Akyurt et al. / Energy Conversion and Management 43 (2002) 1773–1789 1777

Fig. 2. The process of crystallization of water [2].

solutions, however, B0 is not as low as B, since the added solute will promote heterogeneous
nucleation, thereby accelerating the nucleation process. The temperature increases essentially
instantly to the initial freezing temperature, Tf , of the solution at point C or C0 . The presence of
solutes results in depression of the freezing point based on Raoult’s Law, which relates the vapor
pressure of the solution to that of the pure solvent based on solute concentration. Note that C0 is
not as high as C, because the initial freezing point is depressed as a result of the solute. Hence, the
solute has greatly decreased the amount of undercooling for two reasons: faster nucleation and
lowered freezing point. In very concentrated solutions, it is sometimes even difficult to induce
undercooling.
In pure water, the time line from C to D in the figure reflects the time during which crystal
growth is occurring. Fast freezing rates promote the formation of many small ice crystals during
this period. The partially frozen mixture will not cool until all of the ‘‘freezable’’ water has
crystallized, hence, the line CD occurs at nearly constant temperature. The freezing time, tf , is
defined as the time from the onset of nucleation, C, to the complete removal of latent heat at D.
After crystallization is completed, the temperature drops from D to E as sensible heat is released.
During freezing of the aqueous solution, a freeze-concentration process occurs as water freezes
out of solution in the form of pure ice crystals (C0 D0 ). This causes the freezing temperature of the
remaining solution to drop. At temperatures well below the initial freezing point, some liquid water
remains. Also, a large increase in the viscosity of the unfrozen phase occurs, thus decreasing the
diffusion properties of the system and hindering crystallization. At D0 , one of the solutes may
become supersaturated and release its latent heat of crystallization, causing a slight jump in
temperature. These points are known as eutectic points. From E0 onward, continued crystallization
of the solvent, and possibly solute, occurs, until the system is completely crystallized or solidified at
very low temperatures. It is more difficult to assign a freezing time to this process, but it is usually
taken as the time to reach some predetermined temperature below the initial freezing point.
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The grain boundaries within a polycrystalline aggregate of ice are relatively disordered and are
the first regions to liquefy with temperature, or pressure, increase. That is, the melting does not
simply occur at the surface of the aggregate, but rather at the grain boundaries.

5. Analysis of freezing and melting

The transition from one phase to the other, that is, the absorption or release of the latent heat,
occurs at some temperature at which the stability of one phase breaks down in favor of the other
according to the available energy. Most thermophysical properties of a given substance, which
usually vary smoothly with temperature, undergo more or less sudden changes at the freezing
temperature Tf (Fig. 2). For example, the heat capacity of aluminum changes by 11% at its melt
temperature of 659 °C. However, the most fundamental and pronounced effects are due to
changes in density. Typical density changes upon freezing or melting are in the range of 5–10% but
can be as high as 30% [6].
For most materials, the solid is denser than the liquid, resulting in possible formation of voids
during freezing, as in casting, or breaking of the container during melting. Water, on the other
hand, expands on freezing, resulting in broken pipes on cold days and ice floating instead of filling
the bottom of the oceans. The density variation with temperature induces flow by natural con-
vection in the presence of gravity, rapidly equalizing the temperature in the liquid and greatly
affecting heat transfer.
Melting and freezing types of problems are called Stefan-type problems, after J. Stefan, who in
the 19th century formulated the problem of finding the temperature distribution and freezing-
front history of a solidifying slab of water. This type of problem is clearly nonlinear. It is generally
denoted as a ‘‘moving boundary problem’’. Kreith [24] discussed the freezing of a slab of ice on
the surface of a pool of water when the upper surface of the slab is exposed to air at a subfreezing
temperature. He observed that ice formation occurs progressively at the solid–liquid interface as a
result of heat transfer through the ice layer to the cold air. Heat flows by convection from the
water to the ice, by conduction through the ice and by convection to the sink. The ice layer is
subcooled except for the interface in contact with the liquid, which is at the freezing point. A
portion of the heat transferred to the sink is used to cool the liquid at the interface to the freezing
point and to remove its latent heat of solidification. The other portion serves to subcool the ice.
The author proposed that the freezing of a slab can be formulated as a boundary value problem
in which the governing equation is the general conduction equation for the solid phase

o2 T 1 oT
¼
ox2 a oh
where T ¼ temperature, x ¼ thickness of slab, a ¼ thermal diffusivity of the solid phase, and
h ¼ time.
The author perceived that the analytic solution of this problem is very difficult, and that it has
only been obtained for special cases. The reason for the difficulty is that the governing equation is
a partial–differential equation for which particular solutions are unknown when physically real-
istic boundary conditions are imposed.
 M. Akyurt et al. / Energy Conversion and Management 43 (2002) 1773–1789 1779

Approximate solutions to the equation can be obtained by imposing simplifying assumptions.

The simplifying assumptions that have been used by various workers include, among others, (a)
considering the heat capacity of the subcooled solid phase as negligible relative to the latent heat
of solidification and (b) assuming that the physical properties of the ice, such as density and
thermal conductivity, are uniform during the process. It must be emphasized at this point that the
constancy of density assumption is a gross over simplification for water, since there is a consid-
erable change in density during freezing (Table 2). Likewise, the assumption of uniform thermal
conductivity during freezing totally ignores the existence of dendritic ice formation, as explained
below.
Employing strategies similar to that summarized by Kreith, Ingersoll and Zobel [21] presented
an approximate solution for slab-ice formation on the surface of the liquid at the freezing tem-
perature, with the free surface temperature constant. Perkeris and Slichter [30] derived an ap-
proximate solution for the rate of ice formation on the outside of a cylinder for liquid at the
freezing point and infinite surface conductance at the inside cylinder surface. In this solution, the
inside surface temperature may be any function of time. Elmer [12] derived a similar expression
for the rate of ice formation on submerged pipes. Other more exact solutions for slab-ice for-
mation are of considerable complexity and limited to a constant free surface temperature.
A general approximate method for the solution of the freezing problem was presented by
London and Seban [27], with applications to ice formation at spherical, cylindrical and plane
boundaries. The results of the analysis were indicated to be of satisfactory accuracy for the so-
lution of engineering problems. The authors reported that utilization of the analytical results in
the prediction of freezing times for actual systems produced good agreement with quoted per-
formance.

5.1. Supercooling

Most solids are crystalline, meaning that their particles (atoms, molecules, or ions) are arranged
in a repetitive lattice structure extending over significant distances in atomic terms. Since for-
mation of a crystal may require the movement of atoms into the solid lattice structure, it may well
happen that the temperature of the material is reduced below the melt temperature (Tf line in
Fig. 2) without formation of the solid. Thus, supercooled (or undercooled) liquid, that is, liquid at
temperatures below the Tf , may appear. Such a state is thermodynamically metastable [7,32,33]. It
is to be noted that melting requires no such structuring, possibly explaining why superheating is
rarely observed [9].
Fig. 2 essentially shows the temperature of a given liquid as a function of time, as heat is ex-
tracted from the liquid at a constant rate. Note that for the supercooling of pure water, the
temperature rapidly rises back to the melt temperature Tf when crystallization does take place.
This can occur only if the latent heat released upon freezing is sufficient to raise the temperature to
Tf , i.e. the liquid was not cooled too much. Liquid that is cooled to a temperature so low that the
latent heat is not sufficient to raise its temperature to Tf is referred to as being hypercooled.
Fig. 3 [18] illustrates several stages in the freezing process inside a pipe filled with water. Thus
when a water pipe is exposed to subfreezing temperatures, heat is transferred from the water,
through the pipe wall and any insulation layers, to the subfreezing air. The temperature of the
water begins to fall in a steep decline. This is stage 1 of the freezing process. Remarkably, the
1780 M. Akyurt et al. / Energy Conversion and Management 43 (2002) 1773–1789

Fig. 3. Stages of freezing of water in a pipe that is cooled from the outside [18].

water in the pipe does not immediately begin to freeze when it reaches the phase change tem-
perature of 0 °C, but continues to fall and approach the temperature of the surrounding air. This
is a demonstration of supercooling. It is possible for water in a pipe to supercool for a considerable
length of time before any ice forms [18]. The pipe contains only water during stage 1. The tem-
perature at which ice begins to form is known as the ice nucleation temperature. The term nu-
cleation implies a starting point, or a nucleus, for ice formation.
Fig. 4 presents data, obtained by the same researcher, from a four day period when the outdoor
temperature (Tcod ) was below freezing, both day and night, throughout the period. This cold spell
produced an uninterrupted subfreezing temperature in the insulated pipe. Despite the prolonged

Fig. 4. Prolonged supercooling in a water pipe exposed to freezing temperatures [18].

 M. Akyurt et al. / Energy Conversion and Management 43 (2002) 1773–1789 1781

cold spell, ice formation did not occur for the first three days of the four day period. That is, the
pipe underwent supercooling for those three days. During field tests of the same study, super-
cooling was seen to last for up to 80 hours at a time.

5.2. Formation of dendritic ice

In general, the phase transition region where solid and liquid coexist is called the interface. The
thickness of the interface may vary from a few Angstroms to a few centimeters [6], and its mi-
crostructure may be very complex, depending on several factors. These factors include the ma-
terial itself, the rate of cooling, the temperature gradient in the liquid and surface tension. For
most pure materials solidifying under ordinary freezing conditions at a fixed Tf , the interface
appears (locally) planar, and it is of negligible thickness. Thus, it may be thought of as a ‘‘sharp
front,’’ a surface separating solid from liquid at temperature Tf .
The local freezing temperature at a curved solid surface facing the liquid becomes depressed by
an amount depending on the solid–liquid surface tension and the local curvature [31]. This so-
called Gibbs–Thomson effect is small for the overall freezing process but crucial for the resulting
microstructure of the interface [19,25].
When supercooling is present, the phase transition region may have a distinct thickness. This
region may be referred to as a ‘‘mushy zone’’. The microstructure of the material in this zone may
appear to be dendritic, columnar or amorphous, as depicted schematically in Fig. 5, where S and
L refer to solid and liquid, respectively.
It is universally accepted that the phase transition region for water, where solid ice and liquid
water coexist, is characterized by dendritic ice. It is also interesting to note however, that the
totality of the proposed theoretical solutions to the moving boundary (Stefan) problem of ice
formation that were referred to earlier in the discussion, without exception, neglect the presence of
the dendritic zone. The result is that theoretical predictions do not agree with reality in many
instances. Thus, Gilpin [15] remarked that the usual calculations of the time required for a pipe to
become blocked by ice, including those in the ASHRAE handbook [1], are greatly in error because
they are based on the assumption that the ice would grow inward from the pipe walls as a solid
annulus. This and similar engineering references are negligent in not considering that dendritic ice
can form during freezing. The term blocking is used to express the condition in a pipe when

Fig. 5. Common interfacial morphologies [6].

1782 M. Akyurt et al. / Energy Conversion and Management 43 (2002) 1773–1789

sufficient resistance is built up in a pipe such that the water supply will be totally interrupted under
normal residential pump pressures.
In another related study, Gilpin [16] found that stagnant water in a pipe will undergo a sub-
stantial supercooling before ice nucleation occurs. Dorsey [11] observed that for normal tap water,
the nucleation temperature is usually 4–6 °C below freezing. Knight [23] noted that the phe-
nomenon of supercooling is significant because the ice that grows into supercooled water does not
form as a solid layer of ice, which is the form of ice normally observed. Instead, it grows as
dendritic ice, which consists of thin plate-like crystals of ice interspersed in the water.
Gilpin reported that the quantity of dendritic ice that forms in supercooled water is directly
proportional to the amount of supercooling [16]. The nucleation temperature seems to be inde-
pendent of the material of the container as well as the rate of cooling of the water [20]. Only after
the dendritic growth phase is complete is the normally assumed solid annulus of ice initiated and
begins to grow radially inward from the pipe wall.
Fig. 6 demonstrates the distinct stages observed in the growth of ice in a horizontal 150 mm ID
water pipe that was placed in a cold chamber [15]. Fig. 6(a) shows the cross-section of the pipe
containing water that was supercooled to 3 °C just before ice growth was nucleated. Figs. 6(b)–
(d) display the growth of ice dendrites from the nucleation center near the top of the cylinder.
Note that the cross-section has been completely blocked by the dendritics in Fig. 6(e). The total
time required for this dendritic ice growth phase to be completed was only about 30 s. At the end
of this phase, the temperature of the remaining fluid in the pipe returned (rose) to 0 °C. The
author observed that there was no more dendritic ice growth after the water temperature returned
to 0 °C. An annulus of solid ice then began to grow inward, at a very slow pace, from the inside
wall of the pipe. The photographs of Figs. 6(e) and (f) were taken 3 h and 18 h, respectively, after
completion of the dendritic ice phase.
Gilpin later observed that the possibility of dendritic ice formation is an influential factor in the
case of a pipe containing quiescent water. This is because dendritic ice can cause a blockage of the
pipe in as little as 5% of the time required for an annular ring of ice to grow from the pipe wall to
the center of the pipe to block the pipe [17].
Gilpin [15] made an interesting discovery during these tests. He found that ice growth in the
supercooled pipe can be initiated at any desired supercooling by striking the end of the pipe with
a sharp blow. In all cases, the onset of nucleation and ice growth in the pipe could be detected by
a rapid rise to 0 °C of the temperature of the pipe wall. Once initiated, the ice growth spread, in a
few minutes, from the nucleation point throughout the pipe.
While investigating the effect of nucleation temperature on the formation of dendritic ice,
Gilpin [17] conducted a series of tests on a 10 mm ID steel water pipe of 30 m length. During these
tests an artificial nucleating agent was utilized. To this end, approximately 5 g of silver iodide (in a
fine powder form) was placed at the entrance of the precooled but empty pipe. When water was
introduced into the pipe, it was found that complete blockage of the pipe occurred due to the
formation of dendritic ice, at a temperature of 2 °C. The author further noted that only an
extremely small amount of nucleating agent was required to control the nucleation temperature.
After the original introduction of 5 g of the material into the pipe, it remained effective even after
several dozen pipe start-ups and several hundred gallons of water had passed through the pipe.
The nucleation temperature only returned to its previous value after several treatments with dilute
nitric acid.
 M. Akyurt et al. / Energy Conversion and Management 43 (2002) 1773–1789 1783

Fig. 6. The growth of ice inside a horizontal pipe [15].

A further conclusion that follows from the experiments and observations of Gilpin is that if the
temperature at the center of a cylindrical container is 2 °C or less at the time of nucleation, then
1784 M. Akyurt et al. / Energy Conversion and Management 43 (2002) 1773–1789

complete blockage of the cylinder by dendritic ice can be expected [16]. As may be anticipated, the
author also concluded that small diameter pipes are much more likely to be blocked by dendritic
ice than large pipes, and that copper pipes were much more susceptible to dendritic ice blockage
than plastic pipes.

5.3. Bursting of pipes

Damage from burst residential water pipes as a result of freezing is widespread and costly. The
Insurance Institute for Property Loss Reduction estimates that the cost of insured freeze related
losses over the past decade exceeds $4 billion [3] in the US. The problem is particularly acute in
locations where generally warm winter temperatures encourage builders to employ building
practices that are inadequate to protect water pipes from occasional severe subfreezing temper-
atures.
Recent research [18] has verified that the commonly held view that pipes burst when ice growth
simply pushes against pipe walls is not correct. Pipe bursting actually occurs when freezing
temperatures give rise to a solid plug of concentric ice that forms inside a pipe such that this plug
grows into a confined zone of water. Experiments conducted by Gordon [18] also demonstrated
that a mere blockage of water flow by dendritic ice does not constitute a firm enough pressure seal
to cause pipe rupture. Such a blockage can, however, cause stoppage of the flow of water in water
mains due to the build up of excessive flow resistance due to dendritic ice formation.
When concentric rings of solid ice are allowed to grow into solid plugs of ice inside pipes,
dangerously high pressures can be generated in confined volumes of water, resulting in the
fracturing of the wall of the container and the release of the pressure by forcing some of the water
through the cracks. Bursting of pipes can be prevented or delayed by insulating the pipes and by
providing air chambers to accommodate elevated pressures due to freezing. By the same token,
provision of pressure relief fixtures on the pipe would help avoid pipe ruptures, although such
fixtures are not currently available.
With reference to Fig. 3, freeze events within a water pipe can be subdivided into four distinct
stages. The first stage is that of initial cooling through supercooling. Then comes the brief stage of
nucleation and dendritic ice formation. The third stage is that of annular ice formation, and the
fourth stage is that of final cooling of the solid plug of ice to ambient temperature.
At some point below 0 °C, at the end of the first stage of the freezing process, ice nucleation
occurs and ice crystals begin to form in the supercooled water. This initiates the second stage, the
formation of dendritic ice. Dendritic ice is made up of thin, plate-like, feathery crystals inter-
spersed with the water. As the dendritic ice forms, the heat of fusion from the ice formation is
absorbed by the supercooled water, raising the temperature of the water. When the water has
returned to the phase change temperature, 0 °C, the formation of dendritic ice is complete. The
formation of dendritic ice occurs quickly and appears on the graphs as a sudden rise in tem-
perature. Using clear PVC pipes, dendritic ice formation was observed to be completed within
30–60 s of the onset of nucleation [18]. Gilpin [14–17] showed that the volume fraction of (den-
dritic) ice is around 2% of the total volume of water for shallow supercooling to about 2.5 °C.
Dendritic ice forms up to 6% of the total volume, however, for longer supercooling in the 4 to
5 °C range.
 M. Akyurt et al. / Energy Conversion and Management 43 (2002) 1773–1789 1785

When the water in a pipe has completed dendritic ice formation and returned to 0 °C, the
third stage, the growth of annular ice, begins (the constant temperature region in Fig. 3, at or
near 0 °C). Annular ice is the familiar, dense form of ice, and it grows from the outside walls of
the pipe inward. It is during annular ice growth that the remaining 94–98% of the water turns
into ice. The existing dendritic ice is incorporated into the denser annular ice. During this phase,
the pipe that is freezing will remain at phase change temperature until all of the water has turned
into ice.
When all of the water in the pipe has frozen, the pipe starts to cool below the phase change
temperature and eventually approaches the temperature of its environment. This is the region of
falling temperatures at the tail of the constant temperature zone in Fig. 3. This is the fourth stage
in the freezing process. In stage four, the pipe no longer contains water; it is blocked completely
by a solid plug of ice. The solid plug of ice in a pipe will remain in equilibrium with its envi-
ronment until the temperature of the ambient air rises above the phase change temperature. If this
occurs, then the freezing process reverses, and the pipe goes through much the same process, less
the dendritic ice growth stage. Again, there is an extensive phase change stage as the pipe thaws,
and the ice reverts to liquid water.
One of the interesting measurements made by Gordon [18] is depicted in Fig. 7. This figure
shows the variation with time of the temperatures at four points along a pipe that was exposed
to cold ambient air. The same figure describes also the variation of pressure inside the pipe with
time (right-hand ordinate). The usual initial stage of supercooling is observed at the begin-
ning of the experiment. The water is observed to supercool for well over an hour, and then the
brief second stage, i.e. dendritic ice formation, commences at about 1:00 A.M. Annular ice
formation (stage 3) begins immediately afterwards. As the outdoor temperature continues to fall
throughout the night and into the morning, annular ice formation continues throughout the
night.
There is no noticeable pressure variation during the early phases of ice formation. The
pressure inside the pipe stays exactly where it began, at the typical water pressure of the water
system (around 42 psi ¼ 2:9 bars at the test site). Only at 3:30 A.M., when ice formation is
complete at the west end of the pipe (the top three curves), does the pressure within the pipe start
to increase. In fact, it grows dramatically, ultimately leading to a burst event. The pressure in the

Fig. 7. Temperatures and pressures during pipe bursting [18].

1786 M. Akyurt et al. / Energy Conversion and Management 43 (2002) 1773–1789

pipe peaks at about 4000 psi (270 bars), and then it eases down to about 3500 psi (240 bars),
while the diameter of the pipe undergoes plastic deformation under the influence of the imposed
internal pressure. The actual rupture in the wall of the pipe occurs at about 7:15 A.M., when
liquid water is ejected through the crack, almost immediately bringing the gauge pressure down
to essentially zero psi.
It must be stressed here that bursting of pipes and containers occurs after a complete blockage
of solid ice totally isolates a body of water. A typical example is a pipe section that is trapped
between a nonleaking fuacet at one end and a solid plug of ice at the other end. Since water is
essentially incompressible, any further ice growth from the end with ice blockage will result in
spectacular increases in water pressure. Thus, if ice continues to form in the confined pipe section,
the volumetric expansion from freezing results in rapidly increasing water pressure between the
blockage and the closed outlet and causes bursting and other failures. Because the entire pipe
section downstream of the ice blockage experiences the same elevated pressures, the failure can
occur at any point in the system, and the weakest link will be found. Besides pipes themselves,
failures involving solder joints, elbows and fixtures themselves can also occur. Ironically, because
burst events arise from water pressure and not from the ice itself, failures often occur in a part of
the pipe section where almost no ice has formed, even within the heated space of a building.
Examination of a burst pipe shows that a sizable ‘‘bulge’’ in the pipe wall appears at the point of
the rupture. Once the bulge is created, the pipe is subject to rupture at the location of the thinner
pipe wall on the bulge.
It may be pointed out that a burst water pipe does not immediately result in the flooding of a
building. Because a complete ice blockage is necessary to create a rupture, it follows that the
rupture is initially sealed by the ice blockage from any substantial water flow. A flooding con-
dition will occur, however, when the ice blockage thaws out, and the burst location is back in
communication with the water system.
A conclusion that follows from the above observations is that let the water drip is sound advice
for avoiding pipe bursts in regions with freezing temperatures. By leaving a tap slightly open, a
build up of pressure due to the formation of ice will be prevented, and hence, the danger of a burst
will be avoided. Faucets should be left in the slightly open position, even if the upstream ice
blockage causes the dripping to stop or slow down.
While the phase change temperature of water is typically 0 °C (32 °F), the temperature at which
water freezes falls with increasing pressure for pressures up to about 2200 bars (see Fig. 1(a) and
(b)). With reference to Fig. 1(b), it may be verified that at a pressure of 320 bars, which corre-
sponds to the range of pipe burst pressures [18], the freezing point of water is reduced by about 2.4
°C. Since, when the pipe does burst, the excessive pressure in the pipe is relieved, one would expect
that the temperature of the water in the pipe would be several degrees below zero before rupture,
and that it would rise to 0 °C after the rupture.
Interestingly, the measurements of Gordon did reveal the presence of this phenomenon. Fig. 8
[18] displays the temperature graph of two pipes that burst during freezer tests. Notice the small
jumps in temperature when the bursts occurred. The temperature in pipe 1 refers to the unfrozen
water, which bounces back to 0 °C upon rupture. The temperature of pipe 2, however, is that of
the plug of ice in that pipe. During field tests conducted by the same researcher, similar tem-
perature jumps were witnessed upon bursting in those sections of pipe that still contained water at
the time of the rupture.
 M. Akyurt et al. / Energy Conversion and Management 43 (2002) 1773–1789 1787

Fig. 8. Timewise variation of temperatures in two 3/4 in. copper pipes that ruptured [18].

6. Current applications and concluding remarks

Fissuring of rocks without the use of dynamite is a well established procedure engineers employ
when working in freezing weather. They drill holes along the line of the desired fissure, and then
fill the holes with water. The expansion of the resulting ice causes the rocks to split without the
clamor of dynamite.
A more recent mode of application of freezing and thawing, aside from the commercial pro-
duction of ice and the freezing of foodstuffs, is in maintenance work. Engineers have started using
ice plugs on piping to undertake maintenance chores without having to drain piping systems.
Typically, the pipe diameters may be as large as 12 in. One such system [4] uses a bath of liquid
nitrogen to establish and lock in place a solid plug of the fluid inside the pipe. During the ap-
plication of the plug forming process, pressures and temperatures are monitored. Expansion of
water based fluids is anticipated and accommodated. Solid plugs effectively isolate work areas. It
is claimed that such plugs withstand pressures up to 8000 psig (550 bars) or 225,000 lbs (1000 kN)
of axial force [4]. Kits are commercially available for rapidly forming an ice plug in static small
diameter water lines, 3/8 to 2 1/8 in. OD, eliminating the need to drain down a system to make a
repair. Commonly, ice plugs will last 15–20 min, and they can be easily renewed. The coolant used
for such kits is CO2 .
Considering costs of downtime, labor and replacement fluids, pipe freezing is claimed to be
substantially less costly, and in many cases it amounts to a small percentage of the expense of
alternative maintenance procedures. Typical users of the technology include nuclear power plants,
industrial companies, mechanical contractors, hospitals, hotels and facilities which operate on a
24 h schedule. These facilities rely heavily on pipe isolation to establish a condition which allows
for maintenance while remaining on line. The following narration of a chain of events may be
cited as an illustrative example of working with ice plugs.

‘‘Renovations were needed to a wing of a hospital. No valves existed to isolate the wing un-
der construction from the primary building domestic water system. On Thursday, freeze
seals were formed on 6, 8 and 10 in. pipes to allow work on project #1. On Friday, a freeze
seal was formed on a 10 in. line so that a valve could be inserted as part of project #2. On
1788 M. Akyurt et al. / Energy Conversion and Management 43 (2002) 1773–1789

Saturday, with less requirement for utilities from the tenants, heating water risers were taken
out of service but not drained. A total of 14 freezes on 3/4 in. through 2 1/2 in. pipes were
required on project #3 to complete the job.’’

Yet another commercial application of freezing is ground freezing [5,28]. Ground freezing is
recognized by mining and civil engineers as undoubtedly the most effective and consistently re-
liable method of providing temporary support and of preventing groundwater from flowing into
deep excavations. Its use has numerous benefits, including the fact that it does not deplete aquifer
reserves by continuous pumping, nor does it pollute or alter the groundwater regime in any way,
thus eliminating any adverse affect on adjacent structures, installations and populous.
The basic principle of ground freezing is to circulate a cold medium, such as liquid nitrogen,
through a suitable pipe system, which cools the strata and, thus, converts the in situ pore water to
ice. The ice so formed bonds adjacent soil particles together and forms an impermeable structure
with increased strength characteristics. Freezing is adaptable to any shape, size or depth required.
One final remark is in order at this point. Water is abundant on earth. It possesses unusual
properties. Yet, considering how little use is currently being made of many of its properties, it may
not be an overstatement to remark that this precious resource has been hardly tapped. In a
subsequent article, the authors hope to describe some of their own efforts to try to benefit from
one of the many unusual properties of water, that of changes in its density during freezing and
thawing.

Acknowledgements

This work was initiated and sponsored by the Fakieh Center for Applied Research, Makkah
Al-Mukarramah, Saudi Arabia.

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