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Lasse Makkonen ∗
VTT Technical Research Centre of Finland, Box 1000, 02044 VTT, Espoo, Finland
Abstract
In this paper concepts and models for theoretically estimating ice adhesion are presented. The effects of
temperature, ice salinity and properties of the substrate material on ice adhesion are explained by these
theoretical concepts. Major problems caused by ice adhesion are outlined and the applications of the theory
in combating ice adhesion are discussed. Measurement methods of ice adhesion are described and results of
ice adhesion for various material surfaces are reviewed and interpreted in view of the theory. Prospects for
reducing ice adhesion to solve practical problems are discussed and the methods of anti-icing and de-icing
are summarized.
© Koninklijke Brill NV, Leiden, 2012
Keywords
Ice adhesion, interface mechanics, surface energy
1. Introduction
Figure 1. An example of the many practical problems related to ice adhesion: Mechanical ice removal
from ship’s superstructure.
Figure 2. Water drop on a solid surface and the definition of the contact angle θ .
2. Theory
2.1. The Relation between Water Contact Angle and Ice Adhesion
Consider a drop of water (w) on a solid (s) with an interface (w, s) and the cor-
responding surface energies γ and a droplet contact angle of θ . The situation is
schematically shown in Fig. 2.
The Young equation for the equilibrium of this situation reads
γw,s + γw cos θ = γs . (1)
Consider next ice (i) that is frozen on the solid (s). In Fig. 2 this would mean that
the drop is frozen into ice. We are now interested in the work that is required to
L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445 415
remove the ice, i.e., break the bond (i, s) and form two new surfaces (i and s) in
the absence of deformations. We call this the thermodynamic work of adhesion Wa
which then is defined as
Wa = γs + γi − γi,s . (2)
Considering now that the surface energies of water and ice are approximately the
same [1] and assuming that their interfacial energies at the solid interface are also
approximately the same, we obtain
Wa ≈ γw (1 + cos θ ). (4)
According to equation (4) the thermodynamic work of ice adhesion can be closely
approximated by the surface tension of water and the contact angle of water on the
material in question. This is presented graphically in Fig. 3.
Equation (4) and Fig. 3 show that, ideally, we should in ice removal expect a
deterministic dependence between the work of adhesion and the contact angle of
water. Finding a deviation from the curve in Fig. 3 in macro-scale experiments
would imply that work is spent in deformations of the materials or that the ice–
solid contact is somehow complex or incomplete. These possibilities are discussed
in the following sections.
Figure 3. Thermodynamic work of ice adhesion scaled by the surface tension of water as a function
of water contact angle θ .
416 L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445
the failure mechanism at the interface may vary with the flexibility of the interface.
On rigid surfaces, this may theoretically cause a temperature dependence of Fmax ,
so that at low ice temperature, a lower ice adhesion strength would occur. This
is indeed observed at very low temperatures, as discussed later in this paper. At
temperatures close to 0°C there appear to be other mechanisms that override the
effect of deformations. These mechanisms affect the ice–substrate interface already
prior to an attempt to remove the ice and are discussed in the following sections.
Obviously, the nominal adhesional force per unit area between ice and a substrate
is weaker when the true interface area is less than the apparent one. This is the case
when the contact is incomplete, e.g., due to minute bubbles of air at the interface.
Also, micropores of the substrate that are not filled with water due to hydrophobicity
of the substrate surface reduce the effective contact area. On the other hand, the true
contact area is larger than the apparent one when the interface includes perturba-
tions, i.e., is rough on the microscopic scale. For example, if the interface includes
micropores that are filled with water, then the true interface area is large. In such a
case, sometimes called ‘locking’ a purely adhesional failure may become impossi-
ble, and the fracture occurs partly cohesionally within the ice material. Therefore,
the adhesion strength of ice on many materials is higher on a microscopically rough
surface than on a smooth surface [6, 7].
The true interface area of the contact of water with a textured surface can be
estimated theoretically in detail. Apparently the fine details that affect the contact
angle hysteresis, such as the sharpness and spacing of the roughness elements, are
important [8, 9]. The theory can be used as guide for estimating ice adhesion when
bulk water is frozen on textured surfaces, for example those that have a ‘lotus’ or
fractal structure in order to make them super-hydrophobic [8–13]. However, these
ideas are perhaps over-optimistic because they are based on the mechanical equi-
librium between capillary forces only. In many cases of ice accretion in nature the
ice is formed from water droplets that impact the surface at a very high speed.
This involves high droplet inertia and often a high stress due to wind, so that water
droplets may penetrate and freeze into the porous structure of the material, par-
ticularly when they are smaller in diameter than the roughness element spacing.
Small droplets that are highly supercooled also freeze so quickly that they do not
re-bounce from a superhydrophobic surface.
Consequently, the adhesion strength of bulk-formed ice on textured surfaces may
be different from that of ice formed by droplet accretion and the sizes of the surface
roughness elements and the impinging droplets may affect the latter. This conclu-
sion is supported by the fact that Teflon has been found to be quite poor in reducing
adhesion of ice produced by droplet accretion [14, 15], while the adhesion strength
of bulk-formed ice on Teflon has been shown to be very low in many other studies
(Section 3).
418 L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445
Figure 4. Crystal structure of ice photographed through a polarized plate on two substrate surfaces,
concrete (above) and Teflon (below).
The size and orientation of crystals in bulk ice at an interface depend on the ma-
terial on which the ice is frozen, see Fig. 4. When ice forms due to droplet accretion
the growth conditions have an effect as well [16–19]. Generally, hydrophilic and
rough surfaces cause smaller and more randomly oriented ice crystals to form. It
has been proposed that the crystal structure at the interface would affect ice ad-
hesion. However, this is difficult to demonstrate experimentally, because materials
show different ice adhesion strengths for other reasons. Theoretically, it is not clear
why such an effect should be significant, since the surface energies of the crystal
faces of ice are not much different from each other [20].
L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445 419
materials for which γs is high. Second, it is not clear if this theory applies to the
cases where the surface energy of the solid is higher than that of ice, and if both the
dispersion and polar components need to be taken into account.
Hence, the predictive value of equation (6) is, perhaps, limited to the low energy
surfaces, such as those polymers that may have γi,s close to the value of the ice–
water interface, i.e., 29 × 10−3 J/m2 . At such interfaces, pre-melting should occur at
temperatures close to 0°C only, whereas for the polymers that have an even smaller
surface energy should involve a liquid film in a wider temperature range. This may
introduce another mechanism, in addition to the one presented in Section 2.1, which
produces a low ice adhesion at low energy surfaces.
Based on the same theory, the thickness of the liquid water layer on ice can be
estimated [1]. The theory suggests that the water film thickness at an interface of ice
decreases from infinity at 0°C to zero at 0◦ C − δT , being proportional to δT −1/3 .
Such relationship has been found also experimentally [26, 27]. More studies would
be necessary to evaluate such a nanoscale film thickness at interfaces and its relation
with ice adhesion. In any case, qualitatively, the theory predicts an increase in the
adhesion strength of ice with decreasing temperature down to the temperature at
which the liquid film disappears.
2.4.2. Interface Cracking Due to Thermal Expansion
It is noteworthy that an ice/substrate interface always forms at the freezing temper-
ature of water, i.e., 0°C for pure water. Thus, at the time of freezing there exists
no direct effect of ambient temperature on the properties of the interface. However,
since the initial ice/substrate interface is at the freezing temperature, any such inter-
face at a sub-freezing temperature must have been cooled to that temperature in a
solid state. Thermal contraction of both the ice and the substrate is always involved
in such a cooling. Obviously, this may initiate failures of the joint at the interface
and cracking of ice when the thermal expansion coefficients of the ice and the sub-
strate material are different from each other. In most cases they are quite different
as the linear thermal expansion coefficient of ice is 50 × 10−6 /°C [20], whereas that
of many other materials it is much smaller. For steel, as an example the value is
11 × 10−6 /°C. This means that the stress that arises at the interface upon simulta-
neous cooling of the ice and the substrate is mainly caused by contraction of the
ice itself. The ice and the substrate material may also cool at different rates due to
their different heat capacity and coefficient of thermal conduction, causing an addi-
tional stress at the interface. The significance of the stress depends on the cooling
rate because ice creeps. When the substrate material remains elastic down to the
temperature in question, this effect is absent.
That failure of an ice–substrate interface actually takes place by cooling only
can be demonstrated by numerical analysis. Figure 5 shows a finite element method
analysis of the shear stress caused by thermal contraction in a rapid temperature
change of 10°C in the U.S. Army Cold Regions Research and Engineering Lab-
oratory (CRREL) ice adhesion test arrangement (see Fig. 7). This analysis and
the corresponding ones for the other stress components indicate that the thermally
L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445 421
Figure 5. Finite element method analysis of the shear stress (in Pa) caused by thermal contraction in
a rapid temperature change of 10°C in the CRREL ice adhesion test arrangement (see Fig. 7).
induced stresses at the ice–substrate interface already at −10°C are higher than
the adhesional and cohesional strength of ice. Thus, in this test arrangement the
ice–substrate interface has been partly broken and/or the ice itself is damaged by
cracking already prior to the adhesion test. In experiments on ice adhesion this ef-
fect can be alleviated by letting the samples cool very slowly so that the creep of
ice partly relaxes the thermal stresses that arise.
One would expect that thermally induced failures of the ice and of the joint at the
interface will reduce the measured value of the adhesion strength. In other words,
the adhesion strength of ice should theoretically decrease with decreasing tempera-
ture due to the effect of differential thermal expansion, except for elastic materials.
This is indeed observed (see Figs 11 and 12) but only at rather low temperatures.
Apparently, the disappearance of the liquid-like layer with decreasing temperature
(Section 2.4.1) provides a more important mechanism than the thermal expansion
at temperatures close to the freezing point of water. Moreover, as long as the liquid-
422 L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445
like layer exists the interface may be ductile so that it adjusts to the thermal stresses
without fracturing.
2.5. The Effect of Water Salinity
Impurities and chemicals affect the adhesion of all materials. This general subject
will not be discussed here. However, in the case of ice adhesion, salt in sea water
requires attention due to its major role in many problems related to accretion of
ice at sea [28]. Salinity at the interface always is a factor when the ice is formed
out of sea water. The physical processes that are involved in saline ice adhesion are
discussed in the following and an attempt is made to, at least qualitatively, explain
some of the observed phenomena.
Saline ice consists of salt-free ice and the so-called brine pockets that contain
saline water. The salt concentration and relative volume of these brine pockets de-
pend on the bulk salinity and temperature of the ice [20]. The reduction in the
adhesion strength of ice caused by salt is apparently due to reduced effective solid–
solid contact area at the ice–substrate interface. It is reasonable to assume that the
adhesion strength depends linearly on the effective contact area. The effective con-
tact area can be related to the brine volume assuming some geometrical form of the
brine pockets.
Oksanen [29] used these ideas to model saline ice adhesion by adopting the ge-
ometry of brine pockets as vertically oriented cylinders. He assumed in his model
that the ice–substrate interface structure is equal to that of a vertical cut of the ice.
However, this model predicted much higher values of the adhesion strength than
observed since the portion of the brine at a plane cut area is small. It, thus, became
obvious that a liquid layer of salt solution exists at the ice–substrate interface. In-
deed, a liquid layer has been observed in adhesion tests at high salinities [30] and
its existence even in the case of very low concentrations of potassium chloride has
been confirmed [31]. The formation of this saline water layer is discussed below.
Ice freezes at its equilibrium freezing temperature, so that it must cool in the
form of ice to the temperature of the environment. During cooling, water freezes
on the walls of the brine pockets [20]. This raises the salt concentration of the
brine pockets allowing the phase equilibrium between the ice and the brine to be
maintained.
The ice that forms within the brine pockets occupies 9% greater volume than
the liquid brine. There is no evidence that this would result in significant micro-
fracturing of ice. Therefore, upon cooling, some brine is evidently forced out of the
brine pockets and must eventually be expelled out of the ice sample. As a result
of this brine expulsion, a layer of high salt concentration forms on the ice surface.
When ice is adhered to a structure and cooled, a concentrated salt layer forms at the
ice/substrate interface too, and reduces the adhesion strength.
Details of the brine expulsion process during cooling of ice are poorly known,
but the existing data indicate that the brine moves along the grain boundaries [32].
It is, therefore, likely that brine expulsion from an ice sample is not always three-
L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445 423
where Si is the salinity and Mi the mass of the ice sample. Equation (7) can be
presented as
Si (T2 )
ms (T2 ) = Mi Si (T1 ) − Si (T1 ) . (8)
Si (T1 )
Cox and Weeks [35] derived an equation for the salinity ratio Si (T2 )/Si (T1 ). When
using Zubov’s [36] relationship between brine salinity and brine density (ρb in
g/cm3 ),
ρb = 1 + 0.8Sb , (9)
where Ai is the surface area. For a cube of ice with density of ρi and wall length of
L the surface area, Ai , is 6L2 and the mass, Mi , is ρi L3 . It, therefore, follows from
equations (10), (11) and (12) that for a cube of ice with a density of 0.9 g/cm3
0.9L3 Si (T1 ) Si (T2 )
h(T2 ) = 1− . (13)
6L2 (1 + 0.8Sb (T2 ))Sb (T2 ) Si (T1 )
Inserting equation (10) into equation (13) and using the value of 0.917 g/cm3 for
ρpi gives an equation for the thickness of the liquid film on the ice surface at T2 :
0.9LSi (T1 )
h(T2 ) =
6(1 + 0.8Sb (T2 )Sb (T2 ))
Sb (T2 ) −0.0905 1 + 0.85Sb (T2 )
× 1− (14)
Sb (T1 ) 1 + 0.85Sb (T1 )
× exp 0.872(Sb (T1 ) − Sb (T2 )) .
and the final equation for the thickness of the liquid film on the ice surface at a
temperature T is
0.15
h(T ) = LSi
(1 + 0.8Sb (T ))Sb (T )
0.26Sb (T ) −0.0905 1 + 0.8Sb (T )
× 1− (18)
Si 1 + 3.077Si
× exp(3.354Si − 0.872Sb (T )) .
Here Si is the initial salinity of the ice cube and Sb (T ) is solved from equation
(15). An iterative solution for h(T ) as a function of the ultimate salinity could also
be obtained but this would not be justified because equation (17) is only an ap-
proximation. For practical purposes Si can be replaced by the measured ice salinity
in equation (18), as the difference between Si (T1 ) and Si (T2 ) is always small and
equation (18) is insensitive to these small differences.
Examples of the brine layer thickness h calculated at various temperatures and
ice salinities are given in Fig. 6 for an ice cube with L = 10 cm. According to Fig. 6,
the brine layer thickness starts to grow at a certain temperature (e.g., −4.2°C for
Figure 6. Theoretical brine layer thickness on the surface of a three-dimensionally cooled isotropic
10−3 m3 ice cube as a function of its eventual temperature. The curves are for different ice salinities.
426 L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445
54–71]. The principles of different methods have been reviewed by Sayward [72].
Many techniques exist and the size of the ice samples varies from nano-size [66,
67] to microscopic [68] to those faced in large scale applications. Test methods that
are specific to some geometry, such as the leading edge of an airfoil, have also been
developed [73].
Nano-scale experiments on ice adhesion are appealing in that many of the vari-
ables that affect macro-scale ice failure are absent. However, the true contact area
is very difficult to determine in such experiments, and they do not necessarily relate
to the practical situations of ice removal. Therefore, macro-scale ice adhesion mea-
surement methods will be discussed in the following. As an example, the U.S. Army
Cold Regions Science and Engineering Laboratory (CRREL) test arrangement is
shown in Fig. 7. As another example, the ice adhesion test method presently used
at VTT Technical Research Centre of Finland is described in more detail below.
Figure 7. CRREL cylindrical ice adhesion test arrangement (www.crrel.usace.army.mil). The joint
between the coated metal pile and ice is broken by torque.
L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445 429
Figure 8. Ice adhesion test apparatus of VTT and coating samples with ice cylinders frozen on them.
Removed ice pieces are also shown.
In the VTT test the test specimens are 100 mm × 100 mm × 10 mm aluminium
plates on which the coatings have been applied. Ice cylinders with a diameter of
30 mm are frozen on the coating at −10°C by placing a small container filled with
water on the test plate. During freezing the samples are thermally insulated on the
side on which the ice sample is frozen on the plate. Consequently, the latent heat
of freezing is mainly removed by conduction through the aluminium plate. The
purpose of this is to make the freezing front advance from the coating interface
towards the bulk water. This assists in obtaining ice with little or no air bubbles
close to the coating interface.
The ice cylinders are tested by shearing them from the plates after at least 24 h
of storage in a cold room kept at the test temperature. The test device and some
samples are shown in Fig. 8. In the tests, failure at the interface is obtained by a
shear force applied by a belt moving at a constant nominal rate of 3.2 × 10−4 m/s,
which is also measured by a laser device. The resulting force is measured by a
load cell and the force–time curve is recorded. Examples of force–time curves are
shown in Fig. 9. Due to stretching of the belt, used in delivering the force to the ice
cylinder, the increase of the force is somewhat nonlinear with time. The adhesion
strength is determined as the peak shear force divided by the interface area. For
each coating several ice samples are tested and the adhesion strength is calculated
as the mean of the results.
430 L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445
Figure 9. Example of four measurements on the same coating sample in VTT experiments. The ad-
hesion strength in terms of force is based on the mean of the four peak values. Av. force = 441 N,
pressure = 0.49 MPa.
One may evaluate the work done in an ice adhesion test of Fig. 9 by integrating
the force–time curve with respect to the displacement, as the latter is known from
the constant deflection rate applied. Such a calculation gives about 40 J/m2 for the
total work, which can be compared to typical values of about 1 J/m2 for the fracture
energy and about 0.1 J/m2 for the thermodynamic work of adhesion (Section 2.2).
Clearly, the major part of the work spent goes for the irreversible deformations in
the measurement system. This outlines that ice adhesion measurements of this type
provide the adhesion strength only and are inapplicable to determining a relevant
value for the work of adhesion.
A fundamental aspect in measuring ice adhesion is the stress distribution at the
ice–substrate interface upon loading. Ideally, the shear stress should be evenly dis-
tributed on the interface. This situation can be approached by measuring tensile
strength instead of shear strength [57, 61], by a centrifuge adhesion test [63] and by
a test method utilizing laser-pulse induced spallation in which a compressive stress
pulse travels through a substrate disk which has an ice layer grown on its front
surface [69]. However, one needs to consider not only the easiness of the theoreti-
cal interpretation of the ice adhesion measurements, but also their applicability: In
most applications ice removal involves an uneven distribution of stress at the inter-
face. In some applications ice removal in practice is done from curved surfaces and,
accordingly, such laboratory experiments have also been done [73].
In any case, it is essential to understand how the stress in distributed in different
test arrangements. The stress distribution in the basic shear ice adhesion test by
VTT, as calculated by the finite-element method, is shown in Fig. 10.
L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445 431
Figure 10. Shear stress (in Pa) in the VTT test (Fig. 8) as calculated by FEM analysis. The substrate is
at the bottom of the ice sample and the pull is from right to left. The indentation is the ice deformation
by the belt (dimensions exaggerated by a factor of 103 ).
In the VTT test the relative standard deviation of the measured ice adhesion
strength is on average 12% showing that the method provides rather repeatable
results on ice adhesion measurements. A large set of ice adhesion tests on various
materials at different temperatures were made at VTT in the 1980’s using a similar
test procedure but on a larger scale [30, 49]. In those tests the relative standard
deviation was more than in the new method suggesting that it is better to use small
samples in the testing.
Some results of the previous tests at VTT are shown in Figs 11 and 12. The
results in Fig. 11 demonstrate the theoretical predictions (Section 2.4) that the adhe-
sion strength has a maximum at some intermediate temperature. ‘Inerta 400’ which
was manufactured at the time by Teknos Oy is an exception, because it was the
only coating which remained elastic at all test temperatures, thus preventing the
brittle fracturing of the ice due to thermal contraction when cooling down to low
temperatures (see Section 2.4.2).
The results in Fig. 11 and in many other studies referenced in this paper confirm
the theoretical prediction that the materials with a large water contact angle and the
usually related low surface energy tend to have low adhesion strength with ice. In
particular, equation (4) has been verified in that it describes not only the adhesion
energy, but also the adhesion strength on polymers [71]. Experiments on nanoscale
[68] have also confirmed this prediction. There are some experimental results in
which this relationship has been less clear [70], but this is probably due to other
complicating factors causing scatter in the measurement results.
It is noteworthy that polymer surfaces have a high linear thermal expansion co-
efficient: For example the value for poly(vinylchloride) is about the same as for ice.
Following the ideas proposed in Section 2.4.2, this should produce only a small
temperature dependence at low temperatures. This is indeed observed experimen-
432 L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445
Figure 11. Effect of temperature on the ice adhesion strength in shear. Inerta 400 manufactured by
Teknos Oy was a coating that remained elastic at cold temperatures. Vellox 140 was an anti-icing
coating supplied by Clifford W. Estes Co. (USA).
tally (Fig. 11) suggesting that the ice adhesion strength of polymers is affected not
only by the surface energy but also the thermal expansion coefficient.
Figure 12 shows the temperature dependence of the ice adhesion strength for
one substrate material in more detail and also in the case of ice frozen from saline
water. It can be seen that adhesion strength in the case of saline water does not
have a maximum at an intermediate temperature but increases indefinitely. This is
in accordance with the theoretical predictions discussed in Section 2. First, the salt
causes a liquid film that makes the adhesion strength fall to a small fraction of its
value for pure water.
Second, this film makes the interface ductile enough, so that thermal expansion
when going to low temperatures does not cause a reduction in the adhesion strength.
That the adhesion strength of saline ice exceeds that of pure ice at very low tem-
L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445 433
Figure 12. Adhesion strength of ice as a function of temperature for ice formed from fresh water
and water with a 2h NaCl concentration. The substrate material Inerta 160 is an epoxy-based paint
supplied by Teknos Oy.
peratures is because salt eventually nucleates, so that the liquid film completely
disappears at the lowest temperatures.
Adhesion strength of saline ice is typically only 10–20 kPa, except at extremely
low salt concentrations and low temperatures as shown in Fig. 12. However, some-
times an order of magnitude higher values have been reported [45, 74]. The reason
for this discrepancy is probably related to the formation and disappearance of the
liquid layer at the interface. Different methods of freezing the samples, different test
arrangements and varying storage times may all affect the thickness of the liquid
film. Preferred direction of brine expulsion may also depend on crystal orientation
and brine drainage may remove the liquid film. Furthermore, brine drainage may
affect the adhesion strength more on horizontal than on vertical surfaces [44].
The adhesion strength drops to only a fraction of its value for fresh water ice
already at ice salinities below 1h. Also, it has been shown [54, 66, 75] that the
adhesion strength suddenly drops to a very small value when the temperature rises
above the eutectic point of the salt solution, and that this happens also with very low
salt concentrations. This is consistent with Fig. 12 in that the adhesion strength of
saline ice was observed to be considerably higher at −30 to −50°C than at higher
temperatures (the eutectic temperature of NaCl is −23°C).
It was found by Makkonen and Lehmus [30] that the ratio of saline ice adhesion
to fresh water ice adhesion was much higher on a rough polymer surface and on
434 L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445
Figure 13. Field testing of ice adhesion on a navigation lock wall. Samples are made by a bore and
then sheared off by a belt seen in the right hand upper corner.
a concrete surface when compared with other surfaces. It is noteworthy that these
surfaces were much more porous than the other tested surfaces. This suggests that
the liquid film is absorbed by a porous surface, thereby considerably increasing the
adhesion strength. Therefore, roughness of the surface plays a much more important
role in adhesion of saline ice than of fresh water ice.
Measurements of ice adhesion strength have been made not only in the labo-
ratory, but also in the field for naturally formed ice. This has been necessary for
investigating the feasibility of coatings and de-icing systems in practical applica-
tions. Measurements with different coating materials have been made, for example,
onboard ships and offshore structures [76–78] and on navigation lock walls [79, 80]
(Fig. 13).
L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445 435
strength low enough to solve the practical problems of ice adhesion. Furthermore,
the effectiveness of superhydrophobic nano-rough surfaces is hampered by impact
of small cloud droplets and formation of frost within the texture [90–92].
Therefore, new ideas for anti-icing coating are required and have indeed been
recently introduced as commercial products. As it is difficult to remove ice when
it has frozen on a substrate, an obvious solution would seem to be preventing the
freezing of water on a substrate surface. An obvious approach is to make the sur-
face so hydrophobic that water drops will not remain on the surface for a sufficient
time for nucleation to occur, see [9]. The other approaches are more fundamental
in that they attempt to reduce the adhesion strength of ice by surfaces that prevent
nucleation or freezing even in long-term contact. It is well known that the struc-
ture of water is modified in contact with a surface and that lowering of the freezing
temperature of water occurs at some surfaces, for example to the benefit of some
biological species [93–95]. However, theoretically, the matter is less than clear [96,
97] and the development of such new surfaces has been done mainly by experimen-
tal searching.
One idea worth developing is based on extremely low ice adhesion (less than
10 kPa) measured for an organopolysiloxane resin mixed with alkali metal com-
pound manufactured in Japan in the 1980’ [32, 65, 98]. This coating material was
manufactured by Kansai Paint Inc., but is no more on the production line. Its me-
chanical durability was rather low but it appeared not to be self-sacrificing. This
hydrophobic organopolysiloxane resin contained a small amount of polar ingredi-
ents. Lithium ions act as hydrogen bond breakers in the material. It was assumed
in [65] that the four oxygen atoms from water molecules and two oxygen atoms
present in a carboxylic residue associate together and form an octahedron coor-
dination structure. DSC analysis showed that this water does not have a definite
freezing point [65]. It is assumed by the developers of this coating that “the struc-
tural and energetic differences thereof and synergetic effect from silicone matrix
result in preventing ice adhesion”.
A second idea pursued recently at VTT and elsewhere [95, 99] is to synthesize
natural anti-freeze proteins, apply them in coatings, and rely on their ability to re-
duce the freezing point and thus affect ice adhesion. Preliminary experiments on
prototype coatings have, however, shown that once freezing occurs on these ma-
terials, the adhesion strength is high. It appears, therefore, unlikely that anti-freeze
proteins will provide solutions to practical problem of ice adhesion generally. How-
ever, they may be useful in systems that have a very small size and an undisturbed
environment. They may also have an indirect effect in reducing icing by delaying
the freezing of water.
Yet another approach is the ePaint coating which reduces the adhesion strength
of ice using several processes [86]. This coating is hydrophobic but also includes
phase-change material that is thermally activated. As the coating cools below 0°C
the epoxy-like material contracts, and the embedded solid-phase change material
expands, causing little net change in the surface area of the coating. However, as ice
L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445 437
accretes, liberated latent heat from the ice warms the coating surface. This causes
the phase-change material to warm and to expand. The simultaneous contraction of
the epoxy-like material and expansion of the phase-change material causes shear
stress within the coating and failure of the ice–substrate adhesion bond (see Sec-
tion 2.4.2).
As discussed above, the use of the present low-adhesion coatings is not very effec-
tive when used alone. However, combined with mechanical and thermal methods,
coatings and paints can make deicing easier. For example, the time needed for de-
icing a surface by heating is reduced considerably when the surface is coated with
a suitable material [100, 101]. Also, the ease of manual and automatic mechanical
ice removal is very sensitive to the strength of adhesion of the ice to the material.
As an example, polymer coatings have proved to be useful in routine service when
deicing, e.g., navigation lock walls [79].
Manual deicing has historically been the only method in combating ice, for ex-
ample at sea. The ice is removed by crew members using mallets, axes, baseball
bats, etc. (see Fig. 1). This method is unsatisfactory because conditions on a slippery
deck during severe icing are hazardous, and de-icing actions are almost impossible
when most needed. The use of motorized cutters for removing ice on a ship [102]
is usually possible only after an icing storm. It is seldom possible at any time to
manually remove ice from the upper parts of the structures most critical to ship’s
stability or from other types of tall structures on ground.
Because of these problems in manual ice removal, automatic and semiautomatic
deicing methods have been developed. The most effective of these devices is a pneu-
matic deicer, a series of tubes standing alone or built into a rubber mat called a boot.
When the boot is inflated with air it expands and breaks the ice adhered to the sur-
face. The principle is in use for protecting aircraft wings from icing [103, 104].
Pneumatic deicers have proven to be effective also on small cylindrical objects and
large flat surfaces, such as radar dishes and ship superstructure [105–107]. Disad-
vantages of this method are the cost and likelihood of damage to the deicers if used
in working areas.
More recent developments are the electro-expulsive (EESS) and electro-impul-
sive (EEIS) separation systems tested in, e.g., shipboard applications and aircraft
[81, 98, 99]. These methods utilize high repulsive forces to impart expulsive move-
ments to the flexible outer layer. The forces are generated by overlapping conduc-
tive ribbons that receive a very high instantaneous current pulse. A lightweight
retrofitable EESS system consists of a 0.5 mm thick polyurethane blanket with
embedded flexible conducting copper ribbons which are paired and separated by
a dielectric. The instantaneous power pulse is very high, but the pulse width is only
about 20 µs. Thus the energy consumption of the EESS is quite low. Test results and
shipboard applications of the EESS system are described by Embry et al. [109].
438 L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445
sources. The heat consumption of the system has been found to be about 1 kW/m2
in field tests under typical icing conditions. The heat pipe method has also been
used in deicing navigation buoys [118].
Hot water is rather effective in short-term ice prevention and is sometimes used
as a deicing method on ships [119]. A disadvantage of this method, in addition to
high heat consumption, is that water for protecting the upper parts of the structures
falls and flows along the surfaces and may increase icing at lower levels of the
vessel. Thermal and mechanical methods are combined in the so-called seawater
lance, which consists of a high-pressure jet of seawater capable of removing ice by
melting and dynamic pressure. This method has been used on navy vessels [120].
Current-conducting coatings are used for heating small surface areas, such as
automobile and aircraft windows [86]. This method works for larger surfaces too,
when combined with coatings that reduce ice adhesion. Such an approach reduces
the power consumption to a level realistic for some practical applications, such
as wind turbine blades. Detailed analysis of the heat consumption and optimized
design of a wind turbine anti-icing system has been made by Makkonen et al. [116].
The high energy consumption of thermal de-icing is not only due to melting a
sufficiently thick ice layer but due to high loss of heat as conduction to ice and the
substrate while the system is on. This is especially so when heating is applied from
the air and not from the substrate [116]. It is easy to show [117] that the conduction
loss is smaller the quicker the process, i.e., the higher the power used in the de-icing.
Based on this, methods have been developed in which a very high power is applied
directly at the interface by a heated film [121, 122]. This approach is applicable
to many problems, see http://engineering.dartmouth.edu/thayer/research/ice-engg.
html.
In some applications, even a very small amount of rough ice may cause serious
problems. These are related to aircraft wings, helicopter rotors and wind turbines
where aerodynamic penalties due to accreted ice are unacceptable. In these ap-
plications de-icing may not be enough to prevent problems; instead, anti-icing is
required. Such anti-icing systems are presently based on heating, e.g., [116].
4.4. Chemical and Electrical Methods
The application of chemicals on an icing surface to reduce ice adhesion has been
tested, mostly with limited success [102]. Moreover, these chemicals deteriorate
easily by weathering and by the accreting ice [123].
Another kind of chemical measure for preventing ice adhesion is to apply freez-
ing point depressants on surfaces. The major problems of this method are optimiz-
ing the amount of the chemicals and distributing them uniformly on the surface.
When these problems can be overcome, it is possible to reduce icing considerably
by using organic anti-icing fluids, e.g., ethylene glycol [103, 124] or urea [125].
Salts such as calcium nitrate [126] have also been tested and, of course, various
anti-freeze liquids are widely used in removing ice from road surfaces and aircraft.
A detailed review on anti-icing chemicals is available in [86].
440 L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445
5. Summary
The review and theoretical analysis presented above points out the complexity of
ice adhesion. Many mechanisms related to ice adhesion are still poorly understood
and most practical problems caused by ice adhesion are far from being solved, see,
e.g., [134, 135].
The adhesion strength of ice is related not only to the chemical composition,
surface morphology, stiffness and thermal expansion coefficient of the substrate
material, but critically depends on the temperature and the test arrangement as well.
Further studies on these effects are necessary in order to obtain comprehensive
understanding of ice adhesion.
When salt is involved, as in marine icing and road maintenance, the adhesion
strength of ice depends on even more factors. When the liquid film that forms at the
ice–substrate interface is retained, then the adhesion strength of saline ice is very
small at any salinity. Therefore, the concepts presented in this paper regarding the
formation of the liquid film due to brine expulsion should be tested and developed
further. For the same reason, the mechanisms of brine drainage and movement of
brine along the ice/structure interface should be studied.
Generally, the higher the water contact angle of the material the lower the ice
adhesion strength. However, it seems that the routes to find practical solutions for
many problems caused by ice adhesion using hydrophobic surfaces have been fully
explored and will not result in further significant development. There are notable
exceptions from this general rule suggesting that it may be more fruitful to investi-
gate the materials that would prevent freezing on a surface, or at least make the true
contact area smaller. The organosilicone material with lithium ions and antifreeze
L. Makkonen / J. Adhesion Sci. Technol. 26 (2012) 413–445 441
proteins synthesized from insects may provide such solutions. Further fundamental
research on the freezing and properties of water at interfaces is required for devel-
opment in this field.
The work done in mechanically removing ice is typically orders of magnitude
larger than the fracture energy and the thermodynamic work of ice adhesion. This
suggests that there may be room for developing better mechanical de-icing methods
by applying shockwaves or other very high energy pulses with a short duration.
New technologies for manufacturing heated films for thermal anti-icing and de-
icing provide solutions in many applications. That these films now allow heating
at a very high power makes the costs of combating ice more reasonable. However,
energy consuming ice combating methods are expensive to use unless their opera-
tion is optimized by detecting the ice on the surfaces. Therefore, attention should
be paid also to developing reliable ice detection methods.
Acknowledgements
Thank are due to Eila Lehmus, Pieti Marjavaara, Matti Halonen and Erkki Järvi-
nen for assistance in the VTT ice adhesion projects and Kari Kolari for providing
FEM simulations. This work was funded by the Academy of Finland and by the
Nordic Council Top-level Research Initiative project TopNano, as well as the Tekes-
Rescoat project.
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