Anda di halaman 1dari 10

45

CHAPTER 6

Adhesion

6.1 INTRODUCTION

In general terms the phenomenon of fouling represents the interaction between


solids. In the initiation of the fouling process the interaction is between the
surfaces of the heat exchanger and "particles" of foulant. Subsequently as the
deposit thickens, the interaction is between the foulant material clinging to the
surface and the fresh "particles" of foulant arriving at the fluid/solid interface. The
term "particle" is general and may refer to particulate matter, bacteria, corrosion
products and so on. The term "particle" also refers to particles that may be
generated at the surface such as the products of chemical reaction or
crystallisation. Adhesion therefore is clearly a complex process as far as heat
exchanger fouling is concerned, particularly where mixed fouling mechanisms are
present, i.e. cooling water fouling where crystallisation, microbial attachment
corrosion and particle deposition may occur simultaneously. It is useful however,
to consider the underlying theory and the factors that influence the phenomenon of
adhesion. To this end adhesion must normally be considered in terms of a solid
sphere residing on a flat plate [Krupp 1967].
Total forces of adhesion of small particles on surfaces can range from 10.5 to 102
dynes. This total force can correspond to a very large force per unit area perhaps
> 10 9 dynes/cm 2 for micron sized particles [Bowling 1988].

6.2 CLASSIFICATION OF INTERACTIONS

The interactions between solid particles and surfaces can fall into a number of
different categories of forces:
1. Long range attractive forces serve to bring the particle to the surface and to
provide the basis for the contact. The forces involved may include van der
Waals forces, magnetic attraction, and electrostatic forces.

2. Bridging effects. A definite interaction is involved in this process that may


include mutual diffusion or "alloying" between the substance of the particle and
the surface. Liquid/solid bridging may be involved at the interface that invokes
capillary forces.

3. Short range forces can only be effective once there is intimate contact between
the "particle" and the surface, i.e. aRer the long range forces and to a lesser
extent the bridging effects, have established a physical contact. The short
range forces may include chemical bonding and hydrogen bonds [Krupp 1967].
46 Fouling of Heat Exchangers

As far as heat exchanger fouling is concerned it is the long range forces that are
of prime importance since they are responsible for bringing the "particles" and
surface into initial contact. In this respect a general discussion of adhesion is
acceptable whereas the bridging effects and short term forces will be very specific
to a particular condition.
The long range forces have to be considered in terms of particle size. Large
particles, i.e. > 50/on are generally influenced by electrostatic forces and van der
Waals forces generally affect smaller particles in a lower/.on range.
Bowling [1988], Visser [1988] and Oliveira [1992], have reviewed particle
surface interaction and their work is used extensively in the development of the
discussion in this chapter.

6.3 VAN DER WAALS FORCES

Bowling [1988] describes van der Waals forces in the following way. At
absolute zero temperature solids can exhibit local electric fields and above this
temperature additional contributions come from the excitation of the atoms and
molecules making up the solid material. Van der Waals forces include forces
between molecules possessing dipoles and quadrapoles produced by the
polarisation of the atoms and molecules in the material. These dipoles and
quadrapoles may be present naturally or by induced polarity. Non-polar attractive
forces may also be present. The non-polar van der Waals forces may also be
referred to as London-van der Waals dispersion forces because London associated
these forces with the cause of optical dispersion, i.e. spontaneous polarisation
[Corn 1966]. Such dispersion forces will make the major contribution to the
intermolecular forces, except where the opportunity to polarise is small and the
dipole moment is large.
Hamaker [ 1937] extended the theory of London to the interaction between solid
bodies. The theory is based on the interaction between atoms and molecules and
calculates the attraction between larger bodies as an integration involving geometry
and the physical and chemical nature of the interacting bodies. The method
employs the so-called Hamaker constant AH that "takes care" of the properties of
the bodies. Visser [1972] has reviewed Hamaker constants.
For the case of a sphere resting on a fiat plate (Fig. 6.1)

F = AHr (6.1)
w 6X 2

where F , is the van der Waals force

r is the radius of the sphere

x is the separation distance


Adhesion 47

Sphere

X
Plofe

FIGURE 6.1. Sphere resting on a plate

For two flat plates (see Fig. 6.2) the interaction force per unit area is given by

P= 6nx 3 (6.2)

Qte
~ ,==,~==~===,,,,
X

Plofe

FIGURE 6.2. Two plates in contact

The simple additive approach of Hamaker has been criticised as being inaccurate
[Kitchener 1973] and Oliveira [1992] states that it is not valid for condensed media
interactions. Visser [1988] has explained the reason why the original Hamaker
approach was inaccurate being due to the false assumption that the molecular
forces are additive. It cannot be so, since the interactions between molecules with
larger separations than near or direct contact, are screened by any molecules at a
closer distance. As a consequence, layers of adsorbed materials for instance can
influence the interaction between the two interacting macroscopic bodies.
Langbein [1969] has demonstrated that when the thicknesses of the surface layers
on microscopic bodies are larger than the separation distance, their interaction is
48 Fouling of Heat Exchangers

determined by the properties of the layer rather than the underlying material. As
Visser [1988] remarks this has implications for fouling and its prevention.
The objections to the Hamaker theory were overcome by Lifshitz and his co-
workers [Lifshitz 1956, Dzyaloshinskii 1961] using the bulk optical properties of
the interacting bodies. The approach employed by Lifshitz uses the so-called
Lifshitz-van der Waals constant h that depends only on the materials involved
provided the separation distance is relatively small. Under some conditions the
constant h can be related to the Hamaker constant by

h= 4 zrAn (6.3)
3

Rumpf [1977] states that the value ofh generally ranges between about 0.6 and
9.0 eV, depending on the combination of materials, but Visser [1972] presents data
that clearly show that values may be well outside this stated range. Table 6.1 gives
some values for the Lifshitz-van der Waals constant under vacuum conditions and
in water. The presence of the water has a pronounced effect on the constant - i.e.
a reduction in the van der Waals forces. The reduction is higher, the weaker the
van der Waals interaction in vacuum [Visser 1988].

TABLE 6.1

Lifshitz-van der Waals constants for various materials in contact with similar material in vacuum and in
water [Visser 1972]

Material h e V in vacuum h e V in water


Gold 14.3 9.85
Silver 11.7 7.76
Copper 8.03 4.68
Diamond 8.60 3.95
Magnesium oxide 3.03 0.47
Polystyrene 1.91 0.11

Negative values of the Lifshitz-van der Waals constant are possible. For
instance Visser [1988] gives the constant for Si in contact with AI203 in water as
-0.78 eV. According to Oliveira [1992] negative values of the constant will
produce spontaneous separation.
For the combination of two different materials 1 and 2 in vacuum h~z can be
obtained in good approximation by

/112-4h~, .h22 (6.4)


Adhesion 49

6.4 ELECTROSTATIC DOUBLE LAYER FORCES

Solid materials immersed in an aqueous medium generally attain a surface


charge. The charge arises due to the adsorption of specific ions present in the
medium or the dissociation of molecules or groups on the surface of the solid.
The charge may be demonstrated by imposing an electric field on a suspended
colloid when the anode and cathode attract negatively and positively charged
particles respectively. It is possible to measure the so-called Zeta-potential of such
a system by balancing the surface charge of the particle of investigation with a
counter charge of ions of opposite sign in order to make the system
electrostatically neutral.
The redistribution of ions or charged particles, brought about by the immersion
of a charged surface in an aqueous environment will involve particles of similar
charge (co-ions) being repelled from the surface while those of opposite charge
(counter ions) will be attracted to the surface. The overall effect, i.e. a
combination of the distribution of charged particles and Brownian motion, is the
so-called Poisson-Boltzmann distribution of the ions (or particles) throughout the
water phase. A diffuse layer is produced which together with the charged solid
surface, is called the electrical double layer. Fig. 6.3 shows a simplified sketch of
the situation that applies to a spherical particle immersed in water.

I
I

I G

+
ee,e G
I
!

+
@@Q I

I
. i ,

. i , @

D
G
e
Solid Diffuse
surface layer

FIGURE 6.3. Simplified sketch of an electrostatic double layer and a solid spherical particle

Independently Deryagin and Landau [ 1941 ] and Verwey and Overbeek [ 1948]
developed a theory, usually referred to as the DVLO theory, to explain the
complex interactions when electrostatic double layer systems are in contact. On
50 Fouling o f Heat Exchangers

the one hand there is the force of repulsion F R due to the double layer effect, but
on the other there is the attractive van der Waals force (Fw). It is usual to describe
this balance between F , and F R in the form of an energy-distance diagram as shown
on Fig. 6.4. The potential energy of interaction

Vr = Vw + VR (6.5)

where V, and VR are the energy associated with the van der Waals and double layer
interactions respectively.

Vmax
I--

>E : V. = f ( e x p x )
.s
4--
~' Energy
=
I..,
barrier
._c Distance
0
Secondary
I.. minimum
Q.I
C:
eLI

El V w = f (x z)
-4,
{:
-8--
0
EL

Primary minimum

FIGURE 6.4. Energy-distance profiles

As a result of the charges in the relationship between V and x the summed curve
shows a maximum at 1I== at a short separation distance. V,,~ is an energy barrier.
At large distances the energy is a minimum (V~,). If the thermal energy of the
particles is smaller than V u , no interaction will take place and fouling will not
occur. The problem is more complex than the simple approach taking only the van
der Waals forces and the double layer forces into account, since other interactions
are also likely to be present.
Reversible and irreversible adhesion may be explained in terms of the primary
minimum and V,,, [Oliveira 1992]. Reversible adhesion will occur at V,,, and
irreversible adhesion at short distances and high negative values of V. The
implications for the fouling process and deposit removal may be clearly identified.
Adhesion 51

The DVLO theory assumes that the surfaces of two interacting solid bodies
have the same charge and sign. The result is a double layer that is repulsive. There
are situations where surfaces are oppositely charged and electrostatic charge
effects will reinforce the attractive van der Waals forces. Visser [1988] cites clay
particles as an example. Clay particles, e.g. kaolin, have a platelet structure and it
is possible for the edges to acquire a positive charge and the surface to be negative.
Another example is given by Visser [1988] where two negatively charged
surfaces are linked by positively charged ions [see Fig. 6.5].

~~~~,~~~__.~.~xx~Solidsurface .\\\\\\\\
+ + + + +
Ca Ca CQ Ca Ca Calcium
ions
4- + + + +

FIGURE 6.5. Calcium bridging

Other similar situations where ions are involved may be visualised.


Visser [ 1988] also draws attention to the effects of surface hydration and steric
hindrance that also prevent close approach of particles and surfaces thereby
reducing the opportunity for adhesion. In both examples interpenetration of the
adsorbed layers, i.e. a physical barrier of where say, a polymer is adsorbed,
prevents collision and hence adhesion.
In non-immersed systems such as dust particles in flowing air streams, van der
Waals forces will operate leading to adhesion and since there are no barriers,
prevention of fouling is extremely difficult. In gas streams where there are reacting
species and possibly changes in phase such as in combustion flue gases, the
situation is extremely complex.
52 Fouling of Heat Exchangers

6.5 PRACTICAL SYSTEMS

In the theoretical analysis ideal, smooth, surfaces were considered, i.e. flat
plates or spheres on flat plates. In reality the surfaces of industrial equipment will
be far from smooth, and the adhesion forces will be enhanced due to the availability
of larger contact areas. Fig. 6.6 illustrates a spherical particle resting in a "hole" on
a plate; even this is still a very idealised picture.

Solid
e

a in the
surfo.ce

FIGURE 6.6. A sphere resting in a hollow on a plate

For real particles on real surfaces it is conceivable that particles will move over
the surface, under the influence of the fluid flow and viscous sub-layer instabilities,
till it falls into a hole to suit its own particular shape. Particle and surface
morphology are therefore crucial in fouling processes.

6.6 CONCLUDING REMARKS

In summary the principal factors responsible for adhesion include:


1. van der Waals forces of attraction

2. Electrostatic forces in systems of oppositely charged surfaces

3. The larger the contact area the greater the total attractive force

In many respects the theories are limited to simple and ideal situations. In
industrial equipment where conditions are far from ideal and the geometry
complex, it will be difficult to apply the theories outlined in this chapter.
Furthermore Mozes [1994] who has considerable experience in the application of
Adhesion 53

adhesion theory to biofilms, has made some valuable observations on the


attachment of micro-organisms. She states that the following features are
sometimes ignored: A microbial cell
1. is not a homogeneous, rigid, smooth spherical ideal colloid particle

2. is not an inert system and never in equilibrium with its environment

3. may be motile

4. may sense contact with a foreign surface and respond physiologically to this
stimulus

She goes on to say that a true understanding of the adhesion/


flocculation/flotation phenomena must combine and integrate consideration of
biological characteristics of cells as living entities with the simple physico-chemical
approach regarding cells as colloidal particles. Similar specific comments may be
made about all fouling phenomena. Theory has to make simplifying assumptions
that may be unjustified in the context of the phenomena concerned. The purpose
however, is to provide a background to the discussions on the various mechanisms
by which surfaces become fouled.

REFERENCES

Bowling, R.A., 1988, A theoretical review of particle adhesion, in: Mittal, ed.
Particles on Surfaces 1. Detection, Adhesion and Removal. Plenum Press,
New York.
Corn, M., 1966, in: Davies, C.N. ed. Aerosol Science Academic Press, New York.
Derjaguin, B.V. and Landau, L.O., 1941, Theory of the stability of strongly
charged lyophobic solutions and of adhesion of strongly charged particles
in solutions of electrolytes. Acta Physicochim. USSR, 14, 633.
Dzyaloshinskii, I.E., Lifshitz. E.M., Pitaevski, L.P., 1961, Adv. Phys. 10, 165.
Hamaker, H.C., 1937, The London-van der Waals attraction between spherical
particles. Physica (Utrecht) 4, 1058.
Kitchener, J.A., 1973, J. Soc. Cosmet. Chem. 24, 709.
Krupp, H., 1967, Ad. Colloid Interface Science. 1 (2), 111.
Langbein, D., 1969, van der Waals Attraction between macroscopic bodies. J.
Adhes. 1,237.
Lifshitz, E.M., 1956, Sov. Phys. JETP. 2, 73.
Mozes, N., 1994, Living cells and interracial phenomena. 36me R6union
Europ~ennes Adhesion des micro-organisms aux surfaces. Universit~e
Paris-Sud, Facult6 de Pharmacie Laboratoire de Microbiologie Industrielle.
Ch~.tenay-Malabry, France C.I.
54 Fouling of Heat Exchangers

Oliveira, D.R., 1992, Physico-chemical aspects of adhesion, in: Melo, L.F., Bott,
T.R., Fletcher, M. and Capdeville, B. eds. Biofilms - Science and
Technology, Kluwer Academic Publishers, Dordrecht.
Rumpf, H., 1977, in: Sastry, K.V.S. ed. Proc. 2nd Int. Symp. on Agglomeration.
Am. Inst. Mining, Metallurgy and Petroleum Engineers Inc. New York.
Vervey, E.J.W., Overbeek, J.T.G., 1948, Theory of the Stability of Lyophobic
Colloids. Elsevier, Amsterdam.
Visser, J., 1972, On Hamaker constants. A comparison between Hamaker constant
and Lifshitz constants. Adv. Coll. Int. Sci. 3, 331.
Visser, J., 1988, Adhesion and removal of particles I and II, in: Melo, L.F., Bott,
T.R. and Bernardo, C.A. eds. Fouling Science and Technology. Kluwer
Academic Publishers, Dordrecht.