As to micro fouling, distinctions are made between: • Scaling or precipitation fouling, as
crystallization of solid
salts,
oxides, and
hydroxides from water
solutions (e.g., calcium carbonate or calcium sulfate) •
Particulate fouling, i.e., accumulation of particles, typically
colloidal particles, on a surface • Corrosion fouling, i.e., in-situ growth of
corrosion deposits, for example, magnetite on
carbon steel surfaces • Chemical reaction fouling, for example, decomposition or polymerization of organic matter on heating surfaces • Solidification fouling – when components of the flowing fluid with a high-melting point freeze onto a subcooled surface •
Biofouling, like settlements of
bacteria and algae • Composite fouling, whereby fouling involves more than one foulant or fouling mechanism
Precipitation fouling buildup inside a pipe reduces liquid flow through the pipe and reduces thermal conduction from the liquid to the outer pipe shell. Both effects will reduce the pipe's overall thermal efficiency when used as a
heat exchanger. Scaling or precipitation fouling involves
crystallization of solid
salts,
oxides, and
hydroxides from
solutions. These are most often water solutions, but non-aqueous precipitation fouling is also known. Precipitation fouling is a very common problem in boilers and heat exchangers operating with
hard water and often results in
limescale. Through changes in temperature, or solvent
evaporation or
degasification, the concentration of salts may exceed the
saturation, leading to a
precipitation of solids (usually crystals). As an example, the equilibrium between the readily soluble
calcium bicarbonate - always prevailing in natural water - and the poorly soluble
calcium carbonate, the following chemical equation may be written: :\mathsf{{Ca(HCO3)2}_{(aqueous)} -> {CaCO3(v)} + {CO2}\!{\uparrow} + H2O} The calcium carbonate that forms through this reaction precipitates. Due to the temperature dependence of the reaction, and increasing volatility of CO2 with increasing temperature, the scaling is higher at the hotter outlet of the heat exchanger than at the cooler inlet. In general, the dependence of the salt
solubility on temperature or presence of evaporation will often be the driving force for precipitation fouling. The important distinction is between salts with "normal" or "retrograde" dependence of solubility on temperature. Salts with the "normal" solubility increase their solubility with increasing temperature and thus will foul the cooling surfaces. Salts with "inverse" or "retrograde" solubility will foul the heating surfaces. An example of the temperature dependence of solubility is shown in the figure. Calcium sulfate is a common precipitation foulant of heating surfaces due to its retrograde solubility. Precipitation fouling can also occur in the absence of heating or vaporization. For example, calcium sulfate decreases its solubility with decreasing pressure. This can lead to precipitation fouling of reservoirs and wells in oil fields, decreasing their productivity with time. Fouling of membranes in
reverse osmosis systems can occur due to differential solubility of barium sulfate in solutions of different
ionic strength. The deposition rate by precipitation is often described by the following equations: :Transport: \frac {dm} {dt} = k_t (C_b-C_i) :Surface crystallisation: \frac {dm} {dt} = {k_r} (C_i-C_e)^{n_1} :Overall: \frac {dm} {dt} = k_d (C_b-C_e)^{n_2} where: : m – mass of the material (per unit surface area), kg/m2 : t – time, s : C_b – concentration of the substance in the bulk of the fluid, kg/m3 : C_i – concentration of the substance at the interface, kg/m3 : C_e – equilibrium concentration of the substance at the conditions of the interface, kg/m3 : n_1, n_2 –
order of reaction for the crystallization reaction and the overall deposition process, respectively, dimensionless : k_t, k_r, k_d – kinetic rate constants for the transport, the surface reaction, and the overall deposition reaction, respectively; with the dimension of m/s (when n_1 = n_2 = 1)
Particulate fouling Fouling by particles suspended in water ("
crud") or in gas progresses by a mechanism different than precipitation fouling. This process is usually most important for
colloidal particles, i.e., particles smaller than about 1 μm in at least one dimension (but which are much larger than atomic dimensions). Particles are transported to the surface by a number of mechanisms and there they can attach themselves, e.g., by
flocculation or
coagulation. Note that the attachment of colloidal particles typically involves electrical forces and thus the particle behaviour defies the experience from the macroscopic world. The probability of attachment is sometimes referred to as "
sticking probability", P: : \frac {dm} {dt} = {k_a} C_i and then the transport and attachment kinetic coefficients are combined as two processes occurring in series: : k_d = \left( \frac 1 {k_a} + \frac 1 {k_t} \right) ^{-1} : \frac {dm} {dt} = {k_d} C_b where: • \frac{dm}{dt} is the rate of the deposition by particles, kg m−2 s−1, • k_a, k_t, k_d are the kinetic rate constants for deposition, m/s, • C_i and C_b are the concentration of the particle foulant at the interface and in the bulk fluid, respectively; kg m−3. Being essentially a
surface chemistry phenomenon, this fouling mechanism can be very sensitive to factors that affect colloidal stability, e.g.,
zeta potential. A maximum fouling rate is usually observed when the fouling particles and the substrate exhibit opposite electrical charge, or near the
point of zero charge of either of them. Particles larger than those of colloidal dimensions may also foul e.g., by sedimentation ("sedimentation fouling") or straining in small-size openings. With time, the resulting surface deposit may harden through processes collectively known as "deposit consolidation" or, colloquially, "aging". The common particulate fouling deposits formed from aqueous suspensions include: •
iron oxides and iron oxyhydroxides (
magnetite,
hematite,
lepidocrocite,
maghemite,
goethite); •
Sedimentation fouling by
silt and other relatively coarse suspended matter. Fouling by particles from gas
aerosols is also of industrial significance. The particles can be either solid or liquid. The common examples can be fouling by
flue gases, or fouling of air-cooled components by dust in air. The mechanisms are discussed in article on
aerosol deposition.
Corrosion fouling Corrosion deposits are created in-situ by the corrosion of the
substrate. They are distinguished from fouling deposits, which form from material originating ex-situ. Corrosion deposits should not be confused with fouling deposits formed by ex-situ generated corrosion products. Corrosion deposits will normally have composition related to the composition of the substrate. Also, the geometry of the metal-oxide and oxide-fluid interfaces may allow practical distinction between the corrosion and fouling deposits. An example of corrosion fouling can be formation of an iron oxide or oxyhydroxide deposit from corrosion of the carbon steel underneath. Corrosion fouling should not be confused with fouling corrosion, i.e., any of the types of corrosion that may be induced by fouling.
Chemical reaction fouling Chemical reactions may occur on contact of the chemical species in the process fluid with heat transfer surfaces. In such cases, the metallic surface sometimes acts as a
catalyst. For example, corrosion and
polymerization occurs in cooling water for the chemical industry which has a minor content of hydrocarbons. Systems in petroleum processing are prone to polymerization of
olefins or deposition of heavy fractions (
asphaltenes, waxes, etc.). High tube wall temperatures may lead to
carbonizing of organic matter. The food industry, for example milk processing, also experiences fouling problems by chemical reactions. Fouling through an ionic reaction with an evolution of an inorganic solid is commonly classified as precipitation fouling (not chemical reaction fouling).
Solidification fouling Solidification fouling occurs when a component of the flowing fluid "freezes" onto a surface forming a solid fouling deposit. Examples may include solidification of wax (with a high melting point) from a hydrocarbon solution, or of molten ash (carried in a furnace exhaust gas) onto a heat exchanger surface. The surface needs to have a temperature below a certain threshold; therefore, it is said to be subcooled in respect to the solidification point of the foulant.
Biofouling in Northern France, covered with
zebra mussels
Biofouling or biological fouling is the undesirable accumulation of micro-organisms, algae and
diatoms, plants, and animals on surfaces, such as ships and submarine hulls, or piping and reservoirs with untreated water. This can be accompanied by
microbiologically influenced corrosion (MIC). Bacteria can form biofilms or slimes. Thus the organisms can aggregate on surfaces using colloidal hydrogels of water and extracellular polymeric substances (EPS) (
polysaccharides, lipids, nucleic acids, etc.). The biofilm structure is usually complex. Bacterial fouling can occur under either aerobic (with oxygen dissolved in water) or anaerobic (no oxygen) conditions. In practice, aerobic bacteria prefer open systems, when both oxygen and nutrients are constantly delivered, often in warm and sunlit environments. Anaerobic fouling more often occurs in closed systems when sufficient nutrients are present. Examples may include
sulfate-reducing bacteria (or
sulfur-reducing bacteria), which produce sulfide and often cause corrosion of ferrous metals (and other alloys). Sulfide-oxidizing bacteria (e.g.,
Acidithiobacillus), on the other hand, can produce sulfuric acid, and can be involved in corrosion of concrete.
Zebra mussels serve as an example of larger animals that have caused widespread fouling in North America.
Composite fouling Composite fouling is common. This type of fouling involves more than one foulant or more than one fouling mechanism working simultaneously. The multiple foulants or mechanisms may interact with each other resulting in a synergistic fouling which is not a simple arithmetic sum of the individual components.
Fouling on Mars NASA
Mars Exploration Rovers (
Spirit and
Opportunity) experienced (presumably) abiotic fouling of solar panels by dust particles from the Martian atmosphere. Some of the deposits subsequently
spontaneously cleaned off. This illustrates the universal nature of the fouling phenomena. ==Quantification of fouling==