CORROSION CONTROL

A number of techniques are used to combat corrosion, including proper design and materials
selection and the use of coatings, inhibitors, cathodic protection, and passivation.

Design

Proper design of metal structures can slow or even avoid corrosion. Some of the steps that
should be taken to combat corrosion are as follows:
1. Prevent the formation of galvanic cells. This can be achieved by using similar metals or
alloys. For example, steel pipe is frequently connected to brass plumbing fixtures, producing
a galvanic cell that causes the steel to corrode. By using intermediate plastic fittings to
electrically insulate the steel and brass, this problem can be minimized.
2. Make the anode area much larger than the cathode area. For example, copper rivets can be
used to fasten steel sheet. Because of the small area of the copper rivets, a limited cathode
reaction occurs. The copper accepts few electrons, and the steel anode reaction proceeds
slowly. If, on the other hand, steel rivets are used for joining copper sheet, the small steel
anode area gives up many electrons, which are accepted by the large copper cathode area;
corrosion of the steel rivets is then very rapid.

3. Design components so that fluid systems are closed, rather than open, and so that stagnant
pools of liquid do not collect. Partly filled tanks undergo waterline corrosion. Open systems
continuously dissolve gas, providing ions that participate in cathode reaction, and encourage
concentration cells.
4. Avoid crevices between assembled or joined materials. Welding may be a better joining
technique than brazing, soldering, or mechanical fastening. Galvanic cells develop in brazing
or soldering since the filler metals have a different composition from the metal being joined.
Mechanical fasteners produce crevices that lead to concentration cells. If the filler metal is
closely matched to the base metal, welding may prevent these cells from developing.
5. In some cases, the rate of corrosion cannot be reduced to a level that will not interfere with
the expected lifetime of the component. In such cases, the assembly should be designed in
such a manner that the corroded part can be easily and economically replaced.
Coatings

Coatings are used to isolate the anode and cathode regions. Coatings also prevent diffusion of
oxygen or water vapor that initiates corrosion or oxidation. Temporary coatings, such as
grease or oil, provide some protection but are easily disrupted. Organic coatings, such as
paint, or ceramic coatings, such as enamel or glass, provide better protection; however, if the
coating is disrupted, a small anodic site is exposed that undergoes rapid, localized corrosion.
Metallic coatings include tin-plated and hot-dip galvanized (zinc-plated) steel (Figure 1). This
was discussed in earlier chapters on ferrous materials. A continuous coating of either metal
isolates the steel from the electrolyte; however, when the coating is scratched, exposing the
underlying steel, the zinc continues to be effective, because zinc is anodic to steel. Since the
area of the exposed steel cathode is small, the zinc coating corrodes at a very slow rate and
the steel remains protected. In contrast, steel is anodic to tin, so a small steel anode is created
when the tin is scratched, and rapid corrosion of the steel subsequently occurs. Chemical
conversion coatings are produced by a chemical reaction with the surface. Liquids such as
zinc acid orthophosphate solutions form an adherent phosphate layer on the metal surface.
The phosphate layer is, however, rather porous and is more often used to improve paint
adherence. Stable, adherent, nonporous, non-conducting oxide layers form on the surface of
aluminum, chromium, and stainless steel. These oxides exclude the electrolyte and prevent
the formation of galvanic cells. Components such as reaction vessels can also be lined with
corrosion-resistant Teflon or other plastics.

Fig.1. Zinc-plated steel and tin-plated steel are protected differently. Zinc protects steel even
when the coating is scratched since zinc is anodic to steel. Tin does not protect steel when the
coating is disrupted since steel is anodic with respect to tin.
Inhibitors

These are substances that, when added in relatively low concentrations to the environment,
decrease its corrosiveness. Of course, the specific inhibitor depends both on the alloy and on
the corrosive environment. Several mechanisms may account for the effectiveness of
inhibitors. Some react with and virtually eliminate a chemically active species in the solution
(such as dissolved oxygen). Other inhibitor molecules attach themselves to the corroding
surface and interfere with either the oxidation or the reduction reaction, or form a very thin
protective coating. Inhibitors are normally used in closed systems such as automobile
radiators and steam boilers. Several aspects of design consideration have already been
discussed, especially with regard to galvanic and crevice corrosion and erosion–corrosion. In
addition, the design should allow for complete drainage in the case of a shutdown, and easy
washing. Because dissolved oxygen may enhance the corrosivity of many solutions, the
design should, if possible, include provision for the exclusion of air.

Cathodic Protection

We can protect against corrosion by supplying the metal with electrons and forcing the metal
to be a cathode (Figure 2). Cathodic protection can use a sacrificial anode or an impressed
voltage. A sacrificial anode is attached to the material to be protected, forming an
electrochemical circuit. The sacrificial anode corrodes, supplies electrons to the metal, and
thereby prevents an anode reaction at the metal. The sacrificial anode, typically zinc or
magnesium, is consumed and must eventually be replaced. Applications include preventing
the corrosion of buried pipelines, ships, off-shore drilling platforms, and water heaters. A
magnesium rod is used in many water heaters. The Mg serves as an anode and undergoes
dissolution, thus protecting the steel from corroding. An impressed voltage is obtained from a
direct current source connected between an auxiliary anode and the metal to be protected.
Essentially, we have connected a battery so that electrons flow to the metal, causing the metal
to be the cathode. The auxiliary anode, such as scrap iron, corrodes.
Fig.2. Cathodic protection of a buried steel pipeline: (a) A sacrificial magnesium anode
ensures that the galvanic cell makes the pipeline the cathode. (b) An impressed voltage
between a scrap iron auxiliary anode and the pipeline ensures that the pipeline is the cathode.

Passivation or Anodic Protection

Metals near the anodic end of the galvanic series are active and serve as anodes in most
electrolytic cells; however, if these metals are made passive or more cathodic, they corrode at
slower rates than normal. Passivation is accomplished by producing strong anodic
polarization, preventing the normal anode reaction; thus the term anodic protection. We cause
passivation by exposing the metal to highly concentrated oxidizing solutions. If iron is dipped
in very concentrated nitric acid, the iron rapidly and uniformly corrodes to form a thin,
protective iron hydroxide coating. The coating protects the iron from subsequent corrosion in
nitric acid. We can also cause passivation by increasing the potential on the anode above
a critical level. A passive film forms on the metal surface, causing strong anodic polarization,
and the current decreases to a very low level. Passivation of aluminum is called anodizing,
and a thick oxide coating is produced. This oxide layer can be dyed to produce attractive
colors. The Ta2O5 oxide layer formed on tantalum wires is used to make capacitors.

Materials Selection and Treatment

Corrosion can be prevented or minimized by selecting appropriate materials and heat

treatments. In castings, for example, segregation causes tiny, localized galvanic cells that
accelerate corrosion. We can improve corrosion resistance with a homogenization heat
treatment. When metals are formed into finished shapes by bending, differences in the
amount of cold work and residual stresses cause local stress cells. These may be minimized
by a stress-relief anneal or a full recrystallization anneal.
The heat treatment is particularly important in austenitic stainless steels. When the steel cools
slowly from 870 to 425°C, chromium carbides precipitate at the grain boundaries.
Consequently the austenite at the grain boundaries may contain less than 12% chromium,
which is the minimum required to produce a passive oxide layer. The steel is sensitized.
Because the grain boundary regions are small and highly anodic, rapid corrosion of the
austenite at the grain boundaries occurs. We can minimize the problem by several techniques.
1. If the steel contains less than 0.03% C, chromium carbides do not form.
2. If the percent chromium is very high, the austenite may not be depleted to below 12% Cr,
even if chromium carbides form.
3. Addition of titanium or niobium ties up the carbon as TiC or NbC, preventing the
formation of chromium carbide. The steel is said to be stabilized.
4. The sensitization temperature range—425 to 870°C—should be avoided during
manufacture and service.
5. In a quench anneal heat treatment, the stainless steel is heated above 870°C, causing the
chromium carbides to dissolve. The structure, now containing 100% austenite, is rapidly
quenched to prevent formation of carbides.