3.1 Corrosion Data
Carbon and low-alloy steels are primarily affected by general or uniform
corrosion. Iron occurs naturally in the form of various oxides, the ores of
which are refined to produce steel. Therefore, in atmospheric service they
67
tend to return to their oxide form by a process known as rusting. The
corrosion of steel is very complex, with over a dozen variables determining
the rate of corrosion. Water is the most common solvent in everything from
dilute solutions to concentrated acids and salt solutions. Some organic
systems are also capable of causing some severe corrosion.
In dilute water solutions, the most important variable is acidity or solution
pH. Figure 3.1 shows the effect of pH on the corrosion of steel at 228C (778F)
and 408C (1048F). The diagram is suitable for water flowing at a moderate
flow rate. There is a range of pH from 5.5 to 10 where the corrosion rate is
constant at about 10–12 mpy (250–305 mm/year). In this range there is an
alkaline solution of saturated ferrous hydroxide covering the steel’s surface;
this hydroxide solution has a constant pH of about 9.5. The rate-determining
reaction in this corrosive range is the diffusion of oxygen through the ferrous
hydroxide film to feed the electrochemical cathodic reduction of the oxygen
to the hydroxyl ion. Thus, dissolved oxygen is another key variable in
aqueous corrosion.
At lower pH values, the cathodic reduction changes to the relatively rapid
reduction of hydrogen ions in the acidic solution to produce hydrogen gas
bubbles. Different acids have different values of pH where the onset of this
rapid reaction occurs. As shown, carbonic acid (dissolved carbon dioxide)
initiates it at pH 5.5. Hydrochloric acid starts the reaction at pH 4. The effect
is dramatic; at pH 2.7 the corrosion rate reaches 80 mpy (2 mm/year). Under
stagnant conditions the corrosion rate is lower. However, stagnant
conditions are to be avoided when possible because they are exactly
where the various forms of localized corrosion become serious, including
pitting, oxygen concentration cells, and microbiologically influenced
corrosion (MIC). These localized corrosions penetrate faster than overall
general corrosion.
40
30
20
10
0
pH = 10 pH = 5
Water pH
pH = 4
22 C
40 C
CO2
HCI
76 mpy
@
pH = 2.67
Oxygen: 6 mL/L
Corrosion
rate
mpy
FIGURE 3.1
Effect of pH on the corrosion of carbon steel.
68 Fundamentals of Metallic Corrosion: Atmospheric and Media Corrosion of Metals
The next important variable to consider is flow rate. Figure 3.2 shows the
effect of flow on the corrosion of steel from stagnant to 8 ft/s. Note that as
the flow rate rises from zero, the corrosion rate increases to a maximum
around 1 or 2 ft/s. This increase comes from an increase in the oxygen
supplied for the oxygen reduction process occurring on the cathodic areas of
the steel. Higher flow rates then supply enough oxygen so that the adsorbed
oxygen and the ferrous hydroxide layer can cover the entire steel surface, a
complete level of passivation. At 6–8 ft/s (1.8–2.4 m/s), which is the
common range of flow rates in the chemical industry, the corrosion rate
settles at 10–15 mpy (250–380 mm/year). Figure 3.2 also shows the effect of
roughness of the steel, another variable affecting corrosion.
With higher flow rates, the corrosion rate increases up to around 40 ft/s
(12 mm/s) where the attack changes to erosion–corrosion, which means that
any protective oxide or adsorbed layer is stripped away and bare steel is
open to accelerated attack. Turbulence has a similar effect. Figure 3.3 and
Figure 3.4 show the effects of increasing flow velocity for distilled water and
seawater. At 39 ft/s the corrosion rate in distilled water at 508C (1228F)
exceeds 200 mpy (5 mm/year).
With corrosion, as with other chemical reactions, temperature plays a
major role. Figure 3.1 shows the increase in corrosion from increasing
temperature. In neutral or alkaline waters, however, the temperature effect is
more complicated. In an open system, a higher temperature will drive off
oxygen, eventually to very low levels. Because oxygen provides the cathodic
reaction in the corrosion process, if there is no oxygen there will be no
corrosion. Figure 3.5 shows this effect, with the corrosion beginning to
decrease around 808C (1768F) and becoming very low above 1008C (2128F).
The behavior of weathering low-alloy steels in aqueous corrosion tests and
applications is unpredictable. In 1953, early tests on weathering steels
containing copper, chromium, phosphorus, and nickel showed superior
50
40
30
20
10
0
2 4 6 8
Corrosion
rate
mpy
Rough steel
Polished steel
Flow velocity, ft/s
Municipal water @ 21°C in steel tubes
FIGURE 3.2
Effect of water flow velocity on the corrosion of steel. Increased oxygen leads first to higher
corrosion, then to oxygen passivation that lowers corrosion.
Corrosion