1/6/22, 19:22 An Intro to Pipeline Corrosion in Seawater

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An Intro to Pipeline Corrosion in Seawater

By Mehdi Yari

Published: February 22, 2021

KEY TAKEAWAYS
The three important factors in seawater corrosion include chloride concentration, oxygen and temperature.

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When it comes to corrosion engineering, seawater is one of the most important environments to discuss. This may be especially true
when it comes to pipelines, which crisscross the ocean carrying oil and gas worldwide—and which, of course, cause the most problems
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if they fail. (Find out more on this topic in Industry Experts Discuss Subsea Pipeline Corrosion Management .) Here we'll look at the
important factors that affect the corrosion of metals in saltwater and the application of structural materials in saltwater.

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Three Important Factors in Seawater Corrosion

1. Chloride Concentration

The chloride ions in saline water are one of the most aggressive substances in seawater. The chloride concentration in water is usually
called "salinity." In seawater, this usually varies between 3.1 and 3.8 weight percent, depending on the solar evaporation rate of water,
precipitation and the dilution of water by freshwater and circulation.

The corrosivity of chloride ions in seawater can be explained based on three factors:

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Chloride ions can react with dissolved ferrous ions to create ferrous chloride according to the following reactions:

Fe = Fe2+ + 2 e-

Fe2+ + 2 Cl- = FeCl2

The ferrous chloride produced in this reaction can react with dissolved oxygen and produce ferric oxide (Fe2O3) and ferric chloride
(FeCl3), which is considered an oxidizing agent that can enhance the general corrosion rate and pitting corrosion. Ferric ions can
shift the corrosion potential (Ecorr) to values that are more than Eb (pitting potential or breakdown potential) and thus cause more
severe corrosion.
In pitting corrosion, chloride ions are called "aggressive anions" that can influence both pit initiation and growth. They can
penetrate the passive film and further increase pit initiation risk. Also, chlorides can worsen pit growth through an autocatalytic
process. (Related reading: How to Effectively Recognize, Prevent and Treat Pitting Corrosion.)

It should be noted that stagnant water is necessary for pitting corrosion to occur. In other words, pitting corrosion is unlikely to
happen in areas where water is moving and being replaced.

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Dissolved oxygen is another important factor that can influence the corrosivity of seawater. The concentration of chlorides can
influence the solubility of oxygen in seawater. The highest oxygen concentration can be achieved at 3.5 weight percent sodium

chloride, as shown in the following figure:

Figure 1. The graph shows how the combination of chloride concentration and dissolved oxygen concentration results in the maximum
corrosion rate.

2. Oxygen

Since the pH of seawater varies in the range of 7.5 to 8.5, the oxygen reduction reaction is the predominant cathodic reaction in
competition with the hydrogen evolution reaction. In fact, dissolved oxygen can have a significant influence on the corrosion rate of
metals in seawater.

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There are several factors that can influence the oxygen cathodic reaction. The agitation of seawater due to waves can increase the
oxygen concentration in the seawater. Temperature is the other factor, and it produces two opposing effects. At first view, temperature
can have an impact on the solubility of dissolved oxygen and the diffusion rate of dissolved oxygen. The diffusion rate of oxygen in
seawater increases as the temperature of the water rises. In response, the corrosion rate increases as a result of the increasing limit
current density of the oxygen reduction cathodic reaction. On the other hand, at high temperatures, the solubility of oxygen in seawater
decreases. This effect can reduce the corrosion rate. Despite the above-mentioned effects, the solubility of oxygen in saline water is not
affected by temperature as much as the diffusion coefficient is affected.

Moreover, salinity can influence dissolved oxygen concentration. Generally, the maximum oxygen concentration is obtained at 3.5
weight percent of NaCl.

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3. Temperature

Temperature is a factor that can impact both the activation polarization and concentration polarization, which can increase corrosivity in
most types of corrosion. For example, the corrosion of steel in water will increase from 2 to 4% per 1.5°F (1°C) increase. Therefore,
seawater corrosion in tropical areas is more significant than in arctic zones.

Structural Materials in Seawater

Here we'll take a look at the corrosion behavior of the most important structural materials in seawater.

Plain Steels

Unprotected, mild steels are not resistant against corrosion in a marine environment. However, they are usually used in marine
environments in the form of sheet piles, ship bodies, etc. after using a suitable protection technique, such as cathodic protection or the
application of polymeric coatings. (For a case study, see How a Liquid Nylon Coating Can Help Create an Impervious, Pinhole-Free

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Coating Barrier.) For an unprotected steel structure in seawater, the corrosion rate markedly varies depending on its position relative to

the ocean, according to the image below.

(Source: Copper Development Association Inc.)

At the bottom of the sea (immersion zone), the seawater is stagnant and has the lowest temperature and oxygen concentration.
Therefore, in this area, the corrosion rate is expected to be very low in comparison to other zones.

In higher levels from the bottom of the sea, there is the tidal zone, where materials are exposed to a cyclic wetting-drying process. This
cycle repeats every 24 hours and can increase the corrosion rate. According to previous investigations, the corrosion rate of mild steel in
this area is around of 100 µm/yr, while this value for the immersion zone is considered less than 50 µm/yr or even near to zero. High

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temperatures, saturation by oxygen, and the spray or splash of seawater cause the most severe corrosion at a level that is known as
"splash zone." The corrosion in the splash zone reaches to 900 µm/yr (for example in the Cook Inlet in Alaska).

It should be mentioned that exactly beneath the splash zone, the corrosion rate is slightly higher than the other parts of the tidal zone.
This higher corrosion rate is due to the creation of an oxygen concentration cell. In this cell, the anode is located beneath the splash
zone where the O2 partial pressure is low and the cathode is located at the splash zone where the O2 partial pressure is high.

At levels higher than the sea surface, which is called the "marine atmosphere," a thin film of seawater condenses on the metallic
surface and can cause atmospheric corrosion. The intensity of wind, salinity of seawater, and temperature are the most important
parameters that can influence marine atmosphere corrosion.

Cathodic protection, painting and sheathing are three helpful methods to prevent the corrosion of steel columns and piles in seawater.

Stainless Steels

Stainless steels have a high general corrosion resistance in seawater due to their protective chromium oxide layer. However, because
the chloride concentration of seawater is so high, these alloys are susceptible to pitting corrosion in a stagnant seawater environment.
For example, stainless steel type 304, which is a commonly used stainless steel, is not safe against the pitting corrosion in seawater.
The pitting resistance of stainless steel increases to an acceptable value when 2% molybdenum is added to the chemical composition
of stainless steel, which results in stainless steel type 316. Similar to molybdenum, increasing the chromium content in stainless steels
can enhance pitting resistance in still seawater.

Copper Alloys

Copper and its alloys (bronze and brass) are usually resistant against general corrosion in seawater. Therefore, diffident kinds of copper
alloys are suggested for use in the marine industry.

Sometimes the chemical composition of brass alloys is modified to perform in a marine environment more efficiently – for example,
admiralty brass or naval brass alloys, which consist of 1% tin to prevent dezincification, or arsenical brass, which includes very low
amounts of arsenic to inhibit dezincification. Aluminum is usually added to brass in order to improve the erosion corrosion resistance of
brass alloys in ship impellers. Cupronickels (copper with 10–30% nickel alloys) are widely used for marine applications due to their

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great resistance against seawater corrosion. (Learn more about this and other uses in the article 11 Uses for Cupronickel and Why You
Should Be Using It Now.)

Concrete

Chlorides can penetrate into concrete through its flaws (pore spaces and cracks) and touch the reinforced steel rods, which are
passivated by the highly alkaline environment of concrete. This can cause localized corrosion. Eventually, the concrete breaks down due
the internal pressure of rust growth.

Aluminum

The corrosion resistance of aluminum and its alloys in marine environments significantly depends on the alloying elements and surface
finish. For example, the presence of iron and/or copper in aluminum decreases the corrosion resistance of aluminum. However, 5xxx
series aluminum alloys, which include magnesium, are usually good candidates for use in marine applications (such as 5052 alloy).
Moreover, creating a hard anodized layer (thick aluminum oxide layer) on the aluminum surface can inhibit marine corrosion.

Titanium and Titanium Alloys

Titanium and titanium alloys represent one of the best choices in marine services. Despite its high price, titanium should be considered.

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Related Terms

Pitting Corrosion

Chlorides

Steel Corrosion

304 Grade Stainless Steel

Aluminum Alloy Corrosion

Titanium Corrosion

Corrosion Potential

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Breakdown Potential

Hydrogen Evolution Reaction

Concentration Polarization

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Written by Mehdi Yari

| Electrochemistry and Corrosion Laboratory at the University of Western Ontario

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Mehdi Yari currently serves as a postdoctoral fellow in the Electrochemistry and Corrosion Laboratory at the University of Western
Ontario. He was faculty staff in the Materials Engineering department at the Science and Research branch of Azad University (Iran) for
more than eight years. During that time, he became involved in metallurgical industries as a scientific and engineering consulter. He
received B.Sc., M.Sc., and Ph.D. degrees in metallurgical engineering, corrosion engineering, and advanced materials in materials
engineering, respectively. He has obtained several teaching and research awards. He is author and co- author of more than 15 scientific
papers in reputed journals in the field of corrosion and surface engineering.

Read Mehdi Yari’s bio

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