Corrosion Engineering

Lecture 14
CHE 311
Introduction
 From a purely technical stand point of view, an obvious answer to corrosion problems
would be to use more-resistant materials. In many cases, this approach is an
economical alternative to other corrosion control methods. Corrosion resistance is
not the only property to be considered in making material selections, but it is of
major importance in the chemical process industries.
 The choice of a material is the result of several compromises. For example, the
technical appraisal of an alloy will generally be a compromise between corrosion
resistance and some other properties such as strength and weldability and the final
selection will be a compromise between competence and economic factor. In
specifying a material, the task usually requires three stages:
 Listing the requirement
 Selecting and evaluating the candidate materials
 Choosing the most economical material
Materials Selection Processes
Approaches to control corrosion
 There are five general approaches to corrosion control:
 Change of material (partially or totally).
 Change of environment (partially or totally).
 Place a barrier between the material and the environment.
 Apply electrochemical method
 Cathodic protection (CP)
 Anodic protection (AP).
 Design consideration at all stages (from layout until operation)
Cathodic Protection
 Cathodic Protection (CP) is an electrochemical means of corrosion control. CP is
defined as the reduction of corrosion by making a metal a cathode.

 CP can be accomplished by two widely used methods:

 1. The sacrificial anode method
 2. Impressed current method

 1. The sacrificial anode method

 It is achieved by coupling a given structure (say Fe) with a more active metal such as
zinc or magnesium. This produces a galvanic cell in which the active metal works as
an anode and provides a flux of electrons to the structure, which then becomes the
cathode. The cathode is protected and the anode progressively gets destroyed, and
is hence, called a sacrificial anode.
Sacrificial anode
 Circuit setup
 Figure shows the electrical connection for the sacrificial anode method. Assume the
metal to be protected is steel (from the e.m.f series its potential is (+ 0.44) volt,
magnesium (Mg) may be used to protect the steel because its potential is (- 2.34)
volt which is more active than steel. Mg is the source of current (electrons) which
will drive the spontaneity of the reaction from right to left:
Fe Fe+2 + 2e
Sacrificial anode
 An advantage of sacrificial anode systems is the flexibility in application. Anodes can
be installed in a variety of applications and configurations. No outside power is
required for cathodic protection to be effective. Another advantage is the minimal
maintenance required for these systems to function.
 Disadvantages of sacrificial anode systems include the limited protection current
available and limited life. Sacrificial anodes are subject to rapid corrosion
(consumption) and require replacement on a regular basis. Typical design life of a
pipeline system anode is five to ten years.
Sacrificial anode
 What is capacity?
 For example, pure zinc has a theoretical maximum capacity of 820 Ah per kilogram (373
Ah per pound). This means that if a zinc anode were to discharge one ampere
continuously, one kilogram would be consumed in 820 hours. If this kilogram was
discharging one tenth of an ampere, it would be totally consumed in 8200 hours or 48
weeks. Actually, zinc anodes operate, typically, at about 95 % efficiency. This means
that the energy content available for useful current output would be 820 x 0.95, or 779
Ah per kg.
 How to find the expected life of sacrificial anodes
 Equation for "Sacrificial anode expected life:
 Years life = 0.116 * Anode weight (lbs) * Efficiency * UF /current (amp)
 UF: the utilization factor of the anode. It is a constant value. It indicates how much of
the anode can be consumed before it ceases to be effective.
 The anode utilization factor is required because it is not possible to obtain 100%
utilization of the anode material.
 A value of 0.8 for UF indicates that 80% of the anode can be consumed, before it should
be replaced. In this course we will use a typical value of 0.85 for UF.
Sacrificial anode
 Example:
 Assume that a 32 pound magnesium anode is producing 0.1A at 50% efficiency and
that a 30 pound Zinc is producing 0.1 A at 90% efficiency. Compare the expected
operating lives at 0.1 AMPS output.
 Solution

 Mg life = 0.116 * Anode weight( Lbs.) * Efficiency * UF/current(amp)

 = 0.116 * 32 *0.50 *0 .85 / 0.1
 = 15.8 years

 Zn life = 0.0424 * Anode weight( Lbs.) * Efficiency * Utilization factor /current(amp)

 = 0.0424 *30 *0.90 *0.85 / 0.1
 = 9.7 years
Sacrificial anode
 Number of Required Anodes
 N = Y*C*I/W
 N = number of impressed current anodes
 Y = design life in years
 I = total current required in amperes
 C = anode consumption rate in kg/A-yr
 W = weight of a single anode in kg
  
 Example:
 Y = 16 years
 I = 0.1 A
 C (for Mg anode) = 14.24 kg/A.y
 W = 14.55 kg
 N = 1.599 ~ 2 anodes
Applications of Cathodic Protection (CP)
 • Buried pipelines
 • Buried Tanks
 • Buried communication and power cables
 • Ships and marine metallic structures
 • Water and gas distribution systems
 • Internal protection of heat exchangers and hot water tanks
 • Reinforced steel in concrete
Impressed current method
 The second method involves impressing a direct current between an inert anode
and the structure to be protected. Since electrons flow to the structure, it is
protected from becoming the source of electrons (anode). In impressed current
systems, the anode is buried and a low voltage DC current is impressed between the
anode and the cathode.
Impressed current method
 Anode Backfill: Contains materials that absorbs water, expands and makes good
contact between the soil and anode, reducing ground-bed resistance
 The prime purpose of using the backfill is to reduce electrical resistivity. This
provides a lower anode-to-earth resistance and greater current outputs in cases
where the surrounding soil is of high resistivity.
 Gives better current efficiency
 Reduce possibility of local corrosion
 Keeps environment surrounding anode moist
 Increases effective anode size
Impressed current method
Anodic Protection
 It is an electrical protection method. Reduction in corrosion by this method is achieved
by making a metal structure anode (positive electrode) with a low voltage direct
current so that it attains and retains an electrochemically passive state in a particular
environment.
Anodic Protection
 Applications for AP.
 1. To protect storage tanks containing highly corrosive electrolytes.
 2. To protect process vessels containing highly corrosive electrolytes.
 3. To protect stainless heat exchangers in sulfuric acid plants.
Corrosion Inhibitors
 An inhibitor is a chemical substance when added in a small concentration to an
environment, retards the corrosion rate.
 Corrosion inhibitors can be solids, liquids, and gases, and can be used in solid,
liquid, and gaseous media. Solid media can be concrete, coal slurries or organic
coatings (paints). Liquids may be water, aqueous solutions, or organic solvents.

 Mechanism:
 By adsorption as a thin film onto the surface of a corroding metal.
 By inducing formation of a thick corrosion product (oxide film).
 By changing the characteristics of the environment :
 Producing protective precipitate (e.g. CaCO 3).
 Removing or inactivating an aggressive constituent.
Corrosion Inhibitors
 1- Anodic Inhibitors
 They are anion which migrate to anodic sites and reduce the metal dissolution. They
cause the anodic potential to shift in a more positive direction. Sodium Chromate
(Na2CrO4), Sodium nitrite (NaNO2).

 2- Cathodic inhibitors
 Cathodic inhibitors affect the usual cathodic reactions

 The inhibitor react with the hydroxyl ions in (A) to precipitate insoluble compounds
on the cathode site, thus blanketing the cathode from the solution and preventing
the access of oxygen to the cathode site.
Corrosion Inhibitors
 These are cations which migrate towards cathodic areas and slow the reduction
reactions at these areas. This mechanisms causes the potential of the cathode to
shift to a more negative direction. This shift is called cathodic polarization
Corrosion Inhibitors
 Cathodic Poisons (Hydrogen-Evolution Poisons)
 These substances such as antimony, arsenic, sulfur, tellurium, selenium and cyanide ions,
hinder the hydrogen evolution reaction (B).
 2H+ + 2e H2
 As a consequence, these substances are very effective in acid solutions.

 Oxygen-scavengers inhibitors (OSI)

 Dissolved oxygen is found in neutral waters such as boiler feed waters and brines. In
these waters O2 is the principle corrosive factor and it must be removed to avoid
corrosion. Mechanical techniques must be used first to reduce O2 concentration to 1ppm.
Common techniques are stripping and vacuum deaeration. Some processes require O2
concentration at 50 parts per billion or less. Boiler feed water, for example, needs 7ppb
or less of O2 concentration. The OSI are used to reduce O2 concentration below 1ppm.

 1. Hydrazine (N2H4):
 2. Sodium Sulfite (Na2SO3):
Corrosion Inhibitors
 3. Organic inhibitors
 They are also called “adsorptive inhibitors “, and they are complex mixture of many
compounds. They affect both anodic and cathodic areas. They are polar compounds,
their molecules adsorb to the metal surface by the chemisorption process and form
organic film on the surface. Most of the organic inhibitors contain nitrogen, or
sulphur or both.
 The effectiveness of organic inhibitors depends on the chemical composition, their
molecular structure, size of the molecule, and their affinities for the metal surface.
Coatings
 All coatings provide barrier protection; that is, they provide a barrier between the
corrosive environment and the metal substrate.
 1. Noble coatings: which provide only barrier protection. If noble, the coating
must be a perfect barrier layer or galvanic corrosion will attack the base metal at
any bore or scratch in the coating, unless the base metal passivates very readily.
 2. Sacrificial coatings: which, in addition to barrier protection, also provide
cathodic protection
Coatings
 All coatings provide barrier protection; that is, they provide a barrier between the
corrosive environment and the metal substrate.
Exercise:

 A tank made from carbon steel and coated internally with vinyl coatings is used to
store treated water. The diameter of the tank is 29 feet and filled to a height of 31
feet. It is planned to use 60 pound Mg anodes for cathodic protection. The required
current for protection is 10 mA/ft2.
 a) How many amperes are necessary for protection?
 b) How many pounds of Mg anodes will be required for 5 year protection?
 c) How many anodes will be required?
Exercise:

 Answers:
 Given Data: D = 25 ft, H = 30 ft, W/anode = 60 Ib. /anode, I = 10 mA/ft2.

 Solution: Part (a)

 2  10mA
 Contact A = D +  DH = (25)2 + ( ) (25) (30) = 2847.07 ft 2 I (2847.07 ft 2 )  28.47 103 mA = 28.5 A
4 4 ft 2

(0.116) (W ) ( E ) (U )
 Solution: Part (b) Mg life (YL) =
I

W = Anode weight, E= Efficiency = 0.5 for Mg, U = Utilization factor = 0.85 for Mg anode, I = Required current in A

(0.116) (W ) ( E ) (U ) (0.116) (W ) (0.5) (0.85)

Mg life (YL) = =
I 28.5
5 years  1.73E-3 W  W = 2890.5 Ib

 Solution: Part (c)

 # Anodes = 2890.5 Ib / 60 Ib /anode = 48 anodes