Chloride attack on stainless steel.

A guide to leaks, pin holes and heart ache in the food i

ndustry.
Any compound capable of donating free chlorine ions (Cl -) to an aqueous (waterbased) solution has the potential for causing failure in stainless steels. The chlorine
ion is extremely electronegative, and therefore very reactive with certain
compounds and elements. This reactivity is part of its usefulness in certain
situations, but becomes a double-edged sword where stainless steel is concerned.
Chlorine can be introduced into a piping system in many ways, but the most
common seen in food industry applications are as salt (sodium chloride) and in
chlorine-based sterilising solutions such as bleach (sodium hypochlorite.) Salt
water (brine) is known to corrode stainless steel, as is bleach. Evidence of severe
corrosion in seawater applications is frequently found in textbooks dealing with
corrosion. The following picture shows severe corrosion in a 304L stainless steel
tube that carried water used for cooking cheese. The salt in the cheese leached
into the water, creating an ideal environment for corrosion.

Chloride Attack on Stainless Steels

Chloride-induced corrosion is not bulk corrosion. We are all familiar with one of the
most common forms of bulk corrosion: rust. When iron rusts, the attack is fairly
uniform over the surface exposed to the corrosive environment. Chloride attack of
stainless steel is exactly the opposite crevices and pits form and grow
perpendicularly to the surface being attacked, rather than spreading out evenly as
rust does. Some areas may appear essentially untouched by the corrosion, while
others will be severely attacked. This means that thicker tubes and pipes will not
necessarily last much longer than thin ones before failing due to chloride induced
corrosion.
This is an example of pitting:

Stainless steels have excellent corrosion resistance. Water supplies will usually
have chlorine or hydrochloric acid added to prevent bacterial growth, it is important
to use a material that will resist corrosion by such harsh chemicals. 316 stainless is
highly effective in resisting this corrosion.
Stainless steel dissolves very slowly in water, even RO (reverse osmosis) water,
so only a very small amount of chemical compound elements are added to the
water. Using plastic, copper, or iron allows all kinds of unknowns to be added to the
water. Plasticiser, from certain plastics, can be leached into the water system,
especially when aggressive RO water is used.
Stainless steel is a very clean material and can be sanitised easily. If dead spaces
are minimized and surfaces polished to eliminate crevices and pits, bacteria growth
is minimized. This is especially true when the piping system is flushed or has
continuous water circulation at velocities high enough to cause turbulent flow.
Turbulent flow is important because the turbulence creates a scouring of the pipe
surface. Low flow or laminar flow leaves a stagnant film of water next to the pipe
surface and a biofilm can form.
Since corrosion resistance is a primary reason for the use of stainless steels, a
basic understanding of the types of corrosion and how they occur is important.

Definition:
Corrosion is the degradation of a metal by its environment--it literally means to
"gnaw away". Most metals do not exist as a solid metal piece of material. In their
natural state, they exist in the form of oxides. These metal oxides (or other metal
compounds) must be refined to create the pure metals or alloys which become
useful structural materials that can be used to build things.
Pure metals and alloys have a much higher energy state and there is a natural
tendency to return to their lower energy state. Corrosion is the process nature uses
to return metals to their original state. The rate of corrosion depends upon the
environment and the type of material. It can be very rapid in a highly corrosive
environment or take thousands of years in a slightly corrosive environment.
Corrosion, whether in the atmosphere, underwater, or underground, is caused by
the flow of electricity from one metal to another metal, or from one part of the
surface of a piece of metal to another part of the same metal where conditions
permit the flow of electricity. For this to occur there must be a moist conductor or
electrolyte present for the flow of energy to take place.

Different

types:

There are many types of corrosion that can affect metals. They include:
general, electrochemical, galvanic, pitting, crevice, impingement, erosion, stress,
biological,
and
intergranular.
The most likely are:

galvanic / electrochemical

pitting and crevice

intergranular

biological

Galvanic/Electrochemical:
The diagram below illustrates a cell showing the corrosion process in its simplest
form. This cell includes the following essential components.

A metal anode

A metal cathode

A metallic conductor between the anode and the cathode

An electrolyte in contact with the anode and cathode, but not necessarily of
the same composition at the two locations.

The components are arranged to form a closed electrical path or circuit.

Suppose that the anode is iron, the cathode is copper, and the electrolyte is water
containing mineral salts. The anode is negatively charged and the cathode is
positively charged. This difference in charge (voltage) provides potential voltage,
which is the driving force for current to flow in the cell.
Since the iron in the test cell is negatively charged, and the copper is positively
charged, there is a potential voltage difference which causes a flow of electricity.
The anode will give off iron ions in the form of rust (corrosion), while hydrogen gas
would be produced at the cathode and no destruction will occur. Corrosion occurs
only on the anode. The rate of corrosion in the cell will be dependent upon the

relative sizes of the anode and cathode and the potential difference between the
anode and the cathode.
If, for instance, the anode was very small and the cathode was large, the rate of
corrosion would be very rapid. The opposite would be true if there was a very large
anode compared to the cathode. If the anode was nickel and the cathode brass,
there will be very little corrosion, because the voltage potential difference will be
slight.
Galvanistic corrosion occurs when dissimilar metals are used. When the materials
have a large difference in voltage charge they are more likely to corrode. For
instance, if aluminium was the anode and silver was the cathode, the aluminium
would corrode very rapidly, because they are dissimilar metals. Of course, to
corrode there must be an electrolyte presentwater, moist air, etc. Naturally the
closer together the metals or alloys are in the galvanistic series, the less likely that
corrosion will occur.
Galvanic Series of Metals:
The metals below are arranged according to their tendency to corrode galvanically.
Metals with negative voltage charges (anodicleast noble) are listed first, followed
by metals with positive charges (cathodicmore noble).
The
CORRODED
(anodic, or least noble)

Magnesium,

Magnesium alloys

Zinc

Cadmium

Aluminium 2017

END

Steel or iron, Cast iron

Chromium-iron (active)

Ni-Resist irons

18-8
Chromium-nickel-iron
18-8-3 Cr-Ni-Mo-Fe (active)

(active)

Lead-tin solders, Lead, Tin

Nickel
Inconel
Hastelloy C (active)

Brasses,
Monel

Silver Solder

(active)
(active)

Copper,

Bronzes,Copper-nickel

alloys

Nickel (passive), Inconel (passive)

Chromium-iron
Titanium
18-8
18-8-3
Hastelloy C (passive)

(passive)
Chromium-nickel-iron
Cr-Ni-Mo-Fe

(passive)
(passive)

Silver

Graphite
Gold
Platinum

PROTECTED END (cathodic, or more noble)

Pitting
and
Crevice:
These localised attacks on stainless steel can produce surface pitting and crevice
corrosion. Most pits form when there is an inclusion or there has been a breakdown
of the passive film. Crevice corrosion occurs at locations where crevices exist, such
as threads, machining grooves, tears, metal lap joints, etc.
The illustration below shows how corrosion occurs at a crevice created by a lap
joint. At the edge of the lap joint, movement of water (electrolyte) flushes away
metal ions resulting in a lower metal ion concentration. The space between the two
pieces of metal is stagnant and there is a higher concentration of metal ions,
allowing corrosion to occur at the edge of the mechanical joint.

An oxygen concentration cell may also form if there is a depletion of oxygen in the
dead space in the lap joint. If the material is stainless steel and there are high
levels of chlorine in the water, the chlorine will attack metal in the dead space
between the two pieces of metal, breaking down the passive film.

Since there isn't any oxygen available to regenerate the passive film, the stainless
becomes active (anodic) in this cell and the rest of the stainless stays passive
(cathodic) because the passive film remains intact. With this lap joint in water
(electrolyte) conditions are right for current to flow and corrosion occurs in the
crevices formed in the lap joint.
Concentration cells can form in any crevice in watering systems and corrosion is
more likely to occur with the use of chlorine or hydrochloric acid. Corrosion may be
accelerated if there are large amounts of organic material and very low levels of
oxygen in the water along with the use of chlorine. Oxygen is necessary to maintain
the passive film.
Edstrom Industries uses 316 stainless steel to prevent pitting problems due to the
use of chlorine. The molybdenum in 316 helps to stabilize the passive film,
although excessive levels of chlorine will corrode even 316 stainless steel.
Intergranular:
This type of corrosion may occur next to a weld if the carbon content of the
stainless steel is too high. When stainless steel is welded, material next to the weld
reaches a temperature of only 800 to 1500F. At these temperatures, the
chromium and carbon form chromium carbides. Chromium carbides deplete the
chromium at the weld interface and sensitise the material, making it subject to
corrosion.

If a weld interface is deficient, it cannot maintain the passive film. This area
becomes anodic, while the rest of the material is cathodic. When the material is in
water or moist air (the electrolyte), current will flow, resulting in corrosion (rusting)
at the weld interface. By reducing the carbon content, we can prevent carbides
from forming. For this reason, Edstrom Industries uses 316L or 304L stainless steel
when welding to avoid intergranular corrosion.
Biological:
When a metallic surface is immersed in water, a biofilm will begin to form if there is
any bacteria in the water. A biofilm is a microbial mass composed of aquatic
bacteria, algae, or other microorganisms. The biofilm begins when organic material
is absorbed onto the surface of the metal. The flow of water transports microbes to
the surface, and the microorganisms attach and then grow, using nutrients from the
water.
Bioflm formation on the inside surface of a pipe.
The figure below shows a sketch of a biofim
formed on a metal surface in a pipe. The bioflm
begins with the absorption of organic matter to the
metal surface from the water. The flow of water
transports microbes to the surface and the
microorganisms attach and then grow, using
nutrients from the water.

When the microorganisms grow, oxygen is excluded, which creates a place where
the passive film may break down. With the breakdown of the passive film, the site

becomes anodic with the likelihood of corrosion. Biofilm formation is most likely in
spots where the flow of water is low, such as voids, crevices, and thread joints.

Steps in biofilm formation. Formation is initiated when small organic molecules

become attached to an inert surface
(1) Microbiological cells are absorbed onto the resulting layer
(2). The cells send out hair like exopolymers to feed on organic matter and attach
themselves to the surface
(3), adding to the coating
(4). Flowing water detaches dome of the formation
(5), producing an equilibrium layer