Passivation of Stainless Steel

Passivation describes the treating of a metal with a mild oxidant (such as nitric acid) to remove
surface iron or iron compounds by dissolution. This action forms a protective passive film on the
surface of the metal. The trace iron left behind from machining and fabrication can provide sites
for corrosion if left untreated.
The process is performed by first cleaning the surface with solvents or an alkaline solution to
remove organic or metallic residues. Next, the parts are placed into passivation solutions. The
choice for this solution is usually nitric acid. The process is controlled by three key variables:
time, temperature, and concentration.
Typical Range of Key Variables
Time: 20-120 minutes
Temperature: 60 - 160 0F
Concentration: 20 - 50% Nitric Acid by volume
The type of stainless steel alloy being processed typically determines the key variables. For
example, 316 stainless steel would have different conditions than 317L stainless steel.
After the passivation bath, a sodium dichromate bath is often used to promote the formation of a
chromic oxide film. After this final treatment, the sample is placed into a copper sulfate solution.
Any remaining iron will show up as pink spots on the sheet. This would be considered
unacceptable. Other testing methods can include a two hour salt spray or a 24 hour high
humidity test.
What is passivation?
According to ASTM A380, passivation is "the removal of exogenous iron or iron compounds from
the surface of stainless steel by means of a chemical dissolution, most typically by a treatment
with an acid solution that will remove the surface contamination, but will not significantly affect
the stainless steel itself." In addition, it also describes passivation as "the chemical treatment of
stainless steel with a mild oxidant, such as a nitric acid solution, for the purpose of enhancing
the spontaneous formation of the protective passive film."
In lay terms, the passivation process removes "free iron" contamination left behind on the
surface of the stainless steel from machining and fabricating. These contaminants are potential
corrosion sites that result in premature corrosion and ultimately result in deterioration of the
component if not removed. In addition, the passivation process facilitates the formation of a thin,
transparent oxide film that protects the stainless steel from selective oxidation (corrosion). So
what is passivation? Is it cleaning? Is it a protective coating? It is a combination of both.
How is passivation performed?
The process typically begins with a thorough cleaning cycle. It removes oils, greases, forming
compounds, lubricants, coolants, cutting fluids and other undesirable organic and metallic
residue left behind because of fabrication and machining processes.

General degreasing and cleaning can be accomplished many ways, including vapor degreasing,
solvent cleaning and alkaline soaking.
After removing organic and metallic residues, the parts are placed into the appropriate
passivation solution. Although there are many variations of passivating solutions, the
overwhelming choice is still the nitric-acid-based solutions.
Recently, there has been substantial research performed to develop alternative processes and
solutions that are more environmentally friendly, yet equally effective. Although alternative
solutions containing citric acid and other types of proprietary chemistry are available, they have
not been as widely accepted commercially as nitric-acid-based solutions.
The three major variables that must be considered and controlled for the passivation process
selection are time, temperature and concentration. Typical immersion times are between 20 min
and two hours. Typical bath temperatures range between room temperature and 160F. Nitric
acid concentration in the 20 to 50% by volume range is generally specified. Many specifications
include the use of sodium dichromate in the passivation solution or as a post passivation rinse to
aid in the formation of a chromic oxide film. Careful solution control, including water purity, ppm
of metallic impurities and chemical maintenance, are crucial for success.
The type of stainless steel determines the most effective passivation process. Bath selection
(time, temperature and concentration) is a function of the type of alloy processed. A thorough
knowledge of the material types and passivation processes is paramount to achieving the
desired results. Conversely, improper bath and process selection and/or process control will
produce unacceptable results. In extreme cases, this can lead to catastrophic failure, including
extreme pitting, etching and/or total dissolution of the entire component.
Equipment and precautions
Trained, experienced technicians familiar with the potential hazards associated with the science
should only perform passivation. Safety practices must be fully understood when handling
passivation chemicals. Special boots, gloves, aprons and other safety equipment must be used.
Tanks, heaters and ventilation, as well as baskets and racks must be appropriately engineered
to perform the process. Iron or steel parts or equipment must never be introduced to the
process, or the results can be devastating. Furthermore, in order to comply with EPA
requirements, the necessary water and air permits and treatment capabilities must be in place.
The days of mom-and-pop shops performing passivation in a stone crock in the back of the shop
are gone.
Specifications and verification testing
There are a few generally accepted industry specifications available for reference when
choosing a passivation process. They offer time, temperature and concentration information and
subsequent testing requirements to validate the effectiveness of the process. Many large
corporations have developed internal specifications to control their unique requirements
regarding passivation and verification testing. Regardless of the situation, it is usually prudent to
reference a proven procedure when requesting passivation.

By referencing a specification, you do not have to reinvent the wheel. By taking advantage of the
experiences of others, both successes and failures, you can eliminate much of the guesswork
that would otherwise accompany a new process.
Although recently canceled, the most commonly referenced industry specifications regarding
passivation are Federal Specification QQ-P-35C, which is now superseded by ASTM A-967 and
ASTM A-380. All are well-written, well-defined documents that provide guidance on the entire
process, from manufacturing to final testing requirements. If you are not sure what you need,
they can be referenced in full or selectively. The testing requirements can be used or waived,
depending on the individual situation.
One of the most commonly specified verification tests is the copper sulfate test. Passivated parts
are immersed in a copper sulfate solution for six min, rinsed and visually examined. Any copper
(pink) color indicates the presence of free iron and the test is considered unacceptable.
Other validation tests include a two-hr salt spray or 24-hr high-humidity test. Placing passivated
parts in a highly controlled chamber that creates an accelerated corrosive environment performs
these tests. After subjecting the test pieces to the corrosive atmosphere for the prescribed
exposure periods, the parts are removed and evaluated. Although results can be somewhat
subjective, ASTM B-117 is an excellent reference in determining acceptability. It is important to
note that each of the test methods mentioned have different advantages and limitations. Care
should be taken to select the appropriate test methods based on alloy type and end-use
environment.
Machining and heat treating techniques
Perhaps the most overlooked variable in the entire passivation equation is the negative impact
of poor machining and heat treating practices. All too often, cross contamination introduced
during manufacturing and/or thermal processes leads to unacceptable test results. The following
practices will reduce cross contamination during manufacturing and increase the chances of
successful passivation and tests results.
Never use grinding wheels, sanding materials or wire brushes made of iron, iron oxide, steel,

or other undesirable materials that may cause contamination of the stainless-steel surface.
The use of carbide or other non-metallic tooling is recommended.
Grinding wheels, sanding wheels and wire brushes that have been previously used on other

metals should not be used on stainless steel.

Use only clean, unused abrasives such as glass beads or iron-free silica or alumina sand for
abrasive blasting. Never use steel shot, grit or abrasives that have been used to blast other
materials.
Thorough cleaning prior to any thermal processing is critical. Stress relieving, annealing,
drawing or other hot-forming processes can actually draw surface contaminants deeper into
the substrate, making them almost impossible to remove during passivation.
Care should be taken during all thermal processes to avoid the formation of oxides. Passivation
is not designed to remove discoloration and will not penetrate heavy oxide layers.

In extreme situations, additional pickling and descaling operations are required prior to
passivation to remove the discoloration. Controlled atmosphere ovens are highly recommended
for all thermal processes to reduce airborne contamination and prevent oxides from developing.
So how do you get the performance you have paid for from high-dollar stainless steel alloys? It
boils down to a basic understanding that the passivation process is both an art and a science,
and that machining, fabricating and heat treating practices can substantially affect the corrosion
resistance of the component. Passivation will enhance the corrosion resistance of stainless
steels, but to realize the maximum performance from these high-tech alloys, all parties involved
with manufacturing must understand their responsibility in maintaining the integrity of the
material throughout the process.
PITTING
The mechanism of pitting is essentially the same as crevice corrosion. The difference is that
whereas in crevice corrosion the phenomenon is derived from the fact that a crevice already
exists, pitting needs to be initiated - take for example cases of pitting in the tank tops in the
centre of a steel plate, nowhere near a weld seam or a crevice.
Pitting is avoidable. Like crevice corrosion, only one of the factors leading to it has to be
removed to stop the reaction.
When a clean tank is inspected and pitting is observed, then it is a case of locking the stable
door after the horse has bolted. We are seeing the result of a previous corrosion cell. When we
measure the passivity of the steel, even inside a corrosion pit, it almost invariably shows a
passive area. Passivity is the unlikelihood of a particular area to corrode. Inside a pit under
inspection conditions the electrolyte has been removed, as far as is observable. Inside the
pitting the steel has access to oxygen and the passive chromium oxide layer has been restored.
This is no reason, however, to ignore the pitting. The chromium concentration on the surface of
the pit will be less than that of the surface surrounding it. The pit can trap seawater again in the
future and reactivate a corrosion cell.
The pitting has to be removed mechanically and filled by the correct metal. The resulting repair
must be devoid of crevices. In other words, the repair must have the same characteristics as the
surrounding steel. This is achieved by careful welding followed by the minimum removal of new
material by mechanical means to achieve a smooth finish. This is followed by firstly activating
the steel in the area by pickling to remove unwanted oxides and contamination, followed by
passivation to restore the passivating chromium oxide layer. Weld spatter must be similarly
removed from the surrounding area and the area similarly pickled and passivated.
Pitting is often associated with areas of uniform corrosion. For example, an area of steel about
1m2 is rougher than the area surrounding it. Inside this area are examples of even worse
corrosion in the form of pitting, either shallow, open pitting or deep pinpoint pitting.
It is necessary to look at the causes of pitting to avoid it in the future.
Pitting is caused by starving a surface of the steel of oxygen relative to the surrounding
surfaces, followed by exposing both to an electrolyte.

To starve a steel surface of oxygen you need to contaminate it.

Some examples of contamination are :
Free iron. If iron from tools or boots imbeds itself into the stainless steel surface, then the
surface will rust and the rust will form a porous layer on the stainless steel surface. The steel
surface is deprived of oxygen but an electrolyte can penetrate through to the steel surface. We
have created an 'artificial crevice'.
Organic deposits, Mud or silt, Remains of impure cargoes such as wet phosphoric acid. This is
usually the cause of the uniform deterioration of the surface texture of the steel, i.e. it becomes
rough or abrasive.
Following the discharging of wet phosphoric acid, a thorough tank cleaning is required. This is
needed to remove the tightly adhering sediments present in the acid. If this is not done, the large
areas of the tank surface are deprived of oxygen. Subsequent immersion in an electrolyte will
set up a gigantic corrosion cell between the 'clean' areas and the 'dirty' areas. These sediments,
as far as corrosion is concerned, have the same properties as rust - they are adherent and
porous to electrolytes.
The result is, that although through repeated use of the tank, eventually it is clean, a uniform
corrosion has occurred during the time it was dirty and exposed to electrolytes. The dirty areas
having sacrificed themselves as anodes to the clean cathodes.
Similarly, in depressions in the tank top, where sediments and electrolytes can collect
undisturbed, limited uniform and associated pitting can and does occur.
Depending upon the nature of the cargoes to be carried in the future (electrolyte or nonelectrolyte; i.e. aqueous or organic (solvents etc.) then it is advisable during a period such as
dry-docking to restore the surfaces of the affected tanks to a uniform quality by mechanical
means such as pitting repair or even polishing of rough areas, followed by complete picking and
passivation. In that way, the surface quality of the tank will once again be as intended when
new.
Passivation meter for stainless steel surfaces
The passivation meter sets up a temporary corrosion cell. The anode is the stainless steel
surface and the cathode is the reference electrode. The electrolyte is a suitable solution for the
application and is applied drop wise to a piece of absorbent paper, which is then placed on the
steel surface. The tip of the reference electrode is then placed on top of the soaked paper
thereby making a steel / electrolyte / electrode connection. The electrode is connected to a mV
meter and another contact extending from the meter to the steel completes the corrosion cell.
The mV meter contains a microchip, which performs the function of reducing the reference
electrode's absolute potential to zero. The mV reading seen on the LCD gives an indication of
the tendency that the steel will readily corrode.

The manufacturer has set the limit that any reading above 60 mV indicates a passive surface, or
in other words, an intact chromium oxide layer on the steel surface.
A reading of less than 30mV shows that the surface is still in an active state.
A reading of 30mV<reading<60mV shows that the surface is not fully passive, or that the
protective oxide "film" is incomplete.
A reading of more than 60mV and stable or rising indicates a passive surface.
Intergranular corrosion ( IGC)
IGC is a phenomenon whereby if the steel is heated or cooled through the temperature range
425-900oC, then the chromium can combine with carbon to form chromium carbide at the grain,
or crystal boundaries, or edges. The adjacent or surrounding areas are thereby depleted of
chromium and are susceptible to IGC. They are called sensitized areas. By rapid quenching of
the steel with water after welding, the steel can be desensitized and IGC avoided. IGC
avoidance is a combination of choosing the correct alloy and performing the correct quenching
after welding.
German material number 1.4435 is a correct choice of alloy for this application. The carbon level
is low enough to allow welding repairs without quenching, so long as the welded surface is clean
and free of oils. Quenching is something you can only observe during construction. However,
observation of the areas in and around welding seams during inspection indicates correct
compliance with procedures or not, i.e. that the steel surface at these areas was or was not
different to the general surface condition, except where specific instances of crevice or pitting
corrosion had occurred.

Pickling
1. 65 % - 10 Volume Nitric Acid - HNO3
2. 70 % - 2.5 Volume Hydrofluoric Acid - HF
3. 98 % - 2.5 Volume Hydrogen Sulphate - H2SO4
Passivation
1. 65 % - 10 Volume Nitric Acid - HNO3
Neutralisation
1. 5 % Sodium Carbonate - NA2CO3

WHY PICKLE ?
Pickling ensures the corrosion resistance of products made of stainless steel and thus
considerably influences their service life and usefulness.
The corrosion resistance of stainless steel is mainly based on the presence of at least thirteen
per cent chromium in the alloy. In combination with oxygen, the chromium forms a dense
chemically resistant passive layer of chromic oxide on the surface of the component. This
protects the surface against corrosion. The passive layer usually forms a new after abrasion.
The precondition is a metallically pure surface with a sufficiently high percentage of chromium.
Pickled stainless steel surfaces and welding seams

Are metallically pure, free of scales and discolouration.

Have the full corrosion resistance of the component, and
Have a decorative metallic appearance.

Every mechanical treatment damages the top layer of components by contamination with ferric
matter, change in the structure of the layers, development of stresses and reduction of
chromium content. Heat treatment like annealing and welding leads to scaling and
discolouration. These not only deteriorate the appearance of the component but especially its
oxides, which are chemically less resistant. A continuous passive layer of chromic oxide cannot
form here.
Corrosive strain on insufficiently passivated stainless steel leads to the forms of corrosion typical
for this type of material:

Pitting Corrosion
Crevice Corrosion
Stress Corrosion Cracking
Intercrystalline Corrosion
Corrosion resulting from contact with Foreign Metals.

A dense passive layer can only form on metallically pure surfaces.

Passivation Procedure for 300-Series Stainless Steels

Step 1
Prepare a 50% (v/v) nitric acid solution by pouring an equal volume of concentrated nitric acid
into an equal volume of water in a container that will not be attacked by the solution. (Nitric acid
is available in 50% strength. Phosphoric acid may be used as a substitute.) Best results will be
obtained if the temperature of the passivating solution is maintained at 130 F (54 C). Use
extreme caution when using nitric acid; it is a very dangerous chemical.
Step 2
Apply the passivating solution to the complete surface. Cover all areas several times. Keep the
surface wet with the acid solution for about 1 h. With a small vessel (15 gal or less), it is easiest
simply to fill the vessel with the passivating solution and let it soak. When dealing with larger
vessels, passivation via a spray-ball system is very effective.
Step 3
Rinse the vessel thoroughly with clean, warm water to remove all traces of acid. Wipe with a
clean cloth (wet or dry). If no discoloration appears on the cloth, the surface is conditioned and
ready to use.
Passivation is not a permanent treatment. Stainless steel surfaces can become recontaminated
and corroded if proper care is not taken.
Scope:
This pickling and passivation procedure is designed to remove weld discoloration, heat treating
scale, and iron contamination resulting from the fabrication process, from austenitic stainless
steel. Reference: ASTM, A380-88 Wyandotte Technical Service Bulletin I-85
Process requirements:
Parts to be pickled shall be thoroughly cleaned of all grease, oil, or dirt by others, prior to
delivering parts to Orbit Industries, Inc. Use of suitable alkaline cleaner such as Wyandotte
Nuvat is recommended.
Pickling: (Removes weld discoloration, heat treating scale and iron contamination) There are two
methods of pickling: Spraying method. Fill or Immersion method. Contact time to be 4 to 6
hours. Solution is Nitric Acid with additive.
Inspect the pieces and verify that discoloration, scale, and foreign material have been removed.
Passivation: (Removes iron oxide loosened by pickling and renders the metal surface
completely clean)

Rinsing removes all material loosened by the pickling procedure.

The rinsing procedure must follow directly after pickling so that the solution does not dry. Rinse
with clean water, preferably a hot high pressure wash, and a chloride content no greater than 50
mg/liter.
Contact with air after rinsing procedure will establish a passive film on the surface of the
stainless steel (Passivation)
Inspection: Assemblies shall be inspected in accordance with applicable customer requirements
and Job Quality Control Procedures.