METAL FINISHING SOLUTIONS BEYOND THE SURFACE

PASSIVATION OF STAINLESS STEEL

 PASSIVATION OF STAINLESS STEEL

Passivation of Stainless Steel

Getting the Properties You've Paid For

by Dan Englebert, Vice President Technical Services

Imagineering Enterprises, Inc.

The conversation usually starts out something like this: “Hey, this is Joe from Joe's
Machine Shop. We've got a job in here we're working on and the customer wants us to
have some kinda passivate coating something-or-other. You guys do that? How thick is
that stuff? Is that like some kinda plating or paint or something? What color is it? How
much tolerance should I allow for it?” Usually, the opening statement ends with a
phrase like, “I don't even know why they need it. What's the point of using stainless
steel if your gonna put some kinda coating on it anyway?”

The fact of the matter is, “Joe” is not the exception. Many machine shops, purchasing
agents, and engineers alike are somewhat in the dark when it comes to the relationship
between corrosion resistant (stainless) steel and chemical passivation. Even among the
metal finishing community, there is some disagreement about the theory behind the
process of chemical passivation. Some believe it is effective because it is a cleaning
process. Others credit the enhanced corrosion resistant properties to the thin,
transparent oxide film resulting from chemical passivation. Regardless of the argu-
ment, the bottom line is, it works! Verification tests, including copper sulfate immersion,
and accelerated corrosion tests, such as salt spray, high humidity, and water immersion,
undisputedly confirm the effectiveness of chemical passivation. Advanced material engi-
neers in aerospace, electronics, medical, and similar high-tech industries have utilized
chemical passivation for many years. Their applications demand the maximum perform-
ance from components manufactured from corrosion resistant (stainless) steels, and
they realize that passivation is one of the most effective methods of achieving the
desired results.

What is Passivation?
According to ASTM A 380, passivation is “the removal of exogenous iron or iron com-
pounds from the surface of a 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 pas-
sivation as “the chemical treatment of a stainless steel with a mild oxidant, such as a
nitric acid solution, for the purpose of enhancing the spontaneous formation of the pro-
tective passive film.”

In layman's terms, the passivation process removes “free iron” contamination left behind
on the surface of the stainless steel as a result of machining and fabricating processes.
These contaminants are potential corrosion sites which, if not removed, result in prema-
ture corrosion and ultimately result in deterioration of the component. In addition, the
 PASSIVATION OF STAINLESS STEEL

passivation process facilitates the formation of a very thin, transparent oxide film, which
protects the stainless steel from “selective” oxidation (corrosion). So what is passivation? Is
it cleaning? Is it a protective coating? In my opinion, it is a combination of both!

How is the Passivation Process Performed?

The process typically begins with a thorough cleaning cycle. It is intended to remove
oils, greases, forming compounds, lubricants, coolants, cutting fluids, and other undesirable
organic and metallic residue left behind as a result of fabrication and machining
processes. General degreasing and cleaning can be accomplished by a variety of com-
monly accepted methods, including vapor degreasing, solvent cleaning, and alkaline soaking.

After removal of the 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 per-
formed to develop alternative processes
and solutions that are more “environmen- TWO-HOUR salt spray test per ASTM B-117.
tally friendly,” yet equally effective. Although With passivation on the left and without on
alternative solutions containing citric acid the right.
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 minutes and 2 hours. Typical bath temperatures range between room
temperature and 160°F. Nitric acid concentrations in the 20% to 50% by volume range
are 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 (parts per
million) of metallic impurities, and chemical maintenance, is crucial for success.

The type of stainless steel being processed is the determining factor when selecting
the most effective passivation process. Bath selection (time, temperature, and concen-
tration) are all a function of the type of alloy being 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, and in extreme cases, can lead to catastrophic failure,
including extreme pitting, etching and/or totaldissolution of the entire component.
 PASSIVATION OF STAINLESS STEEL

Equipment and Precautions

Passivation should only be performed by trained, experienced technicians familiar with
the potential hazards associated with the science. Safety practices must be fully under-
stood when handling passivation chemicals. Special boots, gloves, aprons and other
safety equipment must be utilized. 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 devastat-
ing! Furthermore, in order to comply with EPA requirements, the necessary water and
air permits and treatment capabilities must be in place. The days of the “mom-and-pop”
shops performing passivation in a stone crock in the back corner of the shop are dimin-
ishing, due to safety and environmental concerns.

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 infor-
mation, 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 don't have to “reinvent the wheel,” and by taking advan-
tage of the past experiences of others, both successes and failures, you can eliminate
much of the guesswork that would otherwise accompany a new process.

Although recently cancelled, the most commonly referenced industry specifications

regarding passivation are Fed. Spec. QQ-P-35C, which is now superseded by ASTM
A-967, and ASTM A-380. All three are well written, well defined documents which pro-
vide guidance on the entire process, from manufacturing to final testing requirements. If
you're not sure what you need, they can be referenced in full, or selectively. The testing
requirements can be utilized or waived, depending upon 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 6 minutes, 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 2 hour Salt Spray or
24 hour high-humidity test. These tests are performed by placing passivated parts in
a highly controlled chamber which creates an accelerated corrosive environment. 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.
 PASSIVATION OF STAINLESS STEEL

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, gross contamination
introduced during manufacturing and/or thermal processes leads to unacceptable test
results. The following practices will reduce gross contamination during manufacturing
and increase the chances of successful passivation and test results:

Stainless steel parts are supposed to be So how does this happen?

rust - resistant.

* Never use grinding wheels, sanding materials, or wire brushes made of iron, iron
oxide, steel, zinc, or other undesirable materials that may cause contamination of the
stainless steel surface.
* The use of carbide or other non-metallic tooling is recommended whenever possible.
* 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 alumi-
na sand for abrasive blasting. Never use steel shot or grit, or abrasives which 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 contami-
nants deeper into the substrate, making them almost impossible to remove during pas-
sivation.
* Care should be taken during all thermal processes to avoid the formation of discol-
oration (oxides). Passivation is not designed to remove discoloration, and will not pene-
trate heavy oxide layers. In extreme situations, additional pickling and descaling opera-
tions 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.
 PASSIVATION OF STAINLESS STEEL

Conclusions
So how do you get “the performance you've
paid for” from high-dollar stainless steel
alloys? It really boils down to a basic under-
standing 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. It's a well known fact that
passivation will enhance the corrosion
resistance of stainless steels, but to realize Copper Sulfate test per MIL-STD-753.
the maximum performance from these high- With passivation on left and without
tech alloys, all parties involved with manu- on right.
facturing must understand their responsibili-
ty in maintaining the integrity of the material
throughout the process.

About the Author:

Dan Englebert is the Vice-President, Technical Services at Imagineering Enterprises,
Inc., a metal finishing and consulting firm located in South Bend, Indiana. TheQS-
9000/ISO 9002 certified company was founded in 1959 and is recognized globally as
an Electroless Nickel Plating expert source. Imagineering is a member of the National
Association of Metal Finishers (NAMF) and the Indiana Association of Metal Finishers
(IAMF). Englebert is a member of the American Electroplaters and Surface Finishers
Society (AESF) and the National Association of Corrosion Engineers (NACE).

References
1. ASTM A 380 - 96 Standard Practice for Cleaning, Descaling, and
Passivation of Stainless Steel Parts, Equipment, and Systems

* ASTM Committee A-1 on Steel, Stainless Steel, and Related Alloys

* ASTM Committee on Standards
100 Barr Harbor Drive
West Conshohocken, PA 19428

2. Fed. Spec. QQ-P-35C October 28, 1988 Passivation Treatments

For Corrosion Resistant Steel

* CANCELLED April 4, 1997

* SUPERSEDED by ASTM A 967 - 96
 PASSIVATION OF STAINLESS STEEL

3. ASTM A 967 - 96 Standard Specification for Chemical

Passivation Treatments for Stainless Steel Parts

* ASTM Committee A-1 on Steel, Stainless Steel, and Related Alloys

* ASTM Committee on Standards
100 Barr Harbor Drive
West Conshohocken, PA 19428

4. ASTM B 117 - 95 Standard Practice for Operating Salt Spray

(Fog) Apparatus

* ASTM Committee G-1 on Corrosion of Metals

* ASTM Committee on Standards
100 Barr Harbor Drive
West Conshohocken, PA 19428