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chemical passivation Learn more about chemical passivation

Coatings including carboxylates for the preservation of metallic heritage artefacts
L.M. Abrantes, A.I. Melato, in Corrosion and Conservation of Cultural Heritage Metallic Artefacts, 2013

Aspects of metal passivation mechanism

Studies on the role of weak acids on the chemical passivation of iron and steel in aqueous solutions have shown
that carboxylates are non-oxidizing inhibitors and as such they only provide protection in aerated solutions [61–
63]. In contact with air, active metals such as iron are covered by a thin oxide layer, with defects where the
corrosion process starts giving rise to the formation of soluble Fe(II) compounds [64]; dissolved oxygen converts
Fe(II) into Fe(III) and, in the presence of carboxylates, Fe(III) compounds suppress the corrosion by sealing those
defects in agreement with the pore plugging concept [62–65]. Along with this effect, when the conditions are
favourable for the adsorption of the inhibitor anions (adequate isoelectric point) [66, 67], the passivation process
might also be enhanced. This appears to be the case with long alkyl chain carboxylates [66, 68] and with mixtures
of azoles and carboxylates [65, 69, 70]. Comparable corrosion protection efficiency for mild steel in aqueous media
has been reported [64] for less harmful mixtures, like mono- and dicarboxylates.
The ability of anions of the monocarboxylic acids to bind to oxide-covered metal surfaces just by dipping the metal
specimens in a solution of mono-carboxylate anions with fairly low concentration has been increasingly used aiming
to replace environmentally non-friendly traditional methods, such as chromate treatment, in inhibiting the
corrosion of various metals. It is widely accepted that the negatively charged carboxylic group reacts with the
positively charged metal surface to form carboxylate bonds [71, 72]. In general, at room temperature, the
formation of those conversion coatings requires long exposure times (24–72 h) which can be reduced by raising
the bath temperature; their corrosion resistance increases with the alkyl chain length and displays good efficiencies
for very long time periods. An example of this is the behaviour of AZ31 Mg alloy treated at 50 °C for 24 h, in 1 mmol
dm−3aqueous solution of sodium salts of dodecanoic (Na-C12) and octadecanoic (Na-C18) carboxylic acids, after
immersion in 0.1 mol dm−3 NaCl [73]. The polarization curves (Fig. 23.5) clearly show that both anodic and cathodic
curves of treated samples shift towards lower currents as the alkyl chain length increases, the layer is resistive to
the presence of Cl− and the protective effect is long lasting (at least up to 216 hr).
The length of the hydrocarbon chain also has a remarkable influence on the copper corrosion inhibition; n-alkanoic
acid potassium salts (CnK) with a chain length of more than six carbon atoms enable the formation of protective
SAMs [74]. It has been demonstrated that information on conditions to enhance copper passivity (anodic currents
lowering) can be retrieved from the observed changes in the electrochemical behavior of copper in potassium
sulphate aqueous solutions (pH 10) when various n-alkanoic acid potassium salts are added [74].
Figure 23.6(b) shows the remarkable difference in the contact angles when copper modified by immersion for 24 hr
in an ethanol/water (3 :1) solution containing C15H31-CO2H + K2SO4 is contrasted to the bare substrate.
Zinc damage is mostly due to atmospheric corrosion that in humid environments promotes the formation of white
products, known as ‘white rust’, mainly composed by Zn5Cl2(OH)8, Zn5(CO3)2(OH)6 and H2O [77], with lamellar
crystallographic structures prone to adsorb chloride and water by exchange reactions or dissolution/co-
precipitation mechanisms [78]. To prevent this kind of corrosion and in searching alternatives to the traditional
application of mineral oils or chromate coatings used in galvanizing industry, anionic inhibitors such as silicate,
phosphate, phosphonate, benzoate and amine derivatives have been considered. More recently, the corrosion
inhibition efficiency of non-toxic linear sodium carboxylates (CH3(CH2)n-2COONa), already proved for other metals,
has been investigated for the protection of zinc surfaces, namely focusing the action of sodium heptanoate in
neutral and aerated solutions [78], in an attempt to reinforce the metal protection by combining carboxylate and
triazol compounds [79]. Although the intercalation of heptanoate anions in the zinc hydroxide layer leads to a
compact inorganic-organic material (zinc hydroxycarboxylate), which acts as a barrier against oxygen and avoiding
the absorption of chloride ions and water [78], the use of sodium carboxylate is not effective to inhibit zinc
corrosion, in conditions of close packing of galvanised steel products. The addition of 3-methyl benzo-triazol
(tolutriazol, TTA) to sodium heptanoate has been suggested as an interesting route to inhibit the formation of
‘white rust’ on zinc; based on electrochemical data (impedance spectroscopy and electrochemical quartz crystal
microbalance), the TTA effect has been reported as inhibiting the cathodic reaction of oxygen reduction on zinc,
whereas the heptanoate anions, forming an insoluble and hydrophobic zinc soap layer, inhibit the anodic reaction.
The associated proposed mechanism assumes an initial oxidation of zinc into Zn2+ cations by the dissolved oxygen
in solution followed by the coprecipitation of a TTA/C7-based compound which forms a thin protective film [79].

Passivation of Copper: Benzotriazole Films on Cu(111)

Federico Grillo*, Daniel W. Tee, Stephen M. Francis, Herbert A. Früchtl, and Neville V. Richardson
EaStCHEM and School of Chemistry, University of St. Andrews, St. Andrews, KY16 9ST, U.K.

J. Phys. Chem. C, 2014, 118 (16), pp 8667–8675

Abstract

Benzotriazole (BTAH) has been used as a copper corrosion inhibitor since the 1950s. However, the molecular level
detail of how adsorption and surface passivation occur remains a matter of debate. BTAH adsorption on a Cu(111)
single crystal has been investigated from medium coverage to multilayer using scanning tunneling microscopy
(STM), temperature-programmed desorption (TPD), high resolution electron energy loss (HREEL) spectroscopy and
supporting density functional theory (DFT) calculations. Both physisorbed and chemisorbed phases are observed.
One extended and highly ordered self-assembled metal−organic phase is seen at saturation coverage and above.
A metastable phase is also observed. Complete desorption occurs at ca. 600 K. Those structures are critically
discussed in the light of some of the various adsorption models reported in the literature and an alternative
adsorption model is proposed. These results allow a further understanding of the interaction between
benzotriazole and copper and, in turn, may help understanding the mechanism for protection of copper and copper
alloys from corrosion, substantially contributing to a long-standing debate.

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What is Passivation? How Does Passivation Process Work? How To Passivate Stainless Steel Parts?

What is passivation?

To answer this question lets look at what stainless steel is first. Stainless steels are naturally corrosion-resistant, &
passivating them would be unnecessary, however stainless steel is not entirely impervious to corrosion. Stainless
steel derives its corrosion resistant properties from its chromium content. The chromium, in the presence of air
(oxygen), forms a thin film of chromium oxide which covers the surface of the stainless steel. Chromium oxide, is
inert or “passive” by nature, and chromium in the material gives stainless steel its corrosion-resistant properties.

Under ideal conditions, pure, cleaned stainless steel (SS) forms an inert, oxide film when exposed to oxygen in
atmosphere which protects the SS from corrosion. Under realistic, normal conditions, foreign material in a
manufacturing environment, sulfides added to the stainless steel for improved machinability or particles of iron
from machining center cutting tools may be transferred to the surface of the stainless steel parts, and these all can
inhibit the formation of the oxide film which protects stainless steel from corrosion. Therefore, these contaminants
need to be removed down to the surface grain boundaries / structure of the stainless steel surface. This removal
and oxide growth process is called passivation.
Passivation is a non-electrolytic process typically using nitric or citric acid which removes free iron from the surface
and forms an inert, protective oxide layer that in turn renders the stainless steel more rust-resistance due to lack
of iron to react with the atmosphere.
The stainless steel passivation process chemically removes these free irons and forms a passive oxide “film” layer
which further improves corrosion resistance. When exposed to air (oxygen), the stainless steel undergoing
passivation will form a chemically inactive or inert chromium oxide surface. Per common passivation specifications
ASTM A380 & A967, 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.” Further ASTM A380 states
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.”

Therefore, a “mild oxidant”, such as a nitric acid or citric acid (mineral or organic acid solution), allows the removal
of excess iron and associated contaminants from the surface of the stainless steel and allow the formation of a
chromic oxide layer when exposed to air which allow for stainless steels corrosion resistant properties.
How does the Passivation Process Work?
Many passivation specifications (ASTM A967, AMS2700, ASTM A380) exist to instruct on the proper process
to passivate stainless steel, titanium and other materials, some of which are listed below. Common to nearly all
the specifications are: cleaning of the surface from any contaminants listed above, chemical treatment via
immersion in an acid bath (typically nitric or citric acid) and testing of the newly passivated stainless steel surface
to ensure the process steps.
This chemical treatment simply augments/expedites the naturally occurring process when the material is exposed
to oxygen in the atmosphere. It simply helps “grow” the inert, oxide layer faster and thicker than found
naturally. Some specifications call for use of sodium dichromate added to the acidic baths solutions to provide
more rapid formation of the oxide layer or passivation film. This practice of using sodium dichromate is becoming
less and less prevalent with the significant advancements in ultrasonics and citric acid known as Citrisurf® which
encourage oxygen formation at the surface of the material while the material is still in immersion of the acid bath.

How To Passivate Stainless Steel Parts? What passivation equipment is needed?

Putting together everything listed above requires a process that will properly clean and acid bath passivate stainless
steel. Common passivation process steps for stainless steel are listed below:

1. Alkaline cleaning of the materials to remove all contaminants, oils, foreign material, etc. – Commonly uses
detergent cleaners like sodium hydroxide, Micro90, Simple Green, tc
2. Water rinse – commonly with DI Water in high precision industries
3. Nitric or citric (Citrisurf) immersion bath to full dissolve any free irons & sulfides and expedite the formation
of passive film or oxide layer.
4. Water rinse – commonly with DI Water in high precision industries
5. Water rinse – commonly with DI Water in high precision industries
6. Dry parts
7. Test sample parts via specification standards using: salt spray, high humidity chamber exposure, or copper
sulfate testing
Types of Passivation Equipment and Passivation Lines
Looking for what equipment and tanks are needed for the passivation process? Be sure to check out passivation
process checklist or contact us to talk with our passivation equipment experts.

Small Benchtop Stainless Steel Passivation Tanks

Automated Ultrasonic Passivation Equipment

MultiTank Passivation Line

Best Technology is recognized as an industry leader in passivation equipment, tanks, systems and lines. Our experts
understand the various passivation specifications below and can design equipment to fit and meet passivation
requirements and specifications.
 https://www.highettmetal.com.au/blog/copper/how-to-passivate-copper
July 2012
How
The term 'passivation' refers to treating metal with chemical baths in order to make them permanently resistant
to corrosion. In some cases, passivation is the name given to the application of anti-corrosives (instead of a bath)
to various metals. The process that is used to passivate copper, however, is a little different, as there is no way to
truly alter this metal through chemical baths.
The easiest way to passivate copper is simply by exposing them to the elements. Leave them outside for
somewhere between four and eight weeks, then check to see whether a dull blue-green patina has begun to form.
This colouring actually helps to prevent further corrosion from forming.
If you do not have the time to leave your copper outside for this long, you can accelerate the process by mixing a
chemical bath. Add together just under three kilograms of ammonium sulfate, a third of a cup of copper sulfate,
an eighth of a cup of ammonia and about 24 litres of water.
This solution should be applied to the copper as a spray and left to dry between each of its six applications. After
waiting six hours, you should begin to see the patina deepening in colour. It will begin to spread around the item
much faster, protecting it from further corrosion immediately.
As you can see, the only way to protect your copper items from corrosion is to allow them to corrode a little. It is
important to take note, however, that this patina will not damage the copper in any way and, should you ever
decide that you want to return the metal to its shiny glory, it can be removed with some thorough cleaning

https://www.wattco.com/casestudy/what-is-passivation-why-do-we-need-to-passivate-flanged-heaters/

Case Study >> What is Passivation? Why do We Need to Passivate Flanged Heaters?

WHAT IS PASSIVATION? WHY DO WE NEED TO PASSIVATE FLANGED HEATERS?

Most of the parts of flanged heaters are made of stainless steel—an alloy that is mainly comprised of iron, carbon,
and chromium. Of these, chromium is the chemical element that makes the steel “stainless” i.e., resistant to rust.
Chromium reacts with the oxygen in the atmosphere to form a thin oxide layer—or a passive film—on the surface
of the metal. When stainless steel objects are cut or scratched, this passive film reacts with oxygen and “repairs”
the exposed surface, preventing the formation of rust. See Figure 1 for the advantages.
Passivation is the process of treating the metal with acids in order to remove the free iron from the surface of the
metal and coat it with this corrosion-preventing oxide layer. This passive layer gets damaged through heat or
chemical damage due to high humidity levels. This may lead to rusting of the parts of the flanged heater. Therefore,
passivation may need to be regularly performed to prevent damage to the parts of the heater.
Though nitric acid is usually used to passivate stainless steel products, in recent times citric acid is being used. It is
safer and has many advantages over nitric acid.
  It is more environment friendly (bio-degradable).
 It does not require special handling equipment.
 It does not emit harmful nitrogen oxide vapors.
 It removes only iron (and not other elements) from the alloy.
 Lesser quantities of citric acid are required (as compared to nitric acid), as the former is more effective at
removing the corrosion.
 It can also clean and brighten the metal.
Though the amount of acid, temperature, and duration of the passivation process depend on the type of alloy being
processed, the process of passivation usually involves the following steps:
1. Thoroughly clean the surface of the flanged heater, or other equipment. This removes oils, greases, and other
deposits from the surface.
2. Immerse the parts in a passivation solution (usually nitric-acid or citric-acid based) for a minimum of twenty
minutes (up to a maximum of two hours), depending on the amount of corrosion. The solution should be at room
temperature or at a maximum temperature of 160 deg. F (about 49 deg. C).
3. Once the passivation process is completed, rinse the parts in water or a solution of sodium dichromate (Na2Cr2O7)
to neutralize any remaining acid on the surface of the parts, and then drying them.
Since passivation involves the use of acids, it should be performed only by trained personnel who have experience
with industrial heating, using these acids, and who have taken adequate protection such as using rubber gloves,
boots, and other equipment to maintain safety during the operation. One can reference industry standards ASTM
A-380 and ASTM A-967 for guidance on the procedure to be followed.
After passivation, various tests can be performed to verify whether passivation has been properly performed. This
includes exposure to a salt-spray for up to two hours, or high humidity conditions for twenty-four hours. A
commonly-used method of verification is to immerse the flange parts in a copper sulphate solution (CuSO4) for a
period of six minutes and then rinse and examine the flange parts. If there is any pink color visible, it indicates the
presence of free iron. This means the passivation process was not satisfactory.

Even though flange heaters and tanks may be made of stainless steel, the non-corrosive coating of the stainless
steel often gets damaged because the flange heating equipment and the tanks are constantly exposed to hot water.
Thus, flanged heaters need to be regularly passivated to maintain the non-corrosiveness of the equipment.

Figure 1
https://rpabrasives.com/resources/citric-acid-passivation-process/

What is Citric Acid Passivation?

As an industry authority, it’s our goal to provide our customers with easy access to information about the extensive
range of services we provide. Some of the more technical processes we use to finish parts can be complicated to
explain; that’s why we think it’s valuable to offer an inside look at the details of our techniques and innovative
services. The citric acid passivation process is one of our most commonly requested services due to its effectiveness
and consistent results.

Passivation as a general term is the technique used for Imparting metal with some sort of protective layer. The goal
of passivation is to protect the metal from corrosion, and there are many different ways to passivate metal. Citric
acid passivation uses concentrated citric acid to passivate metals like stainless steel and titanium. The concentrated
citric acid works to pull iron from the surface, then forms a protective layer on the outside of the part like a
protective shell.

The citric acid passivation process is often confused with another finishing process called pickling, but they are not
the same. The process of acid passivation begins by creating a citric acid solution with citric acid and water, making
sure the liquid is uniform. A uniform solution is integral to an evenly passivated finish. The acid solution is then
heated and the parts to be passivated are added to the solution and fully submerged for an amount of time that’s
decided by the desired finish.

Citric Acid Passivation Applications

The method of citric acid passivation is most commonly employed when parts require some higher level of
corrosion resistance. Parts of all sizes can benefit from the layer of oxidation produced by citric acid passivation,
but the material of the parts dictates how well the passivation will work. While stainless steel parts are the most
commonly passivated using citric acid, other metals like titanium can benefit equally. Industries who use passivated
parts vary from automotive and aerospace to medical, food and beverage processing, defense and most commonly;
chemical and wastewater treatment, where corrosive environments are most common.

Our Passivation Protocol

At RP Abrasives, we offer multiple citric acid passivation options depending on the needs of our customer. We can
passivate a wide range of part sizes, including batches of small parts and individual larger parts. We formulate our
citric acid solution using concentrated citric acid and deionized water, ensuring the best quality and consistently
excellent results. Before we begin the passivation process, we thoroughly clean each part, ensuring all surfaces
passivate evenly. Once we have completed the citric acid passivation process we complete a copper sulfate test
which analyzes the effectiveness of the passivation against corrosive conditions.

For more information about citric acid passivation or our other services, contact us today.
 https://www.ehow.com/how_8586228_passivate-copper.html

How to Passivate Copper By Bjorck DiMarco

Copper has a natural passivation process that can be hastened.

Passivation refers to the treatment of some metals with chemical baths that makes them permanently immune to
corrosion. Passivation also can refer to the application of anti-corrosives. Copper is one metal that cannot truly be
altered through passivation. However, through both natural and chemical means, copper can be made resistant to
corrosion.

Things You'll Need

 Ammonium sulfate
 Copper sulfate
 Ammonia

Expose copper to the elements. Although it is a gradual process that varies in speed depending upon the humidity
and heat in the environment, baring copper to the outdoors is the simplest way to passivate it. Within four to eight
weeks, a dull blue-green patina will form on the copper. This patina is a corrosion inhibitor.
Accelerate the growth of the patina with a chemical bath of ammonium sulfate, 6 pounds; copper sulfate, 3 ounces;
ammonia, 1.34 fluid ounces, and water, 6.5 gallons.
Apply the mixture as a spray. Allow it to dry between six applications. Wait six hours to see the patina deepen in
color. Growth of the patina film will now spread faster.

https://www.nap.edu/read/13032/chapter/3

Research Opportunities in Corrosion Science and Engineering (2011)

Chapter: 1 Corrosion - Its Influence and Control

INTRODUCTION
With much of the world’s population living in close proximity to water and humidity, corrosion of metallic materials
has been an inevitable part of the human experience. While the oxidation of iron (rust) is the most easily identified
form of corrosion, this oxidation process represents only a fraction (albeit substantial) of material losses. The
impact of corrosion on society and the associated degradation of materials are far reaching owing in part to the
increased complexity and diversity of materials systems, which include not only metallic materials but also
ceramics, polymers, and composites, which are subject as well to environmental extremes. While legacy corrosion
concerns remain, advancing technology and the need for global sustainability bring with them new and emerging
corrosion issues whose negative impacts must be minimized through appropriate materials selection, mitigation
and monitoring, and new materials development. See Figure 1.1 for an example of multiple simple mitigation
efforts.

The impacts of corrosion are often described in economic terms. Financial losses have been assessed in several
studies which concluded that premature materials degradation costs industrialized nations approximately 3
percent of their gross domestic product (GDP).1 In the United States it is estimated that between

FIGURE 1.1 A mooring ring, shackle, and thimble with rope illustrate three different techniques for combatting the
effects of materials degradation,. Originally, the ring and eye bolt were painted, the shackle and thimble were
galvanized (zinc coated), and the mooring line was made of nylon.
$2 trillion and $4 trillion are lost to corrosion each decade—on a relative scale, this amount equates to the cost of
repairing the infrastructure damage of three or four hurricanes as large as Hurricane Katrina, which caused massive
damage in New Orleans, southern Mississippi, and Alabama.

However, the true costs of corrosion to society are even more pervasive and, in practice, difficult to compile.
Several studies, including a recent National Research Council (NRC) report on corrosion education,2 have described
both the economic impacts of corrosion and the less measurable impacts such as loss of readiness—that is, the
nation’s ability to respond militarily or otherwise to emergencies or other situations involving national security. For
example, while the maintenance and replacement costs associated with the corrosion of military systems can be
readily estimated, the dollar costs associated with the military’s inability to respond promptly to a national
emergency are difficult to capture directly. Similarly, while the costs of replacing deteriorating bridges and highway
infrastructure can be estimated including the impacts on national productivity and security brought about by
failures and traffic congestion during repairs such estimates require assumptions that are subject to considerable
judgment.

Corrosion can affect public health, the environment, and global sustainability in ways that cannot be quantified
simply in terms of GDP loss. The deterioration of an early generation of medical devices and implants resulting
from interactions with human body fluids, the leaching of corrosion products into the environment, and the
weakening of the nation’s energy and transportation infrastructures all have impacts that greatly exceed those that
are purely financial.
Interestingly, the physical processes that cause materials to degrade may be harnessed for society’s benefit. For
example, the fabrication of semiconductor devices relies on a variety of etching, deposition, and oxidation
processes often operating at the nanometer level. The ability to precisely control the rates and extent of these
processes is critical to that fabrication. Corrosion-associated processes are also relevant to other technologies, both
in terms of routes by which to synthesize materials and as a means to understand their performance from a
mechanistic standpoint. Examples of materials issues include biodegradability and recycling, battery design and
development, nanoporous metals for catalysis and sensing, and fuel cells and gas separation membranes. State-of-
the-art corrosion research therefore has the potential not only to contribute significantly to many other fields of
science and engineering but also to enable them.

TYPES OF CORROSION
Corrosion has historically been defined as the destructive oxidation of metallic materials. More recent definitions
have described corrosion as the degradation of any material and its attendant loss of function by exposure to and
interaction with its environment. The committee, mindful of the increased application of nonmetals in important
structural applications, chose to define corrosion in the following broader context: Corrosion is the environmentally
induced degradation of a material that involves a chemical reaction. Mechanical degradation mechanisms, such as
creep, wear, and fatigue, are not considered to be corrosion, although corrosion processes may accelerate these
degradation modes. Worth mentioning at this point is hydrogen embrittlement, the process by which various
metals and alloys become brittle and crack following exposure to hydrogen. Hydrogen embrittlement or hydrogen
cracking is often the result of the unintentional introduction of hydrogen into susceptible metals and alloys during
formation or finishing operations.

The corrosion processes often involve multiple conjoint effects. Rarely does a single mechanism or event drive
corrosion; rather, a number of events combine to produce severe effects. Thus, we must keep in mind that
corrosion processes usually occur in the context of other factors (loads, wear, crevices, temporally and spatially
varying environments, etc.). One such combination of factors can lead to mechanically assisted corrosion in total
hip replacements :
 Wear (typically fretting),
 Passive oxide abrasion,
 Repassivation,
 Hydrogen ion generation, and
 Crevice environments.
It is the biological inflammatory response to these processes that generates aggressive oxidative environments in
vivo (generation of reactive oxygen species, etc.) that combine to lead to severe attacks on medical alloys. Ti alloys
can become subjected to pitting in vivo, and Co-Cr-Mo alloys can undergo penetrating intergranular corrosion as
well, leading to implant fatigue and fracture.

Another kind of corrosion sustained by medical implants is the metal-ion oxidation sustained by polyurethane
pacemaker leads. This failure mode is highly complex and involves water transport across the insulation of the lead,
allowing contact with the Co-Cr alloy, which then corrodes by a fretting mechanism. The metal ions, in particular
Co2+, then penetrate the polyurethane and oxidize it in a catalytic fashion. This leads ultimately to an electrical
breach in the lead and failure of the pacemaker, often resulting in the death of the patient.

EXAMPLES OF CORROSION MITIGATION CHALLENGES

Corrosion may be inevitable, but there are ways to retard it that is, to slow the kinetics of deterioration. The
mitigation strategy for a material must be tailored to the environment and to the composition and structure of the
material. Some materials are inherently slow to corrode, especially in the absence of oxygen; others corrode slowly
by forming layers of protective corrosion product (Box 1.2).

Materials with different properties will require different mitigation strategies :

Copper-based materials. Owing to the thermodynamic immunity of copper, corrosion is normally slow or absent
unless oxygen or another strong oxidant is present. Aqueous sulfide solutions are an exception. When oxygen is
present or in the presence of acid rain, these materials may react like other non-passive metals (see Figure 1.3).

The copper and its alloys are the structural materials most likely to survive for thousands of years in a world
suddenly depopulated of human beings. This conclusion, based on a strictly thermodynamic criterion (copper
being the most noble structural metal and sometimes found uncombined in nature), may not be correct,
however, given that some invented materials, like stainless steel, will also endure for thousands of years because
their surface is protected by passivating oxide films.

FIGURE 1.3 Bronze statue with a protective layer of patina created by slow chemical alteration of the copper
content, producing a basic carbonate. The statue has been exposed to the coastal weather outside the city hall of
Stockholm.
Polymers. Degradation is due to a wide array of physiochemical processes. One common problem is swelling, where
small molecules infiltrate the structure, reducing strength and stiffness and causing a volume change. Conversely,
many polymers are intentionally swelled with plasticizers, which can be leached out of the structure, causing
brittleness or other undesirable changes. The most common form of degradation, however, is a decrease in
polymer chain length. The mechanisms that break polymer chains are ionizing radiation (most commonly
ultraviolet light), free radicals, and oxidizers such as oxygen, ozone, and chlorine. Additives as simple as a UV-
absorbing pigment (i.e., titanium dioxide or carbon black) can slow these processes very effectively.

Mitigation techniques can be roughly classified as either active or passive. Examples of active mitigation techniques
include inhibitors, external cathodic protection, with or without coatings, and sacrificial anodes. Passive techniques
include material selection, organic, inorganic and metallic coatings (including both barrier and sacrificial coatings).
One other example of mitigation is control of the environment (oxygen, ions, etc.) such as is sometimes done in
boilers when oxygen and ions are removed while inhibitors (amines) are added. The decision to use one technique
or a combination of techniques depends on the type of corrosion that is expected, the tolerance for risk, the cost
of the technique, the material, the environment, and other factors related to the design of a structure, such as
accessibility and size.

The backgrounds; types of corrosion that were of greatest concern; types, costs, and efficacies of mitigation
systems employed; and idealized mitigation systems. Many corrosion mitigation strategies were relied on by the
respondents, the most frequent being material selection, monitoring/inspections, external cathodic protection
with coatings, organic coatings, and inhibitors. A majority of respondents reported having spent more than
$200,000/year on corrosion mitigation.

FIGURE 1.4 Femoral replacement part (T28) with stress corrosion cracking. Courtesy of Stanley A. Brown, U.S. Food
and Drug Administration.

.
SUMMARY OBSERVATIONS
There has been significant progress in the development of corrosion-resistant materials, understanding of basic
mechanisms by which corrosion occurs, and the implementation of mitigation techniques. This progress has
allowed for the current state of materials usage in both common and harsh environments. The primary drivers for
corrosion research have been industrial and government needs. Addressing these needs has led to advances in
science, as well as further practical improvements, which then provide for further scientific advances. Although
there is always a possibility for doing more, the government has played a vital role in the field of corrosion
research—including challenging industry with critical problems (e.g., related to access to space, nuclear power,
reduced maintenance of roads and bridges, and performance of military equipment), funding and conducting
research, establishing standards, and prescribing regulatory requirements for safety and health. Nevertheless, the
industrial research and development base that led to many of the advances in new materials and understanding of
corrosion behavior has eroded, and as such, the government agencies that have responsibilities dependent on the

FIGURE 1.3.1 The underside of a steel bridge member exhibiting significant corrosion.

Semiconductor Science and Technology Volume 27, Number 7 June 2012 •

PAPER
Passivation of copper surfaces for selective-area ALD using a thiol self-assembled monolayer
Elina Färm1, Marko Vehkamäki, Mikko Ritala and Markku Leskelä

Abstract
Self-assembled monolayers (SAMs) of 1-dodecanethiol (CH3(CH2)11SH) were prepared from the vapor phase and
used as a passivation layer for selective-area ALD. For example in the copper damascene process the thiol SAMs
should form only on the copper surface but not on the insulators. In this study, the SAMs were prepared by placing
the substrate and the alkylthiol to the reaction chamber and heating the system to the temperature of 73°C.
Preparation time varied from 0.5 hr to 24 hrs. Passivation properties of SAMs were tested with ALD iridium and
polyimide processes. Iridium was deposited at 250°C for 500 cycles and polyimide at 160 °C for 20 cycles.