Passivation
Overview
 
Passivation is the process of making a material "passive", and thus less reactive with surrounding air, water, or other gases or liquids. The goal is to inhibit corrosion
Corrosion
Corrosion is the disintegration of an engineered material into its constituent atoms due to chemical reactions with its surroundings. In the most common use of the word, this means electrochemical oxidation of metals in reaction with an oxidant such as oxygen...

, whether for structural or cosmetic reasons. Passivation of metals is usually achieved by the deposition of a layer of oxide that adheres to the metal surface
Metal oxide adhesion
The strength of metal oxide adhesion effectively determines the wetting of the metal-oxide interface. The strength of this adhesion is important, for instance, in production of light bulbs and fiber-matrix composites that depend on the optimization of wetting to create metal-ceramic interfaces The...

. In air, passivation affects the properties of almost all metals–notable examples being aluminium
Aluminium
Aluminium or aluminum is a silvery white member of the boron group of chemical elements. It has the symbol Al, and its atomic number is 13. It is not soluble in water under normal circumstances....

, zinc
Zinc
Zinc , or spelter , is a metallic chemical element; it has the symbol Zn and atomic number 30. It is the first element in group 12 of the periodic table. Zinc is, in some respects, chemically similar to magnesium, because its ion is of similar size and its only common oxidation state is +2...

, titanium
Titanium
Titanium is a chemical element with the symbol Ti and atomic number 22. It has a low density and is a strong, lustrous, corrosion-resistant transition metal with a silver color....

, and silicon
Silicon
Silicon is a chemical element with the symbol Si and atomic number 14. A tetravalent metalloid, it is less reactive than its chemical analog carbon, the nonmetal directly above it in the periodic table, but more reactive than germanium, the metalloid directly below it in the table...

 (a metalloid
Metalloid
Metalloid is a term used in chemistry when classifying the chemical elements. On the basis of their general physical and chemical properties, each element can usually be classified as a metal or a nonmetal. However, some elements with intermediate or mixed properties can be harder to characterize...

). In the context of corrosion
Corrosion
Corrosion is the disintegration of an engineered material into its constituent atoms due to chemical reactions with its surroundings. In the most common use of the word, this means electrochemical oxidation of metals in reaction with an oxidant such as oxygen...

, passivation is the spontaneous formation of a hard non-reactive surface film that inhibits further corrosion.
Encyclopedia
Passivation is the process of making a material "passive", and thus less reactive with surrounding air, water, or other gases or liquids. The goal is to inhibit corrosion
Corrosion
Corrosion is the disintegration of an engineered material into its constituent atoms due to chemical reactions with its surroundings. In the most common use of the word, this means electrochemical oxidation of metals in reaction with an oxidant such as oxygen...

, whether for structural or cosmetic reasons. Passivation of metals is usually achieved by the deposition of a layer of oxide that adheres to the metal surface
Metal oxide adhesion
The strength of metal oxide adhesion effectively determines the wetting of the metal-oxide interface. The strength of this adhesion is important, for instance, in production of light bulbs and fiber-matrix composites that depend on the optimization of wetting to create metal-ceramic interfaces The...

. In air, passivation affects the properties of almost all metals–notable examples being aluminium
Aluminium
Aluminium or aluminum is a silvery white member of the boron group of chemical elements. It has the symbol Al, and its atomic number is 13. It is not soluble in water under normal circumstances....

, zinc
Zinc
Zinc , or spelter , is a metallic chemical element; it has the symbol Zn and atomic number 30. It is the first element in group 12 of the periodic table. Zinc is, in some respects, chemically similar to magnesium, because its ion is of similar size and its only common oxidation state is +2...

, titanium
Titanium
Titanium is a chemical element with the symbol Ti and atomic number 22. It has a low density and is a strong, lustrous, corrosion-resistant transition metal with a silver color....

, and silicon
Silicon
Silicon is a chemical element with the symbol Si and atomic number 14. A tetravalent metalloid, it is less reactive than its chemical analog carbon, the nonmetal directly above it in the periodic table, but more reactive than germanium, the metalloid directly below it in the table...

 (a metalloid
Metalloid
Metalloid is a term used in chemistry when classifying the chemical elements. On the basis of their general physical and chemical properties, each element can usually be classified as a metal or a nonmetal. However, some elements with intermediate or mixed properties can be harder to characterize...

). In the context of corrosion
Corrosion
Corrosion is the disintegration of an engineered material into its constituent atoms due to chemical reactions with its surroundings. In the most common use of the word, this means electrochemical oxidation of metals in reaction with an oxidant such as oxygen...

, passivation is the spontaneous formation of a hard non-reactive surface film that inhibits further corrosion. This layer is usually an oxide
Oxide
An oxide is a chemical compound that contains at least one oxygen atom in its chemical formula. Metal oxides typically contain an anion of oxygen in the oxidation state of −2....

 or nitride
Nitride
In chemistry, a nitride is a compound of nitrogen where nitrogen has a formal oxidation state of −3. Nitrides are a large class of compounds with a wide range of properties and applications....

 that is a few nanometers thick.

Mechanisms

The conditions necessary for passivation are recorded in Pourbaix diagram
Pourbaix diagram
In chemistry, a Pourbaix diagram, also known as a potential/pH diagram, maps out possible stable phases of an aqueous electrochemical system. Predominant ion boundaries are represented by lines. As such a Pourbaix diagram can be read much like a standard phase diagram with a different set of axes...

s. Some corrosion inhibitor
Corrosion inhibitor
A corrosion inhibitor is a chemical compound that, when added to a liquid or gas, decreases the corrosion rate of a material, typically a metal or an alloy. The effectiveness of a corrosion inhibitor depends on fluid composition, quantity of water, and flow regime...

s help the formation of a passivation layer on the surface of the metals to which they are applied. Some compounds, dissolving in solutions (chromate
Chromate
Chromate salts contain the chromate anion, CrO42−. Dichromate salts contain the dichromate anion, Cr2O72−. They are oxyanions of chromium in the oxidation state +6. They are moderately strong oxidizing agents.- Chemical properties :...

s, molybdates) form non-reactive and low solubility films on metal surfaces.

Silicon

In the area of microelectronics, the formation of a strongly adhering passivating oxide is important to the performance of silicon.

In the area of photovoltaics, a passivating surface layer such as silicon nitride, silicon dioxide or titanium dioxide can reduce surface recombination - a significant loss mechanism in solar cells.

Aluminium

Pure aluminium
Aluminium
Aluminium or aluminum is a silvery white member of the boron group of chemical elements. It has the symbol Al, and its atomic number is 13. It is not soluble in water under normal circumstances....

 naturally forms a thin surface layer of aluminium oxide
Aluminium oxide
Aluminium oxide is an amphoteric oxide with the chemical formula 23. It is commonly referred to as alumina, or corundum in its crystalline form, as well as many other names, reflecting its widespread occurrence in nature and industry...

 on contact with oxygen
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...

 in the atmosphere through a process called oxidation, which creates a physical barrier to corrosion or further oxidation in most environments. Aluminium alloy
Aluminium alloy
Aluminium alloys are alloys in which aluminium is the predominant metal. The typical alloying elements are copper, magnesium, manganese, silicon and zinc. There are two principal classifications, namely casting alloys and wrought alloys, both of which are further subdivided into the categories...

s, however, offer little protection against corrosion. There are three main ways to passivate these alloys: alclad
Alclad
Alclad is a trademark of Alcoa used as a generic term to describe corrosion resistant aluminium sheet formed from high-purity aluminium surface layers metallurgically bonded to high strength aluminium alloy core material. These sheets are commonly used by the aircraft industry...

ing
, chromate conversion coating
Chromate conversion coating
Chromate conversion coating is a type of conversion coating used to passivate aluminum, zinc, cadmium, copper, silver, magnesium, and tin alloys. It is primarily used as a corrosion inhibitor, primer, decorative finish, or to retain electrical conductivity. The process is named after the chromate...

and anodizing. Alclading is the process of metallurgically bonding a thin layer of pure aluminium to the aluminium alloy. Chromate conversion coating is a common way of passivating not only aluminum, but also zinc
Zinc
Zinc , or spelter , is a metallic chemical element; it has the symbol Zn and atomic number 30. It is the first element in group 12 of the periodic table. Zinc is, in some respects, chemically similar to magnesium, because its ion is of similar size and its only common oxidation state is +2...

, cadmium
Cadmium
Cadmium is a chemical element with the symbol Cd and atomic number 48. This soft, bluish-white metal is chemically similar to the two other stable metals in group 12, zinc and mercury. Similar to zinc, it prefers oxidation state +2 in most of its compounds and similar to mercury it shows a low...

, copper
Copper
Copper is a chemical element with the symbol Cu and atomic number 29. It is a ductile metal with very high thermal and electrical conductivity. Pure copper is soft and malleable; an exposed surface has a reddish-orange tarnish...

, silver
Silver
Silver is a metallic chemical element with the chemical symbol Ag and atomic number 47. A soft, white, lustrous transition metal, it has the highest electrical conductivity of any element and the highest thermal conductivity of any metal...

, magnesium
Magnesium
Magnesium is a chemical element with the symbol Mg, atomic number 12, and common oxidation number +2. It is an alkaline earth metal and the eighth most abundant element in the Earth's crust and ninth in the known universe as a whole...

, and tin
Tin
Tin is a chemical element with the symbol Sn and atomic number 50. It is a main group metal in group 14 of the periodic table. Tin shows chemical similarity to both neighboring group 14 elements, germanium and lead and has two possible oxidation states, +2 and the slightly more stable +4...

 alloys. Anodizing forms a thick oxide coating. This finish is more robust than the other processes and also provides good electrical insulation
Electrical insulation
thumb|250px|[[Coaxial Cable]] with dielectric insulator supporting a central coreThis article refers to electrical insulation. For insulation of heat, see Thermal insulation...

, which the other two processes do not.

For example, prior to storing hydrogen peroxide
Hydrogen peroxide
Hydrogen peroxide is the simplest peroxide and an oxidizer. Hydrogen peroxide is a clear liquid, slightly more viscous than water. In dilute solution, it appears colorless. With its oxidizing properties, hydrogen peroxide is often used as a bleach or cleaning agent...

 in an aluminium container, the container can be passivated by rinsing it with a dilute solution of nitric acid
Nitric acid
Nitric acid , also known as aqua fortis and spirit of nitre, is a highly corrosive and toxic strong acid.Colorless when pure, older samples tend to acquire a yellow cast due to the accumulation of oxides of nitrogen. If the solution contains more than 86% nitric acid, it is referred to as fuming...

 and peroxide alternating with deionized water. The nitric acid and peroxide oxidizes and dissolves any impurities on the inner surface of the container, and the deionized water rinses away the acid and oxidized impurities.

Ferrous materials

Ferrous
Ferrous
Ferrous , in chemistry, indicates a divalent iron compound , as opposed to ferric, which indicates a trivalent iron compound ....

 materials, including steel, may be somewhat protected by promoting oxidation ("rust") and then converting the oxidation to a metalophosphate by using phosphoric acid
Phosphoric acid
Phosphoric acid, also known as orthophosphoric acid or phosphoric acid, is a mineral acid having the chemical formula H3PO4. Orthophosphoric acid molecules can combine with themselves to form a variety of compounds which are also referred to as phosphoric acids, but in a more general way...

 and further protected by surface coating. As the uncoated surface is water-soluble, a preferred method is to form manganese
Manganese
Manganese is a chemical element, designated by the symbol Mn. It has the atomic number 25. It is found as a free element in nature , and in many minerals...

 or zinc compounds by a process commonly known as Parkerizing
Parkerizing
Parkerizing is a method of protecting a steel surface from corrosion and increasing its resistance to wear through the application of an electrochemical phosphate conversion coating...

 or phosphate conversion. Older, less-effective but chemically-similar electrochemical conversion coatings included black oxiding
Black oxide
Black oxide or blackening is a conversion coating for ferrous materials, copper and copper based alloys, zinc, powdered metals, and silver solder. It is used to add mild corrosion resistance and for appearance. To achieve maximum corrosion resistance the black oxide must be impregnated with oil or...

, historically known as bluing
Bluing (steel)
Bluing is a passivation process in which steel is partially protected against rust, and is named after the blue-black appearance of the resulting protective finish. True gun bluing is an electrochemical conversion coating resulting from an oxidizing chemical reaction with iron on the surface...

 or browning. Ordinary steel
Steel
Steel is an alloy that consists mostly of iron and has a carbon content between 0.2% and 2.1% by weight, depending on the grade. Carbon is the most common alloying material for iron, but various other alloying elements are used, such as manganese, chromium, vanadium, and tungsten...

 forms a passivating layer in alkali
Alkali
In chemistry, an alkali is a basic, ionic salt of an alkali metal or alkaline earth metal element. Some authors also define an alkali as a base that dissolves in water. A solution of a soluble base has a pH greater than 7. The adjective alkaline is commonly used in English as a synonym for base,...

 environments, as rebar
Rebar
A rebar , also known as reinforcing steel, reinforcement steel, rerod, or a deformed bar, is a common steel bar, and is commonly used as a tensioning device in reinforced concrete and reinforced masonry structures holding the concrete in compression...

 does in concrete
Concrete
Concrete is a composite construction material, composed of cement and other cementitious materials such as fly ash and slag cement, aggregate , water and chemical admixtures.The word concrete comes from the Latin word...

.

Stainless steel

Stainless steels are corrosion-resistant by nature, which might suggest that passivating them would be unnecessary. However, stainless steels are not completely impervious to rusting. One common mode of corrosion in corrosion-resistant steels is when small spots on the surface rust because grain boundaries or embedded bits of foreign matter (such as grinding swarf
Swarf
Swarf, also known as turnings, chips, or filings, are shavings and chippings of metal — the debris or waste resulting from metalworking operations including milling and grinding. It can usually be recycled, and this is the preferred method of disposal due to the environmental concerns regarding...

) allow water molecules to oxidize some of the iron in those spots despite the alloying chromium. This is called rouging
Rouging
Rouging refers to a form of corrosion found in stainless steel. It can be due to iron contamination of the stainless steel surface due to welding of ferrous steel for support columns, or other temporary means, which when welded off, leaving a low chromium area....

. Some grades of stainless steel are especially resistant to rouging; parts made from them may therefore forgo any passivation step, depending on engineering decisions.

A typical passivation process of cleaning stainless steel tanks involves cleaning with sodium hydroxide and citric acid
Citric acid
Citric acid is a weak organic acid. It is a natural preservative/conservative and is also used to add an acidic, or sour, taste to foods and soft drinks...

 followed by nitric acid (up to 20% at 120 °F) and a complete water rinse. This process will restore the film, remove metal particles, dirt, and welding-generated compounds (e.g. oxides).

One aircraft manufacturer's corporate standard for passivation of stainless steel parts involves coating or submerging them in nitric acid solution for 40 to 60 minutes, then wiping them with water-soaked cloth.

Nickel

Nickel
Nickel
Nickel is a chemical element with the chemical symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel belongs to the transition metals and is hard and ductile...

 can be used for handling elemental fluorine
Fluorine
Fluorine is the chemical element with atomic number 9, represented by the symbol F. It is the lightest element of the halogen column of the periodic table and has a single stable isotope, fluorine-19. At standard pressure and temperature, fluorine is a pale yellow gas composed of diatomic...

, owing to the formation of a passivation layer of nickel fluoride
Nickel(II) fluoride
Nickel fluoride is the chemical compound with the formula NiF2. Unlike many fluorides, NiF2 is stable in air. NiF2 comprises the passivating surface that forms on nickel alloys, e.g. monel, which is why such materials are good to store or transport hydrogen fluoride or elemental fluorine...

. This fact is useful in water treatment
Water treatment
Water treatment describes those processes used to make water more acceptable for a desired end-use. These can include use as drinking water, industrial processes, medical and many other uses. The goal of all water treatment process is to remove existing contaminants in the water, or reduce the...

 and sewage treatment
Sewage treatment
Sewage treatment, or domestic wastewater treatment, is the process of removing contaminants from wastewater and household sewage, both runoff and domestic. It includes physical, chemical, and biological processes to remove physical, chemical and biological contaminants...

 applications.

See also

  • Pilling-Bedworth ratio
    Pilling-Bedworth ratio
    The Pilling-Bedworth ratio , in corrosion of metals, is the ratio of the volume of the elementary cell of a metal oxide to the volume of the elementary cell of the corresponding metal ....

  • Cold welding
    Cold welding
    Cold or contact welding is a solid-state welding process in which joining takes place without fusion/heating at the interface of the two parts to be welded. Unlike in the fusion-welding processes, no liquid or molten phase is present in the joint....

  • Dental implant
    Dental implant
    A dental implant is a "root" device, usually made of titanium, used in dentistry to support restorations that resemble a tooth or group of teeth to replace missing teeth....

    s
  • Mini dental implants
    Mini dental implants
    Mini dental implants are small diameter dental implants.Dental implants may be split into two separate categories based on the diameter of the device...


Further reading

  • Chromate conversion coating
    Chromate conversion coating
    Chromate conversion coating is a type of conversion coating used to passivate aluminum, zinc, cadmium, copper, silver, magnesium, and tin alloys. It is primarily used as a corrosion inhibitor, primer, decorative finish, or to retain electrical conductivity. The process is named after the chromate...

     (chemical film) per MIL-DTL-5541F for aluminium and aluminium alloy parts
  • A standard overview on black oxide coatings is provided in MIL-HDBK-205, Phosphate & Black Oxide Coating of Ferrous Metals. Many of the specifics of Black Oxide coatings may be found in MIL-DTL-13924 (formerly MIL-C-13924). This Mil-Spec document additionally identifies various classes of Black Oxide coatings, for use in a variety of purposes for protecting ferrous metals against rust.
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