Black oxide or blackening is a

conversion coating A conversion coating is a chemical or electro-chemical treatment applied to manufactured parts that superficially converts the material into a thin adhering coating of an insoluble compound. These coatings are commonly applied to protect the part ...

for ferrous materials, stainless steel,

copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkis ...

and copper based alloys,

zinc Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodi ...

powdered metal Powder metallurgy (PM) is a term covering a wide range of ways in which materials or components are made from metal powders. PM processes can reduce or eliminate the need for subtractive processes in manufacturing, lowering material losses and ...

s, and

silver solder Solder (; NA: ) is a fusible metal alloy used to create a permanent bond between metal workpieces. Solder is melted in order to wet the parts of the joint, where it adheres to and connects the pieces after cooling. Metals or alloys suitable ...

. It is used to add mild corrosion resistance, for appearance, and to minimize light reflection. To achieve maximal corrosion resistance the black oxide must be impregnated with oil or wax. One of its advantages over other coatings is its minimal buildup.

Ferrous material

A standard black oxide is

magnetite Magnetite is a mineral and one of the main iron ores, with the chemical formula Fe2+Fe3+2O4. It is one of the oxides of iron, and is ferrimagnetic; it is attracted to a magnet and can be magnetized to become a permanent magnet itself. With the ...

(FeO), which is more mechanically stable on the surface and provides better corrosion protection than red oxide (rust) FeO. Modern industrial approaches to forming black oxide include the hot and mid-temperature processes described below. Traditional methods are described in the article on bluing. They are of interest historically, and are also useful for hobbyists to form black oxide safely with little equipment and without toxic chemicals. Low temperature oxide, also described below, is not a conversion coating—the low-temperature process does not oxidize the iron, but deposits a copper selenium compound.

Hot black oxide

Hot baths of

sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula NaOH. It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly caustic base and alkali ...

(NaOH),

nitrates Nitrate is a polyatomic ion with the chemical formula . Salts containing this ion are called nitrates. Nitrates are common components of fertilizers and explosives. Almost all inorganic nitrates are soluble in water. An example of an insoluble ...

such as

sodium nitrate Sodium nitrate is the chemical compound with the formula . This alkali metal nitrate salt is also known as Chile saltpeter (large deposits of which were historically mined in Chile) to distinguish it from ordinary saltpeter, potassium nitrate. T ...

(), and/or

nitrites The nitrite ion has the chemical formula . Nitrite (mostly sodium nitrite) is widely used throughout chemical and pharmaceutical industries. The nitrite anion is a pervasive intermediate in the nitrogen cycle in nature. The name nitrite also r ...

such as

sodium nitrite Sodium nitrite is an inorganic compound with the chemical formula NaNO2. It is a white to slightly yellowish crystalline powder that is very soluble in water and is hygroscopic. From an industrial perspective, it is the most important nitrite ...

(NaNO₂) at are used to convert the surface of the material into

(FeO). Water must be periodically added to the bath, with proper controls to prevent a

steam explosion A steam explosion is an explosion caused by violent boiling or flashing of water or ice into steam, occurring when water or ice is either superheated, rapidly heated by fine hot debris produced within it, or heated by the interaction of molten m ...

. Hot blackening involves dipping the part into various tanks. The workpiece is usually dipped by automated part carriers for transportation between tanks. These tanks contain, in order,

alkali In chemistry, an alkali (; from ar, القلوي, al-qaly, lit=ashes of the saltwort) is a basic, ionic salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as a base that dissolves in water. A solution of a ...

detergent A detergent is a surfactant or a mixture of surfactants with cleansing properties when in dilute solutions. There are a large variety of detergents, a common family being the alkylbenzene sulfonates, which are soap-like compounds that are more ...

, water,

at (the blackening compound), and finally the sealant, which is usually oil. The NaOH (caustic soda) and elevated temperature cause FeO (black oxide) to form on the surface of the metal instead of FeO (red oxide; rust). While it is physically denser than red oxide, the fresh black oxide is porous, so oil is then applied as post treatment to the heated part, which seals it by "sinking" into it. The combination prevents corrosion of the workpiece. There are many advantages of blackening, including: * Blackening can be done in large batches, which is ideal for small parts. * There is no significant dimensional impact. The blacking process creates a layer about 1 μm thick. * It is far cheaper than similar corrosion protection systems, such as

paint Paint is any pigmented liquid, liquefiable, or solid mastic composition that, after application to a substrate in a thin layer, converts to a solid film. It is most commonly used to protect, color, or provide texture. Paint can be made in many ...

and

electroplating Electroplating, also known as electrochemical deposition or electrodeposition, is a process for producing a metal coating on a solid substrate through the reduction of cations of that metal by means of a direct electric current. The part to be ...

. The oldest and most widely used specification for hot black oxide is MIL-DTL-13924, which covers four classes of processes for different substrates. Alternate specifications include AMS 2485, ASTM D769, and ISO 11408.

Iron(III) chloride Iron(III) chloride is the inorganic compound with the formula . Also called ferric chloride, it is a common compound of iron in the +3 oxidation state. The anhydrous compound is a crystalline solid with a melting point of 307.6 °C. The col ...

(FeCl₃) may also be used for steel blackening by dipping a piece of steel into a hot bath of 50% FeCl₃ solution and then into a hot boiling water. The process is usually repeated several times.

Mid-temperature black oxide

Like hot black oxide, mid-temperature black oxide converts the surface of the metal to magnetite (FeO). However, mid-temperature black oxide blackens at a temperature of , significantly less than hot black oxide. This is advantageous because it is below the solution's boiling point, meaning there are no caustic fumes produced. Since mid-temperature black oxide is most comparable to hot black oxide, it also can meet the

military specification A United States defense standard, often called a military standard, "MIL-STD", "MIL-SPEC", or (informally) "MilSpecs", is used to help achieve standardization objectives by the U.S. Department of Defense. Standardization is beneficial in achievi ...

MIL-DTL-13924, as well as AMS 2485.

Cold black oxide

Cold black oxide, also known as room temperature black oxide, is applied at a temperature of . It is not an oxide conversion coating, but rather a deposited

copper selenide Copper selenide is an inorganic binary compound consisting of copper and selenium. Its formula is sometimes described as CuSe or Cu2Se. The crystalline structure and electronic behavior is determined by its elemental composition. Stoichiometric c ...

(Cu₂Se) compound. Cold black oxide is convenient for in-house blackening. This coating produces a similar color to the one the oxide conversion does, but tends to rub off easily and offers less abrasion resistance. The application of oil, wax, or lacquer brings the corrosion resistance up to par with the hot and mid-temperature. One application for cold black oxide process is in tooling and architectural finishing on steel. It is also known as cold bluing.

Copper

Black oxide for

, sometimes known by the

trade name A trade name, trading name, or business name, is a pseudonym used by companies that do not operate under their registered company name. The term for this type of alternative name is a "fictitious" business name. Registering the fictitious name w ...

''Ebonol C'', converts the copper surface to

cupric oxide Copper(II) oxide or cupric oxide is an inorganic compound with the formula CuO. A black solid, it is one of the two stable oxides of copper, the other being Cu2O or copper(I) oxide (cuprous oxide). As a mineral, it is known as tenorite. It i ...

. For the process to work the surface has to have at least 65% copper; for copper surfaces that have less than 90% copper it must first be pretreated with an activating treatment. The finished coating is chemically stable and very adherent. It is stable up to ; above this temperature the coating degrades due to oxidation of the base copper. To increase corrosion resistance, the surface may be oiled,

lacquer Lacquer is a type of hard and usually shiny coating or finish applied to materials such as wood or metal. It is most often made from resin extracted from trees and waxes and has been in use since antiquity. Asian lacquerware, which may be ca ...

ed, or

wax Waxes are a diverse class of organic compounds that are lipophilic, malleable solids near ambient temperatures. They include higher alkanes and lipids, typically with melting points above about 40 °C (104 °F), melting to giv ...

ed. It is also used as a pre-treatment for

painting Painting is the practice of applying paint, pigment, color or other medium to a solid surface (called the "matrix" or "support"). The medium is commonly applied to the base with a brush, but other implements, such as knives, sponges, and ...

or enamelling. The surface finish is usually

satin A satin weave is a type of fabric weave that produces a characteristically glossy, smooth or lustrous material, typically with a glossy top surface and a dull back. It is one of three fundamental types of textile weaves alongside plain weave ...

, but it can be turned glossy by coating in a clear high-gloss enamel. On a microscopic scale

dendrites Dendrites (from Greek δένδρον ''déndron'', "tree"), also dendrons, are branched protoplasmic extensions of a nerve cell that propagate the electrochemical stimulation received from other neural cells to the cell body, or soma, of the n ...

form on the surface finish, which trap light and increase absorptivity. Because of this property the coating is used in

aerospace Aerospace is a term used to collectively refer to the atmosphere and outer space. Aerospace activity is very diverse, with a multitude of commercial, industrial and military applications. Aerospace engineering consists of aeronautics and astrona ...

microscopy Microscopy is the technical field of using microscopes to view objects and areas of objects that cannot be seen with the naked eye (objects that are not within the resolution range of the normal eye). There are three well-known branches of micr ...

and other optical applications to minimise light reflection. In

printed circuit board A printed circuit board (PCB; also printed wiring board or PWB) is a medium used in Electrical engineering, electrical and electronic engineering to connect electronic components to one another in a controlled manner. It takes the form of a L ...

s (PCBs), the use of black oxide provides better adhesion for the fiberglass laminate layers. The PCB is dipped in a bath containing hydroxide,

hypochlorite In chemistry, hypochlorite is an anion with the chemical formula ClO−. It combines with a number of cations to form hypochlorite salts. Common examples include sodium hypochlorite (household bleach) and calcium hypochlorite (a component of ble ...

, and

cuprate Cuprate loosely refers to a material that can be viewed as containing anionic copper complexes. Examples include tetrachloridocuprate ( uCl4sup>2−), the superconductor YBa2Cu3O7, and the organocuprates (e.g., dimethylcuprate u(CH3)2sup>� ...

, which becomes depleted in all three components. This indicates that the black copper oxide comes partially from the cuprate and partially from the PCB copper circuitry. Under microscopic examination, there is no copper(I) oxide layer. An applicable U.S. military specification is MIL-F-495E.

Stainless steel

Hot black oxide for stainless steel is a mixture of caustic, oxidizing, and sulfur salts. It blackens 300 and 400 series and the precipitation-hardened 17-4 PH stainless steel alloys. The solution can be used on cast iron and mild low-carbon steel. The resulting finish complies with military specification MIL-DTL–13924D Class 4 and offers abrasion resistance. Black oxide finish is used on surgical instruments in light-intensive environments to reduce eye fatigue. Room-temperature blackening for stainless steel occurs by auto-catalytic reaction of copper-selenide depositing on the stainless-steel surface. It offers less abrasion resistance and the same corrosion protection as the hot blackening process.

Zinc

Black oxide for zinc is also known by the trade name ''Ebonol Z''.

References

{{Reflist, 30em Chemical mixtures Coatings Corrosion prevention