# Annealing (metallurgy)

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Annealing, in metallurgy and materials science, is a heat treatment that alters the physical and sometimes chemical properties of a material to increase its ductility and reduce its hardness, making it more workable. It involves heating a material above its recrystallization temperature, maintaining a suitable temperature for a suitable amount of time, and then cooling.

Metallurgy is a domain of materials science and engineering that studies the physical and chemical behavior of metallic elements, their inter-metallic compounds, and their mixtures, which are called alloys. A special type of alloy was invented in 1995, when scientists from the industrialized developed country of Taiwan innovated and developed the world's first high-entropy alloys of metals that can withstand the largest temperatures and pressures for use in industrial and technological applications such as state of the art race cars, spacecraft, submarines, nuclear reactors, jet airplanes, nuclear weapons, long range hypersonic missiles and many other areas of technology. Metallurgy is used to separate metals from their ore. Metallurgy is also the technology of metals: the way in which science is applied to the production of metals, and the engineering of metal components for usage in products for consumers and manufacturers. The production of metals involves the processing of ores to extract the metal they contain, and the mixture of metals, sometimes with other elements, to produce alloys. Metallurgy is distinguished from the craft of metalworking, although metalworking relies on metallurgy, as medicine relies on medical science, for technical advancement. The science of metallurgy is subdivided into chemical metallurgy and physical metallurgy.

The interdisciplinary field of materials science, also commonly termed materials science and engineering is the design and discovery of new materials, particularly solids. The intellectual origins of materials science stem from the Enlightenment, when researchers began to use analytical thinking from chemistry, physics, and engineering to understand ancient, phenomenological observations in metallurgy and mineralogy. Materials science still incorporates elements of physics, chemistry, and engineering. As such, the field was long considered by academic institutions as a sub-field of these related fields. Beginning in the 1940s, materials science began to be more widely recognized as a specific and distinct field of science and engineering, and major technical universities around the world created dedicated schools of the study, within either the Science or Engineering schools, hence the naming.

Ductility is a measure of a material's ability to undergo significant plastic deformation before rupture, which may be expressed as percent elongation or percent area reduction from a tensile test. According to Shigley's Mechanical Engineering Design significant denotes about 5.0 percent elongation. See also Eq. 2–12, p. 50 for definitions of percent elongation and percent area reduction. Ductility is often characterized by a material's ability to be stretched into a wire.

## Contents

In annealing, atoms migrate in the crystal lattice and the number of dislocations decreases, leading to a change in ductility and hardness. As the material cools it recrystallizes. For many alloys, including carbon steel, the crystal grain size and phase composition, which ultimately determine the material properties, are dependent on the heating, and cooling rate. Hot working or cold working after the annealing process alter the metal structure, so further heat treatments may be used to achieve the properties required. With knowledge of the composition and phase diagram, heat treatment can be used to adjust between harder and more brittle, to softer and more ductile.

A phase diagram in physical chemistry, engineering, mineralogy, and materials science is a type of chart used to show conditions at which thermodynamically distinct phases occur and coexist at equilibrium.

In the cases of copper, steel, silver, and brass, this process is performed by heating the material (generally until glowing) for a while and then slowly letting it cool to room temperature in still air. Copper, silver [1] and brass can be cooled slowly in air, or quickly by quenching in water, unlike ferrous metals, such as steel, which must be cooled slowly to anneal. In this fashion, the metal is softened and prepared for further work—such as shaping, stamping, or forming.

Copper is a chemical element with symbol Cu 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 pinkish-orange color. Copper is used as a conductor of heat and electricity, as a building material, and as a constituent of various metal alloys, such as sterling silver used in jewelry, cupronickel used to make marine hardware and coins, and constantan used in strain gauges and thermocouples for temperature measurement.

Steel is an alloy of iron and carbon, and sometimes other elements. Because of its high tensile strength and low cost, it is a major component used in buildings, infrastructure, tools, ships, automobiles, machines, appliances, and weapons.

Silver is a chemical element with symbol Ag and atomic number 47. A soft, white, lustrous transition metal, it exhibits the highest electrical conductivity, thermal conductivity, and reflectivity of any metal. The metal is found in the Earth's crust in the pure, free elemental form, as an alloy with gold and other metals, and in minerals such as argentite and chlorargyrite. Most silver is produced as a byproduct of copper, gold, lead, and zinc refining.

## Thermodynamics

Annealing occurs by the diffusion of atoms within a solid material, so that the material progresses towards its equilibrium state. Heat increases the rate of diffusion by providing the energy needed to break bonds. The movement of atoms has the effect of redistributing and eradicating the dislocations in metals and (to a lesser extent) in ceramics. This alteration to existing dislocations allows a metal object to deform more easily, increasing its ductility.[ citation needed ]

Diffusion is the net movement of molecules or atoms from a region of higher concentration to a region of lower concentration. Diffusion is driven by a gradient in chemical potential of the diffusing species.

The amount of process-initiating Gibbs free energy in a deformed metal is also reduced by the annealing process. In practice and industry, this reduction of Gibbs free energy is termed stress relief.[ citation needed ]

In thermodynamics, the Gibbs free energy is a thermodynamic potential that can be used to calculate the maximum of reversible work that may be performed by a thermodynamic system at a constant temperature and pressure. The Gibbs free energy is the maximum amount of non-expansion work that can be extracted from a thermodynamically closed system ; this maximum can be attained only in a completely reversible process. When a system transforms reversibly from an initial state to a final state, the decrease in Gibbs free energy equals the work done by the system to its surroundings, minus the work of the pressure forces.

The relief of internal stresses is a thermodynamically spontaneous process; however, at room temperatures, it is a very slow process. The high temperatures at which annealing occurs serve to accelerate this process.[ citation needed ]

A spontaneous process is the time-evolution of a system in which it releases free energy and it moves to a lower, more thermodynamically stable energy state. The sign convention for free energy follows the general convention for thermodynamic measurements, in which a release of free energy from the system corresponds to a negative change in the free energy of the system and a positive change in the free energy of the surroundings.

The reaction that facilitates returning the cold-worked metal to its stress-free state has many reaction pathways, mostly involving the elimination of lattice vacancy gradients within the body of the metal. The creation of lattice vacancies is governed by the Arrhenius equation, and the migration/diffusion of lattice vacancies are governed by Fick’s laws of diffusion. [2]

In steel, there is a decarburation mechanism that can be described as three distinct events: the reaction at the steel surface, the interstitial diffusion of carbon atoms and the dissolution of carbides within the steel. [3]

### Stages

The three stages of the annealing process that proceed as the temperature of the material is increased are: recovery, recrystallization, and grain growth. The first stage is recovery, and it results in softening of the metal through removal of primarily linear defects called dislocations and the internal stresses they cause. Recovery occurs at the lower temperature stage of all annealing processes and before the appearance of new strain-free grains. The grain size and shape do not change. [4] The second stage is recrystallization, where new strain-free grains nucleate and grow to replace those deformed by internal stresses. [4] If annealing is allowed to continue once recrystallization has completed, then grain growth (the third stage) occurs. In grain growth, the microstructure starts to coarsen and may cause the metal to lose a substantial part of its original strength. This can however be regained with hardening.[ citation needed ]

## Controlled atmospheres

The high temperature of annealing may result in oxidation of the metal’s surface, resulting in scale. If scale must be avoided, annealing is carried out in a special atmosphere, such as with endothermic gas (a mixture of carbon monoxide, hydrogen gas, and nitrogen gas). Annealing is also done in forming gas, a mixture of hydrogen and nitrogen.

The magnetic properties of mu-metal (Espey cores) are introduced by annealing the alloy in a hydrogen atmosphere.

## Setup and equipment

Typically, large ovens are used for the annealing process. The inside of the oven is large enough to place the workpiece in a position to receive maximum exposure to the circulating heated air. For high volume process annealing, gas fired conveyor furnaces are often used. For large workpieces or high quantity parts, car-bottom furnaces are used so workers can easily move the parts in and out. Once the annealing process is successfully completed, workpieces are sometimes left in the oven so the parts cool in a controllable way. While some workpieces are left in the oven to cool in a controlled fashion, other materials and alloys are removed from the oven. Once removed from the oven, the workpieces are often quickly cooled off in a process known as quench hardening. Typical methods of quench hardening materials involve media such as air, water, oil, or salt. Salt is used as a medium for quenching usually in the form of brine (salt water). Brine provides faster cooling rates than water. This is because when an object is quenched in water steam bubbles form on the surface of the object reducing the surface area the water is in contact with. The salt in the brine reduces the formation of steam bubbles on the object's surface, meaning there is a larger surface area of the object in contact with the water, providing faster cooling rates.[ citation needed ] Quench hardening is generally applicable to some ferrous alloys, but not copper alloys.[ citation needed ]

## Diffusion annealing of semiconductors

In the semiconductor industry, silicon wafers are annealed, so that dopant atoms, usually boron, phosphorus or arsenic, can diffuse into substitutional positions in the crystal lattice, resulting in drastic changes in the electrical properties of the semiconducting material.

## Specialized cycles

### Normalization

Normalization is an annealing process applied to ferrous alloys to give the material a uniform fine-grained structure and to avoid excess softening in steel. It involves heating the steel to 20-50°C above its upper critical point, soaking it for a short period at that temperature and then allowing it to cool in air. Heating the steel just above its upper critical point creates austenitic grains (much smaller than the previous ferritic grains), which during cooling, form new ferritic grains with a further refined grain size. The process produces a tougher, more ductile material, and eliminates columnar grains and dendritic segregation that sometimes occurs during casting. Normalizing improves machinability of a component and provides dimensional stability if subjected to further heat treatment processes.

### Process annealing

Process annealing, also called intermediate annealing, subcritical annealing, or in-process annealing, is a heat treatment cycle that restores some of the ductility to a product being cold-worked so it can be cold-worked further without breaking.

The temperature range for process annealing ranges from 260 °C (500 °F) to 760 °C (1400 °F), depending on the alloy in question. This process is mainly suited for low-carbon steel. The material is heated up to a temperature just below the lower critical temperature of steel. Cold-worked steel normally tends to possess increased hardness and decreased ductility, making it difficult to work. Process annealing tends to improve these characteristics. This is mainly carried out on cold-rolled steel like wire-drawn steel,Centrifugally cast ductile iron pipe etc.

### Full anneal

A full anneal typically results in the second most ductile state a metal can assume for metal alloy. Its purpose is to originate a uniform and stable microstructure that most closely resembles the metal's phase diagram equilibrium microstructure, thus letting the metal attain relatively low levels of hardness, yield strength and ultimate strength with high plasticity and toughness. To perform a full anneal on a steel for example, steel is heated to slightly above the austenitic temperature and held for sufficient time to allow the material to fully form austenite or austenite-cementite grain structure. The material is then allowed to cool very slowly so that the equilibrium microstructure is obtained. In most cases this means the material is allowed to furnace cool (the furnace is turned off and the steel is let cool down inside) but in some cases it is air cooled. The cooling rate of the steel has to be sufficiently slow so as to not let the austenite transform into bainite or martensite, but rather have it completely transform to pearlite and ferrite or cementite. This means that steels that are very hardenable (i.e. tend to form martensite under moderately low cooling rates) have to be furnace cooled. The details of the process depend on the type of metal and the precise alloy involved. In any case the result is a more ductile material but a lower yield strength and a lower tensile strength. This process is also called LP annealing for lamellar pearlite in the steel industry as opposed to a process anneal, which does not specify a microstructure and only has the goal of softening the material. Often the material to be machined is annealed, and then subject to further heat treatment to achieve the final desired properties.

### Short cycle anneal

Short cycle annealing is used for turning normal ferrite into malleable ferrite. It consists of heating, cooling and then heating again from 4 to 8 hours.

## Resistive heating

Resistive heating can be used to efficiently anneal copper wire; the heating system employs a controlled electrical short circuit. It can be advantageous because it does not require a temperature-regulated furnace like other methods of annealing.

The process consists of two conductive pulleys (step pulleys), which the wire passes across after it is drawn. The two pulleys have an electrical potential across them, which causes the wire to form a short circuit. The Joule effect causes the temperature of the wire to rise to approximately 400 °C. This temperature is affected by the rotational speed of the pulleys, the ambient temperature, and the voltage applied. Where t is the temperature of the wire, K is a constant, V is the voltage applied, r is the number of rotations of the pulleys per minute, and ta is the ambient temperature:

${\displaystyle t={\frac {1}{r}}KV^{2}+t_{a}}$

The constant K depends on the diameter of the pulleys and the resistivity of the copper.

Purely in terms of the temperature of the copper wire, an increase in the speed of the wire through the pulley system has the same effect as a decrease in resistance.

## Related Research Articles

An alloy is a combination of metals and of a metal or another element. Alloys are defined by a metallic bonding character. An alloy may be a solid solution of metal elements or a mixture of metallic phases. Intermetallic compounds are alloys with a defined stoichiometry and crystal structure. Zintl phases are also sometimes considered alloys depending on bond types.

Forging is a manufacturing process involving the shaping of metal using localized compressive forces. The blows are delivered with a hammer or a die. Forging is often classified according to the temperature at which it is performed: cold forging, warm forging, or hot forging. For the latter two, the metal is heated, usually in a forge. Forged parts can range in weight from less than a kilogram to hundreds of metric tons. Forging has been done by smiths for millennia; the traditional products were kitchenware, hardware, hand tools, edged weapons, cymbals, and jewellery. Since the Industrial Revolution, forged parts are widely used in mechanisms and machines wherever a component requires high strength; such forgings usually require further processing to achieve a finished part. Today, forging is a major worldwide industry.

Heat treating is a group of industrial and metalworking processes used to alter the physical, and sometimes chemical, properties of a material. The most common application is metallurgical. Heat treatments are also used in the manufacture of many other materials, such as glass. Heat treatment involves the use of heating or chilling, normally to extreme temperatures, to achieve a desired result such as hardening or softening of a material. Heat treatment techniques include annealing, case hardening, precipitation strengthening, tempering, carburizing, normalizing and quenching. It is noteworthy that while the term heat treatment applies only to processes where the heating and cooling are done for the specific purpose of altering properties intentionally, heating and cooling often occur incidentally during other manufacturing processes such as hot forming or welding.

Austenite, also known as gamma-phase iron (γ-Fe), is a metallic, non-magnetic allotrope of iron or a solid solution of iron, with an alloying element. In plain-carbon steel, austenite exists above the critical eutectoid temperature of 1000 K (727 °C); other alloys of steel have different eutectoid temperatures. The austenite allotrope is named after Sir William Chandler Roberts-Austen (1843–1902); it exists at room temperature in stainless steel.

Brazing is a metal-joining process in which two or more metal items are joined together by melting and flowing a filler metal into the joint, the filler metal having a lower melting point than the adjoining metal.

Induction heating is the process of heating an electrically conducting object by electromagnetic induction, through heat generated in the object by eddy currents. An induction heater consists of an electromagnet, and an electronic oscillator that passes a high-frequency alternating current (AC) through the electromagnet. The rapidly alternating magnetic field penetrates the object, generating electric currents inside the conductor called eddy currents. The eddy currents flowing through the resistance of the material heat it by Joule heating. In ferromagnetic materials like iron, heat may also be generated by magnetic hysteresis losses. The frequency of current used depends on the object size, material type, coupling and the penetration depth.

Carbon steel is a steel with carbon content up to 2.1% by weight. The definition of carbon steel from the American Iron and Steel Institute (AISI) states:

In materials science, quenching is the rapid cooling of a workpiece in water, oil or air to obtain certain material properties. A type of heat treating, quenching prevents undesired low-temperature processes, such as phase transformations, from occurring. It does this by reducing the window of time during which these undesired reactions are both thermodynamically favorable, and kinetically accessible; for instance, quenching can reduce the crystal grain size of both metallic and plastic materials, increasing their hardness.

Carburizing, carburising, or carburization is a heat treatment process in which iron or steel absorbs carbon while the metal is heated in the presence of a carbon-bearing material, such as charcoal or carbon monoxide. The intent is to make the metal harder. Depending on the amount of time and temperature, the affected area can vary in carbon content. Longer carburizing times and higher temperatures typically increase the depth of carbon diffusion. When the iron or steel is cooled rapidly by quenching, the higher carbon content on the outer surface becomes hard due to the transformation from austenite to martensite, while the core remains soft and tough as a ferritic and/or pearlite microstructure.

Case-hardening or surface hardening is the process of hardening the surface of a metal object while allowing the metal deeper underneath to remain soft, thus forming a thin layer of harder metal at the surface. For iron or steel with low carbon content, which has poor to no hardenability of its own, the case-hardening process involves infusing additional carbon or nitrogen into the surface layer. Case-hardening is usually done after the part has been formed into its final shape, but can also be done to increase the hardening element content of bars to be used in a pattern welding or similar process. The term face hardening is also used to describe this technique, when discussing modern armour.

Work hardening, also known as strain hardening, is the strengthening of a metal or polymer by plastic deformation. This strengthening occurs because of dislocation movements and dislocation generation within the crystal structure of the material. Many non-brittle metals with a reasonably high melting point as well as several polymers can be strengthened in this fashion. Alloys not amenable to heat treatment, including low-carbon steel, are often work-hardened. Some materials cannot be work-hardened at low temperatures, such as indium, however others can only be strengthened via work hardening, such as pure copper and aluminum.

Tempering is a process of heat treating, which is used to increase the toughness of iron-based alloys. Tempering is usually performed after hardening, to reduce some of the excess hardness, and is done by heating the metal to some temperature below the critical point for a certain period of time, then allowing it to cool in still air. The exact temperature determines the amount of hardness removed, and depends on both the specific composition of the alloy and on the desired properties in the finished product. For instance, very hard tools are often tempered at low temperatures, while springs are tempered to much higher temperatures.

Cryogenic hardening is a cryogenic treatment process where the material is cooled to approximately −185 °C (−301 °F), usually using liquid nitrogen. It can have a profound effect on the mechanical properties of certain steels, provided their composition and prior heat treatment are such that they retain some austenite at room temperature. It is designed to increase the amount of martensite in the steel's crystal structure, increasing its strength and hardness, sometimes at the cost of toughness. Presently this treatment is being practiced over tool steels, high-carbon, and high-chromium steels to obtain excellent wear resistance. Recent research shows that there is precipitation of fine carbides in the matrix during this treatment which imparts very high wear resistance to the steels.

Hardening is a metallurgical metalworking process used to increase the hardness of a metal. The hardness of a metal is directly proportional to the uniaxial yield stress at the location of the imposed strain. A harder metal will have a higher resistance to plastic deformation than a less hard metal.

Recrystallization is a process by which deformed grains are replaced by a new set of defect-free grains that nucleate and grow until the original grains have been entirely consumed. Recrystallization is usually accompanied by a reduction in the strength and hardness of a material and a simultaneous increase in the ductility. Thus, the process may be introduced as a deliberate step in metals processing or may be an undesirable byproduct of another processing step. The most important industrial uses are softening of metals previously hardened or rendered brittle by cold work, and control of the grain structure in the final product.

A vacuum furnace is a type of furnace in which the product in the furnace is surrounded by a vacuum during processing. The absence of air or other gases prevents oxidation, heat loss from the product through convection, and removes a source of contamination. This enables the furnace to heat materials to temperatures as high as 3,000 °C (5,432 °F) with select materials. Maximum furnace temperatures and vacuum levels depend on melting points and vapor pressures of heated materials. Vacuum furnaces are used to carry out processes such as annealing, brazing, sintering and heat treatment with high consistency and low contamination.

Austempering is heat treatment that is applied to ferrous metals, most notably steel and ductile iron. In steel it produces a bainite microstructure whereas in cast irons it produces a structure of acicular ferrite and high carbon, stabilized austenite known as ausferrite. It is primarily used to improve mechanical properties or reduce / eliminate distortion. Austempering is defined by both the process and the resultant microstructure. Typical austempering process parameters applied to an unsuitable material will not result in the formation of bainite or ausferrite and thus the final product will not be called austempered. Both microstructures may also be produced via other methods. For example, they may be produced as-cast or air cooled with the proper alloy content. These materials are also not referred to as austempered.

Hot working process metals are plastically deformed above their recrystallization temperature. Being above the recrystallization temperature allows the material to recrystallize during deformation. This is important because recrystallization keeps the materials from strain hardening, which ultimately keeps the yield strength and hardness low and ductility high. This contrasts with cold working.

Rule based DFM analysis for forging. Forging is the controlled deformation of metal into a specific shape by compressive forces. The forging process goes back to 8000 B.C. and evolved from the manual art of simple blacksmithing. Then as now, a series of compressive hammer blows performs the shaping or forging of the part. Modern forging uses machine driven impact hammers or presses which deform the work-piece by controlled pressure. The forging process is superior to casting in that the parts formed have denser microstructures, more defined grain patterns, and less porosity, making such parts much stronger than a casting. All metals and alloys are forge-able, but each will have a forge-ability rating from high to low or poor. The factors involved are the material’s composition, crystal structure and mechanical properties all considered within a temperature range. The wider the temperature range, the higher the forge-ability rating. Most forging is done on heated work-pieces. "Cold forging" can occur at room temperatures. The most forge-able materials are aluminum, copper, and magnesium. Lower ratings are applied to the various steels, nickel, and titanium alloys. Hot forging temperatures range from 93°C (200°F) to 1650°C (3000°F) for refractory metals.

## References

1. "Archived copy". Archived from the original on 2010-07-24. Retrieved 2010-04-19.CS1 maint: Archived copy as title (link)
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3. Alvarenga, H. D.; Van de Putte, T.; Van Steenberge, N.; Sietsma, J.; Terryn, H. (Apr 2009). "Influence of Carbide Morphology and Microstructure on the Kinetics of Superficial Decarburization of C-Mn Steels". Metal Mater Trans A. doi:10.1007/s11661-014-2600-y.
4. Verhoeven, J.D. Fundamentals of Physical Metallurgy, Wiley, New York, 1975, p. 326
• Thesis of Degree, Cable Manufacture and Tests of General Use and Energy.-Jorge Luis Pedraz (1994), UNI, Files, Peru.
• Dynamic annealing of the Copper wire by using a Controlled Short circuit.=Jorge Luis Pedraz (1999), Peru: Lima, CONIMERA 1999, INTERCON 99,
• Annealing - efunda - engineering fundamentals
• Annealing - Aluminum and Aircraft Metal Alloys