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Chemical milling or industrial etching is the
subtractive manufacturing Machining is a manufacturing process where a desired shape or part is created using the controlled removal of material, most often metal, from a larger piece of raw material by cutting. Machining is a form of subtractive manufacturing, which util ...
process of using baths of temperature-regulated etching chemicals to remove material to create an object with the desired shape. Other names for chemical etching include photo etching, chemical etching, photo chemical etching and
photochemical machining Photochemical machining (PCM), also known as photochemical milling or photo etching, is a chemical milling process used to fabricate sheet metal components using a photoresist and etchants to corrosively machine away selected areas. This proces ...
. It is mostly used on metals, though other materials are increasingly important. It was developed from armor-decorating and printing
etching Etching is traditionally the process of using strong acid or mordant to cut into the unprotected parts of a metal surface to create a design in intaglio (incised) in the metal. In modern manufacturing, other chemicals may be used on other type ...
processes developed during the
Renaissance The Renaissance ( , ) is a Periodization, period of history and a European cultural movement covering the 15th and 16th centuries. It marked the transition from the Middle Ages to modernity and was characterized by an effort to revive and sur ...
as alternatives to
engraving Engraving is the practice of incising a design on a hard, usually flat surface by cutting grooves into it with a Burin (engraving), burin. The result may be a decorated object in itself, as when silver, gold, steel, or Glass engraving, glass ar ...
on metal. The process essentially involves bathing the cutting areas in a corrosive chemical known as an etchant, which reacts with the material in the area to be cut and causes the solid material to be dissolved; inert substances known as maskants are used to protect specific areas of the material as
resist A resist, used in many areas of manufacturing and art, is something that is added to parts of an object to create a pattern by protecting these parts from being affected by a subsequent stage in the process. Often the resist is then removed. For ...
s.


History

Organic chemicals such as lactic acid and citric acid have been used to etch metals and create products as early as 400 BCE, when vinegar was used to corrode
lead Lead () is a chemical element; it has Chemical symbol, symbol Pb (from Latin ) and atomic number 82. It is a Heavy metal (elements), heavy metal that is density, denser than most common materials. Lead is Mohs scale, soft and Ductility, malleabl ...
and create the pigment ceruse, also known as
white lead White lead is the basic lead carbonate 2PbCO3·Pb(OH)2. It is a complex Salt (chemistry), salt, containing both carbonate and hydroxide ions. White lead occurs naturally as a mineral, in which context it is known as hydrocerussite, a hydrate of ...
. Most modern chemical milling methods involve alkaline etchants; these may have been used as early as the first century CE. Armor etching, using strong mineral acids, was not developed until the fifteenth century. Etchants mixed from salt, charcoal, and vinegar were applied to plate armor that had been painted with a maskant of linseed-oil paint. The etchant would bite into the unprotected areas, causing the painted areas to be raised into
relief Relief is a sculpture, sculptural method in which the sculpted pieces remain attached to a solid background of the same material. The term ''wikt:relief, relief'' is from the Latin verb , to raise (). To create a sculpture in relief is to give ...
. Etching in this manner allowed armor to be decorated as if with precise engraving, but without the existence of raised burrs; it also prevented the necessity of the armor being softer than an engraving tool. Late in the seventeenth century, etching became used to produce the graduations on measuring instruments; the thinness of lines that etching could produce allowed for the production of more precise and accurate instruments than were possible before. Not long after, it became used to etch trajectory information plates for cannon and
artillery Artillery consists of ranged weapons that launch Ammunition, munitions far beyond the range and power of infantry firearms. Early artillery development focused on the ability to breach defensive walls and fortifications during sieges, and l ...
operators; paper would rarely survive the rigors of combat, but an etched plate could be quite durable. Often such information (normally ranging marks) was etched onto equipment such as
stiletto A stiletto (plural stilettos) is a specialized dagger with a long slender blade and needle-like point, primarily intended as a thrusting and stabbing weapon.Limburg, Peter R., ''What's In The Names Of Antique Weapons'', Coward, McCann & Geoghega ...
daggers or shovels. In 1782, the discovery was made by John Senebier that certain resins lost their solubility to turpentine when exposed to light; that is, they hardened. This allowed the development of photochemical milling, where a liquid maskant is applied to the entire surface of a material, and the outline of the area to be masked created by exposing it to UV light. Photo-chemical milling was extensively used in the development of photography methods, allowing light to create impressions on metal plates. One of the earliest uses of chemical etching to mill commercial parts was in 1927, when the Swedish company Aktiebolaget Separator patented a method of producing edge filters by chemically milling the gaps in the filters. Later, around the 1940s, it became widely used to machine thin samples of very hard metal; photo-etching from both sides was used to cut sheet metal, foil, and shim stock to create shims, recording heat frets, and other components.


Application

Etching has applications in the
printed circuit board A printed circuit board (PCB), also called printed wiring board (PWB), is a Lamination, laminated sandwich structure of electrical conduction, conductive and Insulator (electricity), insulating layers, each with a pattern of traces, planes ...
and
semiconductor A semiconductor is a material with electrical conductivity between that of a conductor and an insulator. Its conductivity can be modified by adding impurities (" doping") to its crystal structure. When two regions with different doping level ...
fabrication industries. It is also used in the aerospace industry to remove shallow layers of material from large aircraft components, missile skin panels, and extruded parts for airframes. Etching is used widely to manufacture
integrated circuit An integrated circuit (IC), also known as a microchip or simply chip, is a set of electronic circuits, consisting of various electronic components (such as transistors, resistors, and capacitors) and their interconnections. These components a ...
s and
Microelectromechanical systems MEMS (micro-electromechanical systems) is the technology of microscopic devices incorporating both electronic and moving parts. MEMS are made up of components between 1 and 100 micrometres in size (i.e., 0.001 to 0.1 mm), and MEMS devices ...
. In addition to the standard, liquid-based techniques, the semiconductor industry commonly uses
plasma etching Plasma etching is a form of plasma processing used to fabricate integrated circuits. It involves a high-speed stream of glow discharge (Plasma (physics), plasma) of an appropriate gas mixture being shot (in pulses) at a sample. The plasma source, ...
.


Process

Chemical milling is normally performed in a series of five steps: cleaning, masking, scribing, etching, and demasking.Video of chemical milling processLearn more about the video


Cleaning

Cleaning is the preparatory process of ensuring that the surface to be etched is free of contaminants which could negatively impact the quality of the finished part. An improperly cleaned surface could result in poor adhesion of the maskant, causing areas to be etched erroneously, or a non-uniform etch rate which could result in inaccurate final dimensions. The surface must be kept free from oils, grease, primer coatings, markings and other residue from the marking out process, scale (oxidation), and any other foreign contaminants. For most metals, this step can be performed by applying a solvent substance to the surface to be etched, washing away foreign contaminants. The material may also be immersed in alkaline cleaners or specialized de-oxidizing solutions. It is common practice in modern industrial chemical etching facilities that the workpiece never be directly handled after this process, as oils from human skin could easily contaminate the surface.


Masking

Masking is the process of applying the maskant material to the surface to ensure that only desired areas are etched. Liquid maskants may be applied via dip-masking, in which the part is dipped into an open tank of maskant and then the maskant dried. Maskant may also be applied by flow coating: liquid maskant is flowed over the surface of the part. Certain conductive maskants may also be applied by electrostatic deposition, where
electrical charge Electricity is the set of physical phenomena associated with the presence and motion of matter possessing an electric charge. Electricity is related to magnetism, both being part of the phenomenon of electromagnetism, as described by Maxwel ...
s are applied to particles of maskant as it is sprayed onto the surface of the material. The charge causes the particles of maskant to adhere to the surface.


Maskant types

The maskant to be used is determined primarily by the chemical used to etch the material, and the material itself. The maskant must adhere to the surface of the material, and it must also be chemically inert enough with regard to the etchant to protect the workpiece. Most modern chemical milling processes use maskants with an adhesion around ; if the adhesion is too strong, the scribing process may be too difficult to perform. If the adhesion is too low, the etching area may be imprecisely defined. Most industrial chemical milling facilities use maskants based upon neoprene
elastomers An elastomer is a polymer with viscoelasticity (i.e. both viscosity and Elasticity (physics), elasticity) and with weak intermolecular forces, generally low Young's modulus (E) and high failure strain compared with other materials. The term, a ...
or isobutylene-isoprene copolymers.


Scribing

Scribing is the removal of maskant on the areas to be etched. For decorative applications, this is often done by hand through the use of a scribing knife, etching needle or similar tool; modern industrial applications may involve an operator scribing with the aid of a template or use
computer numerical control Computer numerical control (CNC) or CNC machining is the Automation, automated control of machine tools by a computer. It is an evolution of numerical control (NC), where machine tools are directly managed by data storage media such as punched ...
to automate the process. For parts involving multiple stages of etching, complex templates using colour codes and similar devices may be used.


Etching

Etching is the immersion of the part into the chemical bath, and the action of the chemical on the part to be milled. The time spent immersed in the chemical bath determines the depth of the resulting etch; this time is calculated via the formula: :E = \frac s t where ''E'' is the rate of etching (usually abbreviated to ''etch rate''), ''s'' is the depth of the cut required, and ''t'' is the total immersion time. Etch rate varies based on factors such as the concentration and composition of the etchant, the material to be etched, and temperature conditions. Due to its inconstant nature, etch rate is often determined experimentally immediately prior to the etching process. A small sample of the material to be cut, of the same material specification, heat-treatment condition, and approximately the same thickness is etched for a certain time; after this time, the depth of the etch is measured and used with the time to calculate the etch rate.
Aluminium Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...
is commonly etched at rates around , and
magnesium Magnesium is a chemical element; it has Symbol (chemistry), symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 ...
about


Demasking

Demasking is the process of clearing the part of etchant and maskant. Etchant is generally removed with a wash of clear, cold water. A de-oxidizing bath may also be required in the common case that the etching process left a film of oxide on the surface of the material. Various methods may be used to remove the maskant, the most common being hand removal using scraping tools. This is frequently time-consuming and laborious, and for large-scale processes may be automated.


Common etchants

;For
aluminium Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...
*
sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula . It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly corrosive base (chemistry), ...
* Keller's reagent ;For
steel Steel is an alloy of iron and carbon that demonstrates improved mechanical properties compared to the pure form of iron. Due to steel's high Young's modulus, elastic modulus, Yield (engineering), yield strength, Fracture, fracture strength a ...
s * hydrochloric and
nitric acid Nitric acid is an inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into nitrogen oxide, oxides of nitrogen. Most com ...
s *
ferric chloride Iron(III) chloride describes the inorganic compounds with the formula (H2O)x. Also called ferric chloride, these compounds are some of the most important and commonplace compounds of iron. They are available both in anhydrous and in hydrated f ...
for stainless steels * Nital (a mixture of
nitric acid Nitric acid is an inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into nitrogen oxide, oxides of nitrogen. Most com ...
and
ethanol Ethanol (also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound with the chemical formula . It is an Alcohol (chemistry), alcohol, with its formula also written as , or EtOH, where Et is the ps ...
,
methanol Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical compound and the simplest aliphatic Alcohol (chemistry), alcohol, with the chemical formula (a methyl group linked to a hydroxyl group, often ab ...
, or methylated spirits for mild steels. 2% Nital is common etchant for plain carbon steels. ;For
copper Copper is a chemical element; it has symbol Cu (from Latin ) 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-orang ...
*
cupric chloride Copper(II) chloride, also known as cupric chloride, is an inorganic compound with the chemical formula . The monoclinic yellowish-brown anhydrous form slowly absorbs moisture to form the orthorhombic blue-green dihydrate , with two water molecule ...
*
ferric chloride Iron(III) chloride describes the inorganic compounds with the formula (H2O)x. Also called ferric chloride, these compounds are some of the most important and commonplace compounds of iron. They are available both in anhydrous and in hydrated f ...
*
ammonium persulfate Ammonium persulfate (APS) is the inorganic compound with the formula (NH4)2S2O8. It is a colourless (white) salt that is highly soluble in water, much more so than the related potassium salt. It is a strong oxidizing agent that is used as a cataly ...
*
ammonia Ammonia is an inorganic chemical compound of nitrogen and hydrogen with the chemical formula, formula . A Binary compounds of hydrogen, stable binary hydride and the simplest pnictogen hydride, ammonia is a colourless gas with a distinctive pu ...
* 25-50%
nitric acid Nitric acid is an inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into nitrogen oxide, oxides of nitrogen. Most com ...
. *
hydrochloric acid Hydrochloric acid, also known as muriatic acid or spirits of salt, is an aqueous solution of hydrogen chloride (HCl). It is a colorless solution with a distinctive pungency, pungent smell. It is classified as a acid strength, strong acid. It is ...
and
hydrogen peroxide Hydrogen peroxide is a chemical compound with the formula . In its pure form, it is a very pale blue liquid that is slightly more viscosity, viscous than Properties of water, water. It is used as an oxidizer, bleaching agent, and antiseptic, usua ...
;For
silica Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula , commonly found in nature as quartz. In many parts of the world, silica is the major constituent of sand. Silica is one of the most complex and abundant f ...
*
hydrofluoric acid Hydrofluoric acid is a solution of hydrogen fluoride (HF) in water. Solutions of HF are colorless, acidic and highly corrosive. A common concentration is 49% (48–52%) but there are also stronger solutions (e.g. 70%) and pure HF has a boiling p ...


See also

*
Photochemical machining Photochemical machining (PCM), also known as photochemical milling or photo etching, is a chemical milling process used to fabricate sheet metal components using a photoresist and etchants to corrosively machine away selected areas. This proces ...
*
Etching (microfabrication) Etching is used in microfabrication to chemically remove layers from the surface of a wafer (electronics), wafer during manufacturing. Etching is a critically important process module in fabrication, and every wafer undergoes many etching steps b ...
* Electroetching


Notes


References

* {{Decorative arts Etching Metalworking Chemical processes Electrolysis Metallurgical processes