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Chemical milling or industrial etching is the subtractive manufacturing 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. 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 types ...
processes developed during the
Renaissance The Renaissance ( , ) , from , with the same meanings. is a period in European history marking the transition from the Middle Ages to modernity and covering the 15th and 16th centuries, characterized by an effort to revive and surpass ide ...
as alternatives to
engraving Engraving is the practice of incising a design onto a hard, usually flat surface by cutting grooves into it with a burin. The result may be a decorated object in itself, as when silver, gold, steel, or glass are engraved, or may provide an in ...
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 resists.


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 with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cut, ...
and create the pigment
ceruse Venetian ceruse, also known as ''blanc de ceruse de Venise'' and Spirits of Saturn, was a 16th-century cosmetic used as a skin whitener. It was in great demand and considered the best available at the time, supposedly containing the best quality ...
, also known as
white lead White lead is the basic lead carbonate 2PbCO3·Pb(OH)2. It is a complex 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 cerussite. It was ...
. 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 sculptural method in which the sculpted pieces are bonded to a solid background of the same material. The term '' relief'' is from the Latin verb ''relevo'', to raise. To create a sculpture in relief is to give the impression that th ...
. 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 is a class of heavy military ranged weapons that launch munitions far beyond the range and power of infantry firearms. Early artillery development focused on the ability to breach defensive walls and fortifications during si ...
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 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.


Applications

Etching has applications in the
printed circuit board A printed circuit board (PCB; also printed wiring board or PWB) is a medium used in electrical and electronic engineering to connect electronic components to one another in a controlled manner. It takes the form of a laminated sandwich str ...
and
semiconductor A semiconductor is a material which has an electrical conductivity value falling between that of a conductor, such as copper, and an insulator, such as glass. Its resistivity falls as its temperature rises; metals behave in the opposite way ...
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 or monolithic integrated circuit (also referred to as an IC, a chip, or a microchip) is a set of electronic circuits on one small flat piece (or "chip") of semiconductor material, usually silicon. Large numbers of tiny ...
s and
Microelectromechanical systems Microelectromechanical systems (MEMS), also written as micro-electro-mechanical systems (or microelectronic and microelectromechanical systems) and the related micromechatronics and microsystems constitute the technology of microscopic 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) of an appropriate gas mixture being shot (in pulses) at a sample. The plasma source, known as etch spec ...
.


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 that has a property of electric charge. Electricity is related to magnetism, both being part of the phenomenon of electromagnetism, as described ...
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 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 Numerical control (also computer numerical control, and commonly called CNC) is the automated control of machining tools (such as drills, lathes, mills, grinders, routers and 3D printers) by means of a computer. A CNC machine processes a p ...
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 (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. It ha ...
is commonly etched at rates around , and
magnesium Magnesium is a chemical element with the 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 of the periodic ...
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 (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. It ha ...
*
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 al ...
* Keller's reagent ;For
steel Steel is an alloy made up of iron with added carbon to improve its strength and fracture resistance compared to other forms of iron. Many other elements may be present or added. Stainless steels that are corrosion- and oxidation-resistan ...
s * hydrochloric and
nitric acid Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available ni ...
s *
ferric 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 ...
for stainless steels * Nital (a mixture of
nitric acid Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available ni ...
and
ethanol Ethanol (abbr. EtOH; also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound. It is an alcohol with the chemical formula . Its formula can be also written as or (an ethyl group linked to a ...
,
methanol Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical and the simplest aliphatic alcohol, with the formula C H3 O H (a methyl group linked to a hydroxyl group, often abbreviated as MeOH). It is ...
, or methylated spirits for mild steels. 2% Nital is common etchant for plain carbon steels. ;For
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 pink ...
* cupric chloride *
ferric 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 ...
* ammonium persulfate *
ammonia Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous ...
* 25-50%
nitric acid Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available ni ...
. *
hydrochloric acid Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid. It is a component of the gastric acid in the dige ...
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 viscous than water. It is used as an oxidizer, bleaching agent, and antiseptic, usually as a dilute solution (3 ...
;For
silica Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula , most commonly found in nature as quartz and in various living organisms. In many parts of the world, silica is the major constituent of sand. Silica is ...
*
hydrofluoric acid Hydrofluoric acid is a solution of hydrogen fluoride (HF) in water. Solutions of HF are colourless, acidic and highly corrosive. It is used to make most fluorine-containing compounds; examples include the commonly used pharmaceutical antidepres ...


See also

* Photochemical machining *
Etching (microfabrication) Etching is used in microfabrication to chemically remove layers from the surface of a wafer during manufacturing. Etching is a critically important process module, and every wafer undergoes many etching steps before it is complete. For many etch ...
*
Electroetching Electroetching is a metal etching process that involves the use of a solution of an electrolyte, an anode, and a cathode. The metal piece to be etched is connected to the positive pole of a source of direct electric current. A piece of the same m ...


Notes


References

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