Electroplating
Overview
 
Electroplating is a plating
Plating
Plating is a surface covering in which a metal is deposited on a conductive surface. Plating has been done for hundreds of years, but it is also critical for modern technology...

 process in which metal ions in a solution are moved by an electric field to coat an electrode. The process uses electrical current
Direct current
Direct current is the unidirectional flow of electric charge. Direct current is produced by such sources as batteries, thermocouples, solar cells, and commutator-type electric machines of the dynamo type. Direct current may flow in a conductor such as a wire, but can also flow through...

 to reduce
Redox
Redox reactions describe all chemical reactions in which atoms have their oxidation state changed....

 cations of a desired material from a solution and coat a conductive object with a thin layer of the material, such as a metal. Electroplating is primarily used for depositing a layer of material to bestow a desired property (e.g., abrasion
Abrasion (mechanical)
Abrasion is the process of scuffing, scratching, wearing down, marring, or rubbing away. It can be intentionally imposed in a controlled process using an abrasive...

 and wear resistance, 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...

 protection, lubricity
Lubrication
Lubrication is the process, or technique employed to reduce wear of one or both surfaces in close proximity, and moving relative to each another, by interposing a substance called lubricant between the surfaces to carry or to help carry the load between the opposing surfaces. The interposed...

, aesthetic qualities, etc.) to a surface that otherwise lacks that property.
Encyclopedia
Electroplating is a plating
Plating
Plating is a surface covering in which a metal is deposited on a conductive surface. Plating has been done for hundreds of years, but it is also critical for modern technology...

 process in which metal ions in a solution are moved by an electric field to coat an electrode. The process uses electrical current
Direct current
Direct current is the unidirectional flow of electric charge. Direct current is produced by such sources as batteries, thermocouples, solar cells, and commutator-type electric machines of the dynamo type. Direct current may flow in a conductor such as a wire, but can also flow through...

 to reduce
Redox
Redox reactions describe all chemical reactions in which atoms have their oxidation state changed....

 cations of a desired material from a solution and coat a conductive object with a thin layer of the material, such as a metal. Electroplating is primarily used for depositing a layer of material to bestow a desired property (e.g., abrasion
Abrasion (mechanical)
Abrasion is the process of scuffing, scratching, wearing down, marring, or rubbing away. It can be intentionally imposed in a controlled process using an abrasive...

 and wear resistance, 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...

 protection, lubricity
Lubrication
Lubrication is the process, or technique employed to reduce wear of one or both surfaces in close proximity, and moving relative to each another, by interposing a substance called lubricant between the surfaces to carry or to help carry the load between the opposing surfaces. The interposed...

, aesthetic qualities, etc.) to a surface that otherwise lacks that property. Another application uses electroplating to build up thickness on undersized parts.

The process used in electroplating is called electrodeposition. It is analogous to a galvanic cell
Galvanic cell
A Galvanic cell, or Voltaic cell, named after Luigi Galvani, or Alessandro Volta respectively, is an electrochemical cell that derives electrical energy from spontaneous redox reaction taking place within the cell...

 acting in reverse. The part to be plated is the cathode
Cathode
A cathode is an electrode through which electric current flows out of a polarized electrical device. Mnemonic: CCD .Cathode polarity is not always negative...

 of the circuit. In one technique, the anode
Anode
An anode is an electrode through which electric current flows into a polarized electrical device. Mnemonic: ACID ....

 is made of the metal to be plated on the part. Both components are immersed in a solution
Solution
In chemistry, a solution is a homogeneous mixture composed of only one phase. In such a mixture, a solute is dissolved in another substance, known as a solvent. The solvent does the dissolving.- Types of solutions :...

 called an electrolyte
Electrolyte
In chemistry, an electrolyte is any substance containing free ions that make the substance electrically conductive. The most typical electrolyte is an ionic solution, but molten electrolytes and solid electrolytes are also possible....

 containing one or more dissolved metal salts as well as other ion
Ion
An ion is an atom or molecule in which the total number of electrons is not equal to the total number of protons, giving it a net positive or negative electrical charge. The name was given by physicist Michael Faraday for the substances that allow a current to pass between electrodes in a...

s that permit the flow of electricity. A power supply
Power supply
A power supply is a device that supplies electrical energy to one or more electric loads. The term is most commonly applied to devices that convert one form of electrical energy to another, though it may also refer to devices that convert another form of energy to electrical energy...

 supplies a direct current
Direct current
Direct current is the unidirectional flow of electric charge. Direct current is produced by such sources as batteries, thermocouples, solar cells, and commutator-type electric machines of the dynamo type. Direct current may flow in a conductor such as a wire, but can also flow through...

 to the anode
Anode
An anode is an electrode through which electric current flows into a polarized electrical device. Mnemonic: ACID ....

, oxidizing the metal atoms that comprise it and allowing them to dissolve in the solution. At the cathode, the dissolved metal ions in the electrolyte solution are reduced at the interface between the solution and the cathode, such that they "plate out" onto the cathode. The rate at which the anode is dissolved is equal to the rate at which the cathode is plated, vis-a-vis the current flowing through the circuit. In this manner, the ions in the electrolyte bath are continuously replenished by the anode.

Other electroplating processes may use a non-consumable anode such as lead. In these techniques, ions of the metal to be plated must be periodically replenished in the bath as they are drawn out of the solution.

Process

The anode and cathode in the electroplating cell are both connected to an external supply of direct current — a battery or, more commonly, a rectifier. The anode is connected to the positive terminal of the supply, and the cathode (article to be plated) is connected to the negative terminal. When the external power supply is switched on, the metal at the anode is oxidized from the zero valence
Valence (chemistry)
In chemistry, valence, also known as valency or valence number, is a measure of the number of bonds formed by an atom of a given element. "Valence" can be defined as the number of valence bonds...

 state to form cations with a positive charge. These cations associate with the anions in the solution. The cations are reduced at the cathode to deposit in the metallic, zero valence state. For example, in an acid solution, 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...

 is oxidized at the anode to Cu2+ by losing two electrons. The Cu2+ associates with the anion SO42- in the solution to form copper sulfate. At the cathode, the Cu2+ is reduced to metallic copper by gaining two electrons. The result is the effective transfer of copper from the anode source to a plate covering the cathode.

The plating is most commonly a single metallic element
Chemical element
A chemical element is a pure chemical substance consisting of one type of atom distinguished by its atomic number, which is the number of protons in its nucleus. Familiar examples of elements include carbon, oxygen, aluminum, iron, copper, gold, mercury, and lead.As of November 2011, 118 elements...

, not an alloy
Alloy
An alloy is a mixture or metallic solid solution composed of two or more elements. Complete solid solution alloys give single solid phase microstructure, while partial solutions give two or more phases that may or may not be homogeneous in distribution, depending on thermal history...

. However, some alloys can be electrodeposited, notably brass
Brass
Brass is an alloy of copper and zinc; the proportions of zinc and copper can be varied to create a range of brasses with varying properties.In comparison, bronze is principally an alloy of copper and tin...

 and solder
Solder
Solder is a fusible metal alloy used to join together metal workpieces and having a melting point below that of the workpiece.Soft solder is what is most often thought of when solder or soldering are mentioned and it typically has a melting range of . It is commonly used in electronics and...

.

Many plating baths include cyanide
Cyanide
A cyanide is a chemical compound that contains the cyano group, -C≡N, which consists of a carbon atom triple-bonded to a nitrogen atom. Cyanides most commonly refer to salts of the anion CN−. Most cyanides are highly toxic....

s of other metals (e.g., potassium cyanide
Potassium cyanide
Potassium cyanide is an inorganic compound with the formula KCN. This colorless crystalline compound, similar in appearance to sugar, is highly soluble in water. Most KCN is used in gold mining, organic synthesis, and electroplating. Smaller applications include jewelry for chemical gilding and...

) in addition to cyanides of the metal to be deposited. These free cyanides facilitate anode corrosion, help to maintain a constant metal ion level and contribute to conductivity. Additionally, non-metal chemicals such as carbonate
Carbonate
In chemistry, a carbonate is a salt of carbonic acid, characterized by the presence of the carbonate ion, . The name may also mean an ester of carbonic acid, an organic compound containing the carbonate group C2....

s and phosphate
Phosphate
A phosphate, an inorganic chemical, is a salt of phosphoric acid. In organic chemistry, a phosphate, or organophosphate, is an ester of phosphoric acid. Organic phosphates are important in biochemistry and biogeochemistry or ecology. Inorganic phosphates are mined to obtain phosphorus for use in...

s may be added to increase conductivity.

When plating is not desired on certain areas of the substrate, stop-offs are applied to prevent the bath from coming in contact with the substrate. Typical stop-offs include tape, foil, lacquer
Lacquer
In a general sense, lacquer is a somewhat imprecise term for a clear or coloured varnish that dries by solvent evaporation and often a curing process as well that produces a hard, durable finish, in any sheen level from ultra matte to high gloss and that can be further polished as required...

s, and wax
Wax
thumb|right|[[Cetyl palmitate]], a typical wax ester.Wax refers to a class of chemical compounds that are plastic near ambient temperatures. Characteristically, they melt above 45 °C to give a low viscosity liquid. Waxes are insoluble in water but soluble in organic, nonpolar solvents...

es.

Strike

Initially, a special plating deposit called a "strike" or "flash" may be used to form a very thin (typically less than 0.1 micrometer thick) plating with high quality and good adherence to the substrate. This serves as a foundation for subsequent plating processes. A strike uses a high current density and a bath with a low ion concentration. The process is slow, so more efficient plating processes are used once the desired strike thickness is obtained.

The striking method is also used in combination with the plating of different metals. If it is desirable to plate one type of deposit onto a metal to improve corrosion resistance but this metal has inherently poor adhesion to the substrate, a strike can be first deposited that is compatible with both. One example of this situation is the poor adhesion of electrolytic 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...

 on 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...

 alloys, in which case a copper strike is used, which has good adherence to both.

Brush electroplating

A closely related process is brush electroplating, in which localized areas or entire items are plated using a brush saturated with plating solution. The brush, typically a stainless steel
Stainless steel
In metallurgy, stainless steel, also known as inox steel or inox from French "inoxydable", is defined as a steel alloy with a minimum of 10.5 or 11% chromium content by mass....

 body wrapped with a cloth material that both holds the plating solution and prevents direct contact with the item being plated, is connected to the positive side of a low voltage direct-current power source, and the item to be plated connected to the negative. The operator dips the brush in plating solution then applies it to the item, moving the brush continually to get an even distribution of the plating material.
Brush electroplating has several advantages over tank plating, including portability, ability to plate items that for some reason cannot be tank plated (one application was the plating of portions of very large decorative support columns in a building restoration), low or no masking requirements, and comparatively low plating solution volume requirements. Disadvantages compared to tank plating can include greater operator involvement (tank plating can frequently be done with minimal attention), and inability to achieve as great a plate thickness.

Electroless deposition

Usually an electrolytic cell
Electrolytic cell
An electrolytic cell decomposes chemical compounds by means of electrical energy, in a process called electrolysis; the Greek word lysis means to break up. The result is that the chemical energy is increased...

 (consisting of two electrodes, electrolyte, and external source of current) is used for electrodeposition. In contrast, an electroless deposition process uses only one electrode and no external source of electric current. However, the solution for the electroless process needs to contain a reducing agent so that the electrode reaction has the form:

In principle any water-based reducer can be used although the redox potential of the reducer half-cell must be high enough to overcome the energy barriers inherent in liquid chemistry. Electroless nickel plating
Electroless nickel plating
Electroless nickel plating is an auto-catalytic chemical technique used to deposit a layer of nickel-phosphorus or nickel-boron alloy on a solid workpiece, such as metal or plastic. The process relies on the presence of a reducing agent, for example hydrated sodium hypophosphite which reacts with...

 uses hypophosphite as the reducer while plating of other metals like silver, gold and copper typically use low molecular weight aldehydes.

A major benefit of this approach over electroplating is that power sources and plating baths are not needed, reducing the cost of production. The technique can also plate diverse shapes and types of surface. The downside is that the plating process is usually slower and cannot create such thick plates of metal. As a consequence of these characteristics, electroless deposition is quite common in the decorative arts.

Cleanliness

Cleanliness
Parts cleaning
Parts cleaning is essential to many industrial processes, as a prelude to surface finishing or to protect sensitive components. Electroplating is particularly sensitive to part cleanliness, since molecular layers of oil can prevent adhesion of the coating. ASTM B322 is a standard guide for cleaning...

 is essential to successful electroplating, since molecular layers of oil can prevent adhesion of the coating. ASTM B322 is a standard guide for cleaning metals prior to electroplating. Cleaning processes include solvent cleaning, hot alkaline detergent cleaning, electro-cleaning, and acid treatment etc. The most common industrial test for cleanliness is the waterbreak test, in which the surface is thoroughly rinsed and held vertical. Hydrophobic contaminants such as oils cause the water to bead and break up, allowing the water to drain rapidly. Perfectly clean metal surfaces are hydrophilic and will retain an unbroken sheet of water that does not bead up or drain off. ASTM F22 describes a version of this test. This test does not detect hydrophilic contaminants, but the electroplating process can displace these easily since the solutions are water-based. Surfactants such as soap reduce the sensitivity of the test and must be thoroughly rinsed off.

Effects

Electroplating changes the chemical, physical, and mechanical properties of the workpiece. An example of a chemical change is when nickel plating improves corrosion resistance. An example of a physical change is a change in the outward appearance. An example of a mechanical change is a change in tensile strength
Tensile strength
Ultimate tensile strength , often shortened to tensile strength or ultimate strength, is the maximum stress that a material can withstand while being stretched or pulled before necking, which is when the specimen's cross-section starts to significantly contract...

 or surface hardness which is a required attribute in tooling industry.

History

Although it is not confirmed, the Parthian Battery may have been the first system used for electroplating.

Modern electrochemistry was invented by Italian chemist Luigi V. Brugnatelli in 1805. Brugnatelli used his colleague Alessandro Volta
Alessandro Volta
Count Alessandro Giuseppe Antonio Anastasio Gerolamo Umberto Volta was a Lombard physicist known especially for the invention of the battery in 1800.-Early life and works:...

's invention of five years earlier, the voltaic pile
Voltaic pile
A voltaic pile is a set of individual Galvanic cells placed in series. The voltaic pile, invented by Alessandro Volta in 1800, was the first electric battery...

, to facilitate the first electrodeposition. Brugnatelli's inventions were suppressed by the French Academy of Sciences
French Academy of Sciences
The French Academy of Sciences is a learned society, founded in 1666 by Louis XIV at the suggestion of Jean-Baptiste Colbert, to encourage and protect the spirit of French scientific research...

 and did not become used in general industry for the following thirty years.

By 1839, scientists in Britain
United Kingdom
The United Kingdom of Great Britain and Northern IrelandIn the United Kingdom and Dependencies, other languages have been officially recognised as legitimate autochthonous languages under the European Charter for Regional or Minority Languages...

 and Russia
Russia
Russia or , officially known as both Russia and the Russian Federation , is a country in northern Eurasia. It is a federal semi-presidential republic, comprising 83 federal subjects...

 had independently devised metal deposition processes similar to Brugnatelli's for the copper electroplating of printing press
Printing press
A printing press is a device for applying pressure to an inked surface resting upon a print medium , thereby transferring the ink...

 plates.
Boris Jacobi in Russia not only rediscovered galvanoplastics, but developed electrotyping
Electrotyping
Electrotyping is a chemical method for forming metal parts that exactly reproduce a model. The method was invented by Moritz von Jacobi in Russia in 1838, and was immediately adopted for applications in printing and several other fields...

 and galvanoplastic sculpture. Galvanoplactics quickly came into fashion in Russia, with such people as inventor Peter Bagration
Peter Bagrationi
Peter Bagrationi or Pyotr Romanovich Bagration, the son of a Russian-Georgian general, was a Russian-Georgian statesman, general and scientist who invented the first dry galvanic cell.- Biography :...

, scientist Heinrich Lenz
Heinrich Lenz
Heinrich Friedrich Emil Lenz was a Russian physicist of Baltic German ethnicity. He is most noted for formulating Lenz's law in electrodynamics in 1833....

 and science fiction author Vladimir Odoyevsky all contributing to further development of the technology. Among the most notorious cases of electroplating usage in mid-19th century Russia were gigantic galvanoplastic sculptures of St. Isaac's Cathedral in Saint Petersburg
Saint Petersburg
Saint Petersburg is a city and a federal subject of Russia located on the Neva River at the head of the Gulf of Finland on the Baltic Sea...

 and gold-electroplated dome
Dome
A dome is a structural element of architecture that resembles the hollow upper half of a sphere. Dome structures made of various materials have a long architectural lineage extending into prehistory....

 of the Cathedral of Christ the Saviour in Moscow
Moscow
Moscow is the capital, the most populous city, and the most populous federal subject of Russia. The city is a major political, economic, cultural, scientific, religious, financial, educational, and transportation centre of Russia and the continent...

, the tallest Orthodox church in the world.
Soon after, John Wright
John Wright (inventor)
John Wright was a surgeon from Birmingham, England who invented a process of electroplating involving potassium cyanide. The process was patented in 1840 by Wright's associate George Richards Elkington....

 of Birmingham
Birmingham
Birmingham is a city and metropolitan borough in the West Midlands of England. It is the most populous British city outside the capital London, with a population of 1,036,900 , and lies at the heart of the West Midlands conurbation, the second most populous urban area in the United Kingdom with a...

, England discovered that potassium cyanide
Potassium cyanide
Potassium cyanide is an inorganic compound with the formula KCN. This colorless crystalline compound, similar in appearance to sugar, is highly soluble in water. Most KCN is used in gold mining, organic synthesis, and electroplating. Smaller applications include jewelry for chemical gilding and...

 was a suitable electrolyte
Electrolyte
In chemistry, an electrolyte is any substance containing free ions that make the substance electrically conductive. The most typical electrolyte is an ionic solution, but molten electrolytes and solid electrolytes are also possible....

 for gold and silver electroplating. Wright's associates, George Elkington
George Elkington
George Richards Elkington was a manufacturer from Birmingham, England. He patented the first commercial electroplating process.Elkington was born in Birmingham, the son of a spectacle manufacturer...

 and Henry Elkington were awarded the first patents for electroplating in 1840. These two then founded the electroplating industry in Birmingham
Birmingham
Birmingham is a city and metropolitan borough in the West Midlands of England. It is the most populous British city outside the capital London, with a population of 1,036,900 , and lies at the heart of the West Midlands conurbation, the second most populous urban area in the United Kingdom with a...

 from where it spread around the world.

The Norddeutsche Affinerie in Hamburg
Hamburg
-History:The first historic name for the city was, according to Claudius Ptolemy's reports, Treva.But the city takes its modern name, Hamburg, from the first permanent building on the site, a castle whose construction was ordered by the Emperor Charlemagne in AD 808...

 was the first modern electroplating plant starting its production in 1876.

As the science of electrochemistry
Electrochemistry
Electrochemistry is a branch of chemistry that studies chemical reactions which take place in a solution at the interface of an electron conductor and an ionic conductor , and which involve electron transfer between the electrode and the electrolyte or species in solution.If a chemical reaction is...

 grew, its relationship to the electroplating process became understood and other types of non-decorative metal electroplating processes were developed. Commercial electroplating of nickel, brass, 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...

, and zinc were developed by the 1850s. Electroplating baths and equipment based on the patents of the Elkingtons were scaled up to accommodate the plating of numerous large scale objects and for specific manufacturing and engineering applications.

The plating industry received a big boost from the advent of the development of electric generators in the late 19th century. With the higher currents, available metal machine components, hardware, and automotive parts requiring corrosion protection and enhanced wear properties, along with better appearance, could be processed in bulk.

The two World Wars and the growing aviation
Aviation
Aviation is the design, development, production, operation, and use of aircraft, especially heavier-than-air aircraft. Aviation is derived from avis, the Latin word for bird.-History:...

 industry gave impetus to further developments and refinements including such processes as hard chromium plating, bronze
Bronze
Bronze is a metal alloy consisting primarily of copper, usually with tin as the main additive. It is hard and brittle, and it was particularly significant in antiquity, so much so that the Bronze Age was named after the metal...

 alloy plating, sulfamate nickel plating, along with numerous other plating processes. Plating equipment evolved from manually operated tar-lined wooden tanks to automated equipment, capable of processing thousands of kilograms per hour of parts.

One of the American physicist Richard Feynman
Richard Feynman
Richard Phillips Feynman was an American physicist known for his work in the path integral formulation of quantum mechanics, the theory of quantum electrodynamics and the physics of the superfluidity of supercooled liquid helium, as well as in particle physics...

's first projects was to develop technology for electroplating metal onto plastic. Feynman developed the original idea of his friend into a successful invention, allowing his employer (and friend) to keep commercial promises he had made but could not have fulfilled otherwise.

Hull cell

The Hull cell is a type of test cell used to qualitatively check the condition of an electroplating bath. It allows for optimization for current density range, optimization of additive concentration, recognition of impurity effects and indication of macro-throwing power capability. The Hull cell replicates the plating bath on a lab scale. It is filled with a sample of the plating solution, an appropriate anode which is connected to a rectifier
Rectifier
A rectifier is an electrical device that converts alternating current , which periodically reverses direction, to direct current , which flows in only one direction. The process is known as rectification...

. The "work" is replaced with a hull cell test panel that will be plated to show the "health" of the bath.

The Hull cell is a trapezoidal container that holds 267 ml of solution. This shape allows one to place the test panel on an angle to the anode. As a result, the deposit is plated at different current densities which can be measured with a hull cell ruler. The solution volume allows for a quantitative optimization of additive concentration: 1 gram addition to 267 mL is equivalent to 0.5 oz/gal in the plating tank.
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