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[[File:PCB copper layer electroplating machine.jpg|thumb|Copper electroplating machine for layering [[Printed circuit board|PCBs]]]]
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'''Electroplating''' is a process that uses electrical [[direct current|current]] to [[redox|reduce]] dissolved metal [[cation]]s so that they form a coherent metal coating on an [[electrode]]. The term is also used for electrical [[redox|oxidation]] of [[anions]] onto a solid subtrate, as in the formation silver chloride on silver wire to make [[silver chloride electrode|silver/silver-chloride electrodes]]. Electroplating is primarily used to change the surface properties of an object (e.g. [[abrasion (mechanical)|abrasion]] and wear resistance, [[corrosion]] protection, [[lubrication|lubricity]], aesthetic qualities, etc.), but may also be used to build up thickness on undersized parts or to form objects by [[electroforming]].
 
The process used in electroplating is called '''electrodeposition'''. It is analogous to a [[galvanic cell]] [[electrolytic cell|acting in reverse]]. The part to be plated is the [[cathode]] of the circuit. In one technique, the [[anode]] is made of the metal to be plated on the part. Both components are immersed in a [[solution]] called an [[electrolyte]] containing one or more dissolved [[salt (chemistry)|metal salts]] as well as other [[ion]]s that permit the flow of electricity. A [[power supply]] supplies a [[direct current]] to the [[anode]], 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.<ref>Dufour, IX-1.</ref>
 
Other electroplating processes may use a non-consumable anode such as lead or carbon. 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.<ref name="Dufour, IX-2">Dufour, IX-2.</ref> The most common form of electroplating is used for creating coins such as [[pennies]], which are small [[zinc]] plates covered in a layer of [[copper]].
<ref>{{cite web|title=US Mint Virtual Tour|url=http://www.usmint.gov/mint_tours/?action=VTShell|publisher=US Mint}}</ref>
 
==Process==
[[File:Copper electroplating.svg|thumb|Electroplating of a metal (Me) with copper in a copper sulfate bath]]
 
The cations associate with the [[anion]]s in the solution. These cations are reduced at the cathode to deposit in the metallic, zero valence state. For example, in an acid solution, [[copper]] is oxidized at the anode to Cu<sup>2+</sup> by losing two electrons. The Cu<sup>2+</sup> associates with the anion SO<sub>4</sub><sup>2-</sup> in the solution to form copper sulfate. At the cathode, the Cu<sup>2+</sup> 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 [[chemical element|element]], not an [[alloy]]. However, some alloys can be electrodeposited, notably [[brass]] and [[solder]].
 
Many plating baths include [[cyanide]]s of other metals (e.g., [[potassium cyanide]]) 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]]s and [[phosphate]]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]]s, and [[wax]]es.<ref name="dufour3">Dufour, IX-3.</ref>
 
===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]] on [[zinc]] alloys, in which case a copper strike is used, which has good adherence to both.<ref name="Dufour, IX-2"/>
 
===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]] 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]] (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:
:<math>M^{z+} + Red_{solution} \stackrel{\text{catalytic surface}} \Longrightarrow M_{solid} + Oxy_{solution}</math>
 
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]] 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 ===
[[Parts cleaning|Cleanliness]] 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]] or surface [[hardness]] which is a required attribute in tooling industry.<ref>{{cite book
| first = Robert H.
| last = Todd
| coauthors = Dell K. Allen and Leo Alting
| year = 1994
| title = Manufacturing Processes Reference Guide
| chapter = Surface Coating
| publisher = Industrial Press Inc
| isbn = 0-8311-3049-0
| url = http://books.google.com/?id=6x1smAf_PAcC |pages= 454–458}}</ref>
 
==History==
[[Image:Early Electro-Plating.jpg|thumb|right|Nickel plating]]
{{also|Johann Wilhelm Ritter}}
 
Although it is not confirmed, the [[Parthian Battery]] may have been the first system used for electroplating.<!-- See link to [[Parthian Battery]] for refs -->
 
Modern electrochemistry was invented by Italian chemist [[Luigi V. Brugnatelli]] in 1805.  Brugnatelli used his colleague [[Alessandro Volta]]'s invention of five years earlier, the [[voltaic pile]], to facilitate the first electrodeposition.  Brugnatelli's inventions were suppressed by the [[French Academy of Sciences]] and did not become used in general industry for the following thirty years.
 
By 1839, scientists in [[United Kingdom|Britain]] and [[Russia]] had independently devised metal deposition processes similar to Brugnatelli's for the copper electroplating of [[printing press]] plates.
 
[[File:Moritz Hermann von Jacobi 1856.jpg|thumb|180px|left|[[Boris Jacobi]] developed electroplating, [[electrotyping]] and [[galvanoplastic sculpture]] in [[Russia]]]]
[[Boris Jacobi]] in Russia not only rediscovered galvanoplastics, but developed [[electrotyping]] and [[galvanoplastic sculpture]]. Galvanoplastics quickly came into fashion in Russia, with such people as inventor [[Peter Bagrationi|Peter Bagration]], scientist [[Heinrich Lenz]] 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]] and gold-electroplated [[dome]] of the [[Cathedral of Christ the Saviour]] in [[Moscow]], [[List of tallest Orthodox churches|the tallest Orthodox church in the world]].<ref name="galteh">[http://www.galteh.ru/article_galvanotehnika.html The history of galvanotechnology in Russia] {{ru icon}}</ref>
[[File:Fragment of west barelief on St.Isaac cathedral.jpg|thumb|220px|right|[[Galvanoplastic sculpture]] on [[St. Isaac's Cathedral]] in [[Saint Petersburg]].]]
 
Soon after, [[John Wright (inventor)|John Wright]] of [[Birmingham]], England discovered that [[potassium cyanide]] was a suitable [[electrolyte]] for gold and silver electroplating.  Wright's associates, [[George Elkington]] and Henry Elkington were awarded the first patents for electroplating in 1840.  These two then founded the electroplating industry in [[Birmingham]] from where it spread around the world.
 
The [[Norddeutsche Affinerie]] in [[Hamburg]] was the first modern electroplating plant starting its production in 1876.<ref>{{cite journal|doi = 10.1002/adem.200400403|title = Process Optimization in Copper Electrorefining|year = 2004|author = Stelter, M.|journal = Advanced Engineering Materials|volume = 6|page=558|last2 = Bombach|first2 = H.}}</ref>
 
As the science of [[electrochemistry]] 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]], 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 with the advent of the development of [[electric generator]]s 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]] industry gave impetus to further developments and refinements including such processes as hard [[chromium plating]], [[bronze]] 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]]'s first projects was to develop technology for electroplating metal onto [[plastics|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.<ref>Richard Feynman, ''[[Surely You're Joking, Mr. Feynman!]]'' (1985), in chap. 6: [http://www.tenniselbow.org/scott/feyn_surely.pdf "The Chief Research Chemist of the Metaplast Corporation"]</ref>
 
==Use==
 
Electroplating is a useful process. It is widely used in industry for coating metal objects with a thin layer of a different metal. The layer of metal deposited has some desired property, which metal of the object lacks. For example chromium plating is done on many objects such as car parts, bath taps, kitchen gas burners, wheel rims and many others.
 
[[Image:Hullcell.jpg|thumb|A zinc solution tested in a hull cell]]
 
==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.<ref>{{Cite book | title = Metal Finishing: Guidebook and Directory. Issue 98 | page = 588 | year = 1998 | volume = 95}}</ref> 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]]. 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&nbsp;gram addition to 267 mL is equivalent to 0.5 oz/gal in the plating tank.<ref>[http://www.allbusiness.com/manufacturing/chemical-manufacturing-paint/3993213-1.html Hull Cell 101]</ref>
 
==References==
{{Reflist|30em}}
 
===Bibliography===
*{{cite book
  | last = Dufour
  | first = Jim
  | title = An Introduction to Metallurgy, 5th
 
  | publisher = Cameron
  | year = 2006
  }}
 
[[Category:Metal plating]]

Latest revision as of 11:46, 16 November 2014

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