Electroplating is a process that uses an electric current to reduce dissolved metal cations so that they form a thin coherent metal coating on an electrode. The term is also used for electrical oxidation of anions on to a solid substrate, as in the formation of silver chloride on silver wire to make silver/silver-chloride electrodes. Electroplating is primarily used to change the surface properties of an object (such as abrasion and wear resistance, corrosion protection, lubricity, aesthetic qualities), 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 concentration 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 metal salts as well as other ions that permit the flow of electricity. A power supply supplies a direct current to the anode, oxidizing the metal atoms that it comprises 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 and thus the ions in the electrolyte bath are continuously replenished by the anode.
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. The most common form of electroplating is used for creating coins, such as US pennies, which are made of zinc covered in a layer of copper.
The cations associate with the anions in the solution. This cations are reduced at the cathode to deposit in the metallic, zero valence state. For example, for copper plating, in an acid solution, copper is oxidized at the anode to Cu2+ by losing two electrons. The Cu2+ associates with the anion SO2−
4 in the solution to form copper(II) 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.
Many plating baths include cyanides of other metals (such as 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 carbonates and phosphates 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, lacquers, and waxes.
The ability of a plating to cover uniformly is called throwing power; the better the throwing power the more uniform the coating.
Initially, a special plating deposit called a strike or flash may be used to form a very thin (typically less than 0.1 μm 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.
Electrochemical deposition is generally used for the growth of metals and conducting metal oxides because of the following advantages: the thickness and morphology of the nanostructure can be precisely controlled by adjusting the electrochemical parameters; relatively uniform and compact deposits can be synthesized in template-based structures; higher deposition rates are obtained; and the equipment is inexpensive due to the non-requirements of either a high vacuum or a high reaction temperature.
A simple modification in electroplating is pulse electroplating. This process involves the swift alternating of the potential or current between two different values resulting in a series of pulses of equal amplitude, duration and polarity, separated by zero current. By changing the pulse amplitude and width, it is possible to change the deposited film's composition and thickness.
The experimental parameters of pulse electroplating usually consist of peak current/potential, duty cycle, frequency and effective current/potential. Peak current/potential is the maximum setting of electroplating current or potential. Duty cycle is the effective portion of time in certain electroplating period with the current or potential applied. The effective current/potential is calculated by multiplying the duty cycle and peak value of current or potential. Pulse electroplating could help to improve the quality of electroplated film and release the internal stress built up during fast deposition. Combination of the short duty cycle and high frequency could decrease the surface cracks. However, in order to maintain the constant effective current or potential, a high performance power supply may be required to provide high peak current/potential and fast switch. Another common problem of pulse electroplating is that the anode material could get plated and contaminated during the reverse electroplating, especially for the high cost, inert electrode like platinum.
Other factors that could affect the pulse electroplating include temperature, anode-to-cathode gap and stirring. Sometimes the pulse electroplating can be performed in heated electroplating bath to increase the depositing rate since the rate of almost all the chemical reaction increases exponentially with temperature per Arrhenius law. The anode-to-cathode gap is related to the current distribution between anode and cathode. Small gap to sample area ratio may cause uneven distribution of current and affect the surface topology of plated sample. Stirring may increase the transfer/diffusion rate of metal ions from bulk solution to the electrode surface. Stirring setting varies for different metal electroplating processes.
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 an absorbent cloth material that both holds the plating solution and prevents direct contact with the item being plated, is connected to the anode of a low voltage direct current power source, and the item to be plated connected to the cathode. 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.
Usually an electrolytic cell (consisting of two electrodes, electrolyte, and external source of current) is used for electrodeposition. In contrast, electroless deposition uses only one electrode and no external source of electric current. However, the solution for electroless deposition needs to contain a reducing agent so that the electrode reaction has the form:
In principle any hydrogen-based reducing agent can be used although the redox potential of the reducing 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 the power sources and plating baths are not needed, reducing the cost of production. This technique can also plate diverse shapes and types of surface. The downside is that plating is usually slower and cannot create thick plates of metal. As a consequence of these characteristics, electroless deposition is quite common in the decorative arts.
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 includes solvent cleaning, hot alkaline detergent cleaning, electrocleaning, 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 electroplating 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.
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. Electroplating of acid gold on underlying copper- or nickel-plated circuits reduces contact resistance as well as surface hardness. Copper-plated areas of mild steel act as a mask if case hardening of such areas are not desired. Tin-plated steel is chromium-plated to prevent dulling of the surface due to oxidation of tin.
Electroplating, or electroless plating may be used as a way to render a metal part radioactive, by using an aqueous solution prepared from nickel–phosphorus concentrates which contain radioactive hypophosphite 32P ions.
Modern electrochemistry was invented by Italian chemist Luigi Valentino 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 Britain and Russia had independently devised metal-deposition processes similar to Brugnatelli's for the copper electroplating of printing press plates.
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 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, the tallest Orthodox church in the world.
Soon after, 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 Woolrich Electrical Generator of 1844, now in Thinktank, Birmingham Science Museum, is the earliest electrical generator used in industry. It was used by Elkingtons.
As the science of electrochemistry grew, its relationship to electroplating became understood and other types of non-decorative metal electroplating 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 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 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 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.
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. 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.
The Haring–Blum cell is used to determine the macro throwing power of a plating bath. The cell consists of two parallel cathodes with a fixed anode in the middle. The cathodes are at distances from the anode in the ratio of 1:5. The macro throwing power is calculated from the thickness of plating at the two cathodes when a direct current is passed for a specific period of time. The cell is fabricated out of perspex or glass.
Alexander Parkes (29 December 1813 – 29 June 1890) was a metallurgist and inventor from Birmingham, England. He created Parkesine, the first man-made plastic.Baghdad Battery
The Baghdad Battery or Parthian Battery is a set of three artifacts which were found together: a ceramic pot, a tube of copper, and a rod of iron. It was discovered in modern Khujut Rabu, Iraq, close to the metropolis of Ctesiphon, the capital of the Parthian (150 BC – 223 AD) and Sasanian (224–650 AD) empires, and it is considered to date from either of these periods.
Its origin and purpose remain unclear, and further evidence is needed to explain its purpose. It was hypothesized by some researchers that the object functioned as a galvanic cell, possibly used for electroplating, or some kind of electrotherapy, but there is no electrogilded object known from this period. An alternative explanation is that it functioned as a storage vessel for sacred scrolls.Cathode
A cathode is the electrode from which a conventional current leaves a polarized electrical device. This definition can be recalled by using the mnemonic CCD for Cathode Current Departs. A conventional current describes the direction in which positive charges move. Electrons have a negative electrical charge, so the movement of electrons is opposite to that of the conventional current flow. Consequently, the mnemonic cathode current departs also means that electrons flow into the device's cathode from the external circuit.
The electrode through which conventional current flows the other way, into the device, is termed an anode.Chrome plating
Chrome plating (less commonly chromium plating), often referred to simply as chrome, is a technique of electroplating a thin layer of chromium onto a metal object. The chromed layer can be decorative, provide corrosion resistance, ease cleaning procedures, or increase surface hardness. Sometimes, a less expensive imitator of chrome may be used for aesthetic purposes.Chromium trioxide
Chromium trioxide is an inorganic compound with the formula CrO3. It is the acidic anhydride of chromic acid, and is sometimes marketed under the same name.
This compound is a dark-purple solid under anhydrous conditions, bright orange when wet and which dissolves in water concomitant with hydrolysis. Millions of kilograms are produced annually, mainly for electroplating. Chromium trioxide is a powerful oxidiser and a suspected carcinogen.Copper(I) cyanide
Copper(I) cyanide is an inorganic compound with the formula CuCN. This off-white solid occurs in two polymorphs; impure samples can be green due to the presence of Cu(II) impurities. The compound is useful as a catalyst, in electroplating copper, and as a reagent in the preparation of nitriles.Diamond blade
A diamond blade is a saw blade which has diamonds fixed on its edge for cutting hard or abrasive materials. There are many types of diamond blade, and they have many uses, including cutting stone, concrete, asphalt, bricks, coal balls, glass, and ceramics in the construction industry; cutting semiconductor materials in the IT industry; and cutting gemstones, including diamonds, in the gem industry.Electrogalvanization
Electrogalvanizing is a process in which a layer of zinc is bonded to steel in order to protect against corrosion. The process involves electroplating, running a current of electricity through a saline/zinc solution with a zinc anode and steel conductor.
Zinc electroplating maintains a dominant position among other electroplating process options, based upon electroplated tonnage per annum. According to the International Zinc Association, more than 5 million tons are used yearly for both hot dip galvanizing and electroplating. The plating of zinc was developed at the beginning of the 20th century. At that time, the electrolyte was cyanide based. A significant innovation occurred in the 1960s, with the introduction of the first acid chloride based electrolyte. The 1980s saw a return to alkaline electrolytes, only this time, without the use of cyanide. The most commonly used electrogalvanized cold rolled steel is SECC steel. Compared to hot dip galvanizing, electroplated zinc offers these significant advantages:
Lower thickness deposits to achieve comparable performance
Broader conversion coating availability for increased performance and colour options
Brighter, more aesthetically appealing, depositsElectrometallurgy
Electrometallurgy is the field concerned with the processes of metal electrodeposition There are four categories of these processes:
Electrowinning, the extraction of metal from ores
Electrorefining, the purification of metals. Metal powder production by electrodeposition is included in this category, or sometimes electrowinning, or a separate category depending on application.
Electroplating, the deposition of a layer of one metal on another
Electroforming, the manufacture of, usually thin, metal parts through electroplatingElectrowinning
Electrowinning, also called electroextraction, is the electrodeposition of metals from their ores that have been put in solution via a process commonly referred to as leaching. Electrorefining uses a similar process to remove impurities from a metal. Both processes use electroplating on a large scale and are important techniques for the economical and straightforward purification of non-ferrous metals. The resulting metals are said to be electrowon.
In electrowinning, a current is passed from an inert anode through a liquid leach solution containing the metal so that the metal is extracted as it is deposited in an electroplating process onto the cathode. In electrorefining, the anodes consist of unrefined impure metal, and as the current passes through the acidic electrolyte the anodes are corroded into the solution so that the electroplating process deposits refined pure metal onto the cathodes.Industrial processes
Industrial processes are procedures involving chemical, physical, electrical or mechanical steps to aid in the manufacturng of an item or items, usually carried out on a very large scale. Industrial processes are the key components of heavy industry.LIGA
LIGA is a German acronym for Lithographie, Galvanoformung, Abformung (Lithography, Electroplating, and Molding) that describes a fabrication technology used to create high-aspect-ratio microstructures.Magneto
A magneto is an electrical generator that uses permanent magnets to produce periodic pulses of alternating current. Unlike a dynamo, a magneto does not contain a commutator to produce direct current. It is categorized as a form of alternator, although it is usually considered distinct from most other alternators, which use field coils rather than permanent magnets.
Hand-cranked magneto generators were used to provide ringing current in telephone systems. Magnetos were also adapted to produce pulses of high voltage in the ignition systems of some gasoline-powered internal combustion engines to provide power to the spark plugs. Use of such ignition magnetos for ignition is now limited mainly to the following kinds of engines:
Engines without a low-voltage electrical system, such as lawnmowers and chainsaws.
Aircraft engines, in which keeping the ignition independent of the rest of the electrical system ensures that the engine continues running in the event of alternator or battery failure. For redundancy, virtually all piston engine aircraft are fitted with two magneto systems, each supplying power to one of two spark plugs in each cylinder.Magnetos were used for specialized isolated power systems such as arc lamp systems or lighthouses, for which their simplicity was an advantage. They have never been widely applied for the purposes of bulk electricity generation, for the same purposes or to the same extent as either dynamos or alternators. Only in a few specialised cases, as described here, have they been used for power generation.Nickel(II) sulfate
Nickel(II) sulfate, or just nickel sulfate, usually refers to the inorganic compound with the formula NiSO4(H2O)6. This highly soluble blue-coloured salt is a common source of the Ni2+ ion for electroplating.
Approximately 40,000 tonnes were produced in 2005. It is mainly used for electroplating of nickel.In 2005–06, nickel sulfate was the top allergen in patch tests (19.0%).Nickel electroplating
Nickel electroplating is a technique of electroplating a thin layer of nickel onto a metal object. The nickel layer can be decorative, provide corrosion resistance, wear resistance, or used to build up worn or undersized parts for salvage purposes.Plating
Plating is a surface covering in which a metal is deposited on a conductive surface. Plating has been done for hundreds of years; it is also critical for modern technology. Plating is used to decorate objects, for corrosion inhibition, to improve solderability, to harden, to improve wearability, to reduce friction, to improve paint adhesion, to alter conductivity, to improve IR reflectivity, for radiation shielding, and for other purposes. Jewelry typically uses plating to give a silver or gold finish.
Thin-film deposition has plated objects as small as an atom, therefore plating finds uses in nanotechnology.
There are several plating methods, and many variations. In one method, a solid surface is covered with a metal sheet, and then heat and pressure are applied to fuse them (a version of this is Sheffield plate). Other plating techniques include electroplating, vapor deposition under vacuum and sputter deposition. Recently, plating often refers to using liquids. Metallizing refers to coating metal on non-metallic objects.Tartrate
A tartrate is a salt or ester of the organic compound tartaric acid, a dicarboxylic acid. The formula of the tartrate dianion is O−OC-CH(OH)-CH(OH)-COO− or C4H4O62−.The main forms of tartrates used commercially are pure crystalline tartaric acid used as an acidulant in non-alcoholic drinks and foods, cream of tartar used in baking, and Rochelle Salt, commonly used in electroplating solutions.Total metal jacket
Total metal jacket (or full metal case) bullets are made by electroplating a thin jacket of ductile metal (usually copper) over a core of different metal requiring protection from abrasion or corrosion. Similar full metal jacket bullets mechanically swage a thin sheet of metal over the core. The swaging process leaves an opening exposing the core on the base of the bullet, while electroplating deposits a jacket over the entire bullet surface. Protecting the base of a lead-core bullet from burning powder gas may prevent molten lead from being released as a fine spray in turbulent gas leaving the muzzle of a firearm. Electrolytic deposition can create very thin jackets, while jackets applied by swaging must be thick enough to avoid being torn during the swaging process. Uniformly electroplated jackets may produce more accurate bullets than jacket and core materials deformed during swaging. Thinner electroplated jackets may not be as strong as conventional swaged jackets of similar metal, and may not prevent leading at higher bullet velocities. Thinner jackets may be damaged by and foul barrel ports for gas-operated reloading or recoil compensation.Zinc cyanide
Zinc cyanide is the inorganic compound with the formula Zn(CN)2. It is a white solid that is used mainly for electroplating zinc but also has more specialized applications for the synthesis of organic compounds.