Galvanic corrosion (also called bimetallic corrosion or dissimilar metal corrosion) is an electrochemical process in which one metal corrodes preferentially when it is in electrical contact with another, in the presence of an electrolyte. A similar galvanic reaction is exploited in primary cells to generate a useful electrical voltage to power portable devices. This phenomenon is named after Italian physician Luigi Galvani (1737–1798).
Dissimilar metals and alloys have different electrode potentials, and when two or more come into contact in an electrolyte, one metal (that is more reactive) acts as anode and the other (that is less reactive) as cathode. The electropotential difference between the reactions at the two electrodes is the driving force for an accelerated attack on the anode metal, which dissolves into the electrolyte. This leads to the metal at the anode corroding more quickly than it otherwise would and corrosion at the cathode being inhibited. The presence of an electrolyte and an electrical conducting path between the metals is essential for galvanic corrosion to occur. The electrolyte provides a means for ion migration whereby ions move to prevent charge build-up that would otherwise stop the reaction. If the electrolyte contains only metal ions that are not easily reduced (such as Na+, Ca2+, K+, Mg2+, or Zn2+), the cathode reaction is the reduction of dissolved H+ to H2 or O2 to OH−. [1] [2] [3] [4]
In some cases, this type of reaction is intentionally encouraged. For example, low-cost household batteries typically contain carbon-zinc cells. As part of a closed circuit (the electron pathway), the zinc within the cell will corrode preferentially (the ion pathway) as an essential part of the battery producing electricity. Another example is the cathodic protection of buried or submerged structures as well as hot water storage tanks. In this case, sacrificial anodes work as part of a galvanic couple, promoting corrosion of the anode, while protecting the cathode metal.
In other cases, such as mixed metals in piping (for example, copper, cast iron and other cast metals), galvanic corrosion will contribute to accelerated corrosion of parts of the system. Corrosion inhibitors such as sodium nitrite or sodium molybdate can be injected into these systems to reduce the galvanic potential. However, the application of these corrosion inhibitors must be monitored closely. If the application of corrosion inhibitors increases the conductivity of the water within the system, the galvanic corrosion potential can be greatly increased.
Acidity or alkalinity (pH) is also a major consideration with regard to closed loop bimetallic circulating systems. Should the pH and corrosion inhibition doses be incorrect, galvanic corrosion will be accelerated. In most HVAC systems, the use of sacrificial anodes and cathodes is not an option, as they would need to be applied within the plumbing of the system and, over time, would corrode and release particles that could cause potential mechanical damage to circulating pumps, heat exchangers, etc. [5]
A common example of galvanic corrosion occurs in galvanized iron, a sheet of iron or steel covered with a zinc coating. Even when the protective zinc coating is broken, the underlying steel is not attacked. Instead, the zinc is corroded because it is less "noble". Only after it has been consumed can rusting of the base metal occur. By contrast, with a conventional tin can, the opposite of a protective effect occurs: because the tin is more noble than the underlying steel, when the tin coating is broken, the steel beneath is immediately attacked preferentially.
A spectacular example of galvanic corrosion occurred in the Statue of Liberty when regular maintenance checks in the 1980s revealed that corrosion had taken place between the outer copper skin and the wrought iron support structure. Although the problem had been anticipated when the structure was built by Gustave Eiffel to Frédéric Bartholdi's design in the 1880s, the insulation layer of shellac between the two metals had failed over time and resulted in rusting of the iron supports. An extensive renovation was carried out with replacement of the original insulation with PTFE. The structure was far from unsafe owing to the large number of unaffected connections, but it was regarded as a precautionary measure to preserve a national symbol of the United States. [6]
In 1681, Samuel Pepys (then serving as Admiralty Secretary) agreed to the removal of lead sheathing from English Royal Navy vessels to prevent the mysterious disintegration of their rudder-irons and bolt-heads, though he confessed himself baffled as to the reason the lead caused the corrosion. [7] [8]
The problem recurred when vessels were sheathed in copper to reduce marine weed accumulation and protect against shipworm. In an experiment, the Royal Navy in 1761 had tried fitting the hull of the frigate HMS Alarm with 12-ounce copper plating. Upon her return from a voyage to the West Indies, it was found that although the copper remained in fine condition and had indeed deterred shipworm, it had also become detached from the wooden hull in many places because the iron nails used during its installation "were found dissolved into a kind of rusty Paste". [9] To the surprise of the inspection teams, however, some of the iron nails were virtually undamaged. Closer inspection revealed that water-resistant brown paper trapped under the nail head had inadvertently protected some of the nails: "Where this covering was perfect, the Iron was preserved from Injury". The copper sheathing had been delivered to the dockyard wrapped in the paper which was not always removed before the sheets were nailed to the hull. The conclusion therefore reported to the Admiralty in 1763 was that iron should not be allowed direct contact with copper in sea water. [10] [11]
Serious galvanic corrosion has been reported on the latest US Navy attack littoral combat vessel the USS Independence caused by steel water jet propulsion systems attached to an aluminium hull. Without electrical isolation between the steel and aluminium, the aluminium hull acts as an anode to the stainless steel, resulting in aggressive galvanic corrosion. [12]
The unexpected fall in 2011 of a heavy light fixture from the ceiling of the Big Dig vehicular tunnel in Boston revealed that corrosion had weakened its support. Improper use of aluminium in contact with stainless steel had caused rapid corrosion in the presence of salt water. [13] The electrochemical potential difference between stainless steel and aluminium is in the range of 0.5 to 1.0 V, depending on the exact alloys involved, and can cause considerable corrosion within months under unfavorable conditions. Thousands of failing lights would have to be replaced, at an estimated cost of $54 million. [14]
A "lasagna cell" is accidentally produced when salty moist food such as lasagna is stored in a steel baking pan and is covered with aluminium foil. After a few hours the foil develops small holes where it touches the lasagna, and the food surface becomes covered with small spots composed of corroded aluminium. [15] In this example, the salty food (lasagna) is the electrolyte, the aluminium foil is the anode, and the steel pan is the cathode. If the aluminium foil touches the electrolyte only in small areas, the galvanic corrosion is concentrated, and corrosion can occur fairly rapidly. If the aluminium foil was not used with a dissimilar metal container, the reaction was probably a chemical one. It is possible for heavy concentrations of salt, vinegar or some other acidic compounds to cause the foil to disintegrate. The product of either of these reactions is an aluminium salt. It does not harm the food, but any deposit may impart an undesired flavor and color. [16]
The common technique of cleaning silverware by immersion of the silver or sterling silver (or even just silver plated objects) and a piece of aluminium (foil is preferred because of its much greater surface area than that of ingots, although if the foil has a "non-stick" face, this must be removed with steel wool first) in a hot electrolytic bath (usually composed of water and sodium bicarbonate, i.e., household baking soda) is an example of galvanic corrosion. Silver darkens and corrodes in the presence of airborne sulfur molecules, and the copper in sterling silver corrodes under a variety of conditions. These layers of corrosion can be largely removed through the electrochemical reduction of silver sulfide molecules: the presence of aluminium (which is less noble than either silver or copper) in the bath of sodium bicarbonate strips the sulfur atoms off the silver sulfide and transfers them onto and thereby corrodes the piece of aluminium foil (a much more reactive metal), leaving elemental silver behind. No silver is lost in the process. [17]
There are several ways of reducing and preventing this form of corrosion:
All metals can be classified into a galvanic series representing the electrical potential they develop in a given electrolyte against a standard reference electrode. The relative position of two metals on such a series gives a good indication of which metal is more likely to corrode more quickly. However, other factors such as water aeration and flow rate can influence the rate of the process markedly.
The compatibility of two different metals may be predicted by consideration of their anodic index. This parameter is a measure of the electrochemical voltage that will be developed between the metal and gold. To find the relative voltage of a pair of metals it is only required to subtract their anodic indices. [18]
To reduce galvanic corrosion for metals stored in normal environments such as storage in warehouses or non-temperature and humidity controlled environments, there should not be more than 0.25 V difference in the anodic index of the two metals in contact. For controlled environments in which temperature and humidity are controlled, 0.50 V can be tolerated. For harsh environments such as outdoors, high humidity, and salty environments, there should be not more than 0.15 V difference in the anodic index. For example: gold and silver have a difference of 0.15 V, therefore the two metals will not experience significant corrosion even in a harsh environment. [19] [ page needed ]
When design considerations require that dissimilar metals come in contact, the difference in anodic index is often managed by finishes and plating. The finishing and plating selected allow the dissimilar materials to be in contact, while protecting the more base materials from corrosion by the more noble. [19] [ page needed ] It will always be the metal with the most negative anodic index which will ultimately suffer from corrosion when galvanic incompatibility is in play. This is why sterling silver and stainless steel tableware should never be placed together in a dishwasher at the same time, as the steel items will likely experience corrosion by the end of the cycle (soap and water having served as the chemical electrolyte, and heat having accelerated the process).
| Metal | Index (V) |
|---|---|
| Most cathodic | |
| Gold, solid and plated; gold-platinum alloy | −0.00 |
| Rhodium-plated on silver-plated copper | −0.05 |
| Silver, solid or plated; monel metal; high nickel-copper alloys | −0.15 |
| Nickel, solid or plated; titanium and its alloys; monel | −0.30 |
| Copper, solid or plated; low brasses or bronzes; silver solder; German silvery high copper-nickel alloys; nickel-chromium alloys | −0.35 |
| Brass and bronzes | −0.40 |
| High brasses and bronzes | −0.45 |
| 18%-chromium-type corrosion-resistant steels | −0.50 |
| Chromium plated; tin plated; 12%-chromium-type corrosion-resistant steels | −0.60 |
| Tin-plate; tin-lead solder | −0.65 |
| Lead, solid or plated; high lead alloys | −0.70 |
| 2000 series wrought aluminium | −0.75 |
| Iron, wrought, gray, or malleable; low alloy and plain carbon steels | −0.85 |
| Aluminium, wrought alloys other than 2000 series aluminium, cast alloys of the silicon type | −0.90 |
| Aluminium, cast alloys (other than silicon type); cadmium, plated and chromate | −0.95 |
| Hot-dip-zinc plate; galvanized steel | −1.20 |
| Zinc, wrought; zinc-base die-casting alloys; zinc plated | −1.25 |
| Magnesium and magnesium-base alloys; cast or wrought | −1.75 |
| Beryllium | −1.85 |
| Most anodic |
An anode is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, an electrode of the device through which conventional current leaves the device. A common mnemonic is ACID, for "anode current into device". The direction of conventional current in a circuit is opposite to the direction of electron flow, so electrons flow from the anode of a galvanic cell, into an outside or external circuit connected to the cell. For example, the end of a household battery marked with a "+" is the cathode.
Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference and identifiable chemical change. These reactions involve electrons moving via an electronically-conducting phase between electrodes separated by an ionically conducting and electronically insulating electrolyte.
An electrochemical cell is a device that generates electrical energy from chemical reactions. Electrical energy can also be applied to these cells to cause chemical reactions to occur. Electrochemical cells that generate an electric current are called voltaic or galvanic cells and those that generate chemical reactions, via electrolysis for example, are called electrolytic cells.
Galvanization or galvanizing is the process of applying a protective zinc coating to steel or iron, to prevent rusting. The most common method is hot-dip galvanizing, in which the parts are coated by submerging them in a bath of hot, molten zinc.
Rust is an iron oxide, a usually reddish-brown oxide formed by the reaction of iron and oxygen in the catalytic presence of water or air moisture. Rust consists of hydrous iron(III) oxides (Fe2O3·nH2O) and iron(III) oxide-hydroxide (FeO(OH), Fe(OH)3), and is typically associated with the corrosion of refined iron.
In chemistry and manufacturing, electrolysis is a technique that uses direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from naturally occurring sources such as ores using an electrolytic cell. The voltage that is needed for electrolysis to occur is called the decomposition potential. The word "lysis" means to separate or break, so in terms, electrolysis would mean "breakdown via electricity."
Electroplating, also known as electrochemical deposition or electrodeposition, is a process for producing a metal coating on a solid substrate through the reduction of cations of that metal by means of a direct electric current. The part to be coated acts as the cathode of an electrolytic cell; the electrolyte is a solution of a salt of the metal to be coated, and the anode is usually either a block of that metal, or of some inert conductive material. The current is provided by an external power supply.
Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials by chemical or electrochemical reaction with their environment. Corrosion engineering is the field dedicated to controlling and preventing corrosion.
A galvanic anode, or sacrificial anode, is the main component of a galvanic cathodic protection system used to protect buried or submerged metal structures from corrosion.
A galvanic cell or voltaic cell, named after the scientists Luigi Galvani and Alessandro Volta, respectively, is an electrochemical cell in which an electric current is generated from spontaneous oxidation–reduction reactions. A common apparatus generally consists of two different metals, each immersed in separate beakers containing their respective metal ions in solution that are connected by a salt bridge or separated by a porous membrane.
Cathodic protection is a technique used to control the corrosion of a metal surface by making it the cathode of an electrochemical cell. A simple method of protection connects the metal to be protected to a more easily corroded "sacrificial metal" to act as the anode. The sacrificial metal then corrodes instead of the protected metal. For structures such as long pipelines, where passive galvanic cathodic protection is not adequate, an external DC electrical power source is used to provide sufficient current.
Anodizing is an electrolytic passivation process used to increase the thickness of the natural oxide layer on the surface of metal parts.
Plating is a finishing process in which a metal is deposited on a 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.
The galvanic series determines the nobility of metals and semi-metals. When two metals are submerged in an electrolyte, while also electrically connected by some external conductor, the less noble (base) will experience galvanic corrosion. The rate of corrosion is determined by the electrolyte, the difference in nobility, and the relative areas of the anode and cathode exposed to the electrolyte. The difference can be measured as a difference in voltage potential: the less noble metal is the one with a lower electrode potential than the nobler one, and will function as the anode within the electrolyte device functioning as described above. Galvanic reaction is the principle upon which batteries are based.
Pitting corrosion, or pitting, is a form of extremely localized corrosion that leads to the random creation of small holes in metal. The driving power for pitting corrosion is the depassivation of a small area, which becomes anodic while an unknown but potentially vast area becomes cathodic, leading to very localized galvanic corrosion. The corrosion penetrates the mass of the metal, with a limited diffusion of ions.
In battery technology, a concentration cell is a limited form of a galvanic cell that has two equivalent half-cells of the same composition differing only in concentrations. One can calculate the potential developed by such a cell using the Nernst equation. A concentration cell produces a small voltage as it attempts to reach chemical equilibrium, which occurs when the concentration of reactant in both half-cells are equal. Because an order of magnitude concentration difference produces less than 60 millivolts at room temperature, concentration cells are not typically used for energy storage.
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. Such Zinc electroplating or Zinc alloy 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, acronym of "Steel, Electrogalvanized, Cold-rolled, Commercial quality". Compared to hot dip galvanizing, electroplated zinc offers these significant advantages:
Corrosion engineering is an engineering specialty that applies scientific, technical, engineering skills, and knowledge of natural laws and physical resources to design and implement materials, structures, devices, systems, and procedures to manage corrosion. From a holistic perspective, corrosion is the phenomenon of metals returning to the state they are found in nature. The driving force that causes metals to corrode is a consequence of their temporary existence in metallic form. To produce metals starting from naturally occurring minerals and ores, it is necessary to provide a certain amount of energy, e.g. Iron ore in a blast furnace. It is therefore thermodynamically inevitable that these metals when exposed to various environments would revert to their state found in nature. Corrosion and corrosion engineering thus involves a study of chemical kinetics, thermodynamics, electrochemistry and materials science.
A sacrificial metal is a metal used as a sacrificial anode in cathodic protection that corrodes to prevent a primary metal from corrosion or rusting. It may also be used for galvanization.
Electrochemical coloring of metals is a process in which the surface color of metal is changed by electrochemical techniques, i.e. cathodic or anodic polarization. The first method of electrochemical coloring of metals are certainly Nobili's colored rings, discovered by Leopoldo Nobili, an Italian physicist in 1826. In addition to the multicolored coatings mentioned, he has also been able to obtain monochrome coatings, and he called that technique metallocromia. Electrochemical coloring of metals based processes are black, green and blue nickel plating, black chromium plating, black rhodium plating and black ruthenium plating. Anodic oxidation of aluminum, titanium, niobium, tantalum and stainless steel are also electrochemical colouring processes. Multi-colored and green electrolytic patinas for copper and its alloys are also significant.
During the action of a simple circle, as of zinc and copper, excited by dilute sulfuric acid, all of the hydrogen developed in the voltaic action is evolved at the surface of the copper.
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