Thermite is a pyrotechnic composition of a metal powder and a metal oxide that produces an exothermic oxidation-reduction reaction known as a thermite reaction. If aluminium is the reducing agent it is called an aluminothermic reaction. Most varieties are not explosive, but can create short bursts of extremely high temperatures focused on a very small area for a short period of time. The thermite is simply a mixture of metal, often called the "fuel" and an oxidizer. Its form of action is very similar to other fuel-oxidizer mixtures like black powder.
Thermites can be a diverse class of compositions. Some "fuels" that can be used include aluminium, magnesium, calcium, titanium, zinc, silicon, and boron and others. One commonly-used fuel in thermite mixtures is aluminium, because of its high boiling point. The oxidizers can be boron(III) oxide, silicon(IV) oxide, chromium(III) oxide, manganese(IV) oxide, iron(III) oxide, iron(II,III) oxide, copper(II) oxide, and lead(II,III,IV) oxide and others.[1]
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The aluminium reduces the oxide of another metal, most commonly iron oxide, because aluminium is highly reactive:
The products are aluminium oxide, free elemental iron,[2] and a large amount of heat. The reactants are commonly powdered and mixed with a binder to keep the material solid and prevent separation.
The reaction is used for thermite welding, often used to join rail tracks. Other metal oxides can be used, such as chromium oxide, to generate the given metal in its elemental form. Copper thermite, using copper oxide, is used for creating electric joints in a process called cadwelding:
Some thermite-like mixtures are used as pyrotechnic initiators such as fireworks.
Thermites with nanosized particles are described through a variety of terms, such as metastable intermolecular composites, super-thermite,[3] nano-thermite,[4] and nanocomposite energetic materials.[5][6]
The thermite (thermit) reaction was discovered in 1893 and patented in 1895 by German chemist Hans Goldschmidt.[7] Consequently, the reaction is sometimes called the "Goldschmidt reaction" or "Goldschmidt process".[8] Dr. Goldschmidt was originally interested in producing very pure metals by avoiding the use of carbon in smelting, but he soon discovered the value of thermite in welding.[8]
The first commercial application of thermite was the welding of tram tracks in Essen, Germany, in 1899.[9]
Red iron(III) oxide (Fe2O3, commonly known as rust) is the most common iron oxide used in thermite.[10][11][12] Magnetite also works.[13] Other oxides are occasionally used, such as MnO2 in manganese thermite, Cr2O3 in chromium thermite, or copper(II) oxide in copper thermite, but only for specialized purposes.[13] All of these examples use aluminium as the reactive metal. Fluoropolymers can be used in special formulations, Teflon with magnesium or aluminium being a relatively common example. Magnesium/teflon/viton is another pyrolant of this type.[14]
In principle, any reactive metal could be used instead of aluminium. This is rarely done, however, because the properties of aluminium are nearly ideal for this reaction. It is by far the cheapest of the highly reactive metals; it also forms a passivation layer making it safer to handle than many other reactive metals.[15] The melting and boiling points of aluminium also make it ideal for thermite reactions. Its relatively low melting point (660 °C (1,220 °F)) means that it is easy to melt the metal, so that the reaction can occur mainly in the liquid phase and thus proceeds fairly quickly. At the same time, its high boiling point (2,519 °C (4,566 °F)) enables the reaction to reach very high temperatures, since several processes tend to limit the maximum temperature to just below the boiling point. Such a high boiling point is common among transition metals (e.g., iron and copper boil at 2,887 °C (5,229 °F) and 2,582 °C (4,680 °F) respectively), but is especially unusual among the highly reactive metals (cf. magnesium and sodium which boil at 1,090 °C (1,990 °F) and 883 °C (1,621 °F) respectively). Further, the low density of the aluminium oxide formed as a result of the reaction tends to cause it to float on the iron, reducing contamination of the weld.
Although the reactants are stable at room temperature, they burn with an extremely intense exothermic reaction when they are heated to ignition temperature. The products emerge as liquids due to the high temperatures reached (up to 2,500 °C (4,530 °F) with iron(III) oxide)—although the actual temperature reached depends on how quickly heat can escape to the surrounding environment. Thermite contains its own supply of oxygen and does not require any external source of air. Consequently, it cannot be smothered and may ignite in any environment, given sufficient initial heat. It will burn well while wet and cannot be easily extinguished with water, although enough water will remove heat and may stop the reaction.[16] Small amounts of water will boil before reaching the reaction. Although thermite is used for welding underwater,[17] this can produce hydrogen which will in turn burn also.
The thermites are characterized by almost complete absence of gas production during burning, high reaction temperature, and production of molten slag. The fuel should have high heat of combustion and produce oxides with low melting point and high boiling point. The oxidizer should contain at least 25% oxygen, have high density, low heat of formation, and produce metal with low melting and high boiling point (so the energy released is not consumed in evaporation of reaction products). Organic binders can be added to the composition to improve its mechanical properties, however they tend to produce endothermic decomposition products, causing some loss of reaction heat and production of gases.[18]
The temperature achieved during the reaction determines the outcome. In ideal case, the reaction produces a well-separated melt of metal and slag. For this, the temperature has to be high enough to melt both the reaction products, the resulting metal and the fuel oxide. Too low temperature will result in a mixture of sintered metal and slag, too high temperature - above boiling point of any reactant or product - will lead to rapid production of gas, dispersing the burning reaction mixture, sometimes with effects similar to a low-yield explosion. (Moisture in composition or adjanced materials can result in similar effect, a steam explosion.) In compositions intended for production of metal by aluminothermic reaction, these effects can be counteracted. Too low reaction temperature (e.g. when producing silicon from sand) can be boosted with addition of a suitable oxidizer (e.g. sulfur in aluminium-sulfur-sand compositions), too high temperatures can be reduced by using a suitable coolant and/or slag flux. The flux often used in amateur compositions is calcium fluoride, as it reacts only minimally, has relatively low melting point, low melt viscosity at high temperatures (therefore increasing fluidity of the slag) and forms an eutectic with alumina. Too much of flux however dilutes the reactants to the point of not being able to sustain combustion. The type of metal oxide also has dramatic influence to the amount of energy produced; the higher the oxide, the higher the amount of energy produced. A good example is the difference between manganese(IV) oxide and manganese(II) oxide, where the former produces too high temperature and the latter is barely able to sustain combustion; to achieve good results a mixture with proper ratio of both oxides should be used.[19]
The reaction rate can be also tuned with particle sizes; coarser particles burn slower than finer particles. The effect is more pronounced with the particles requiring being heated to higher temperature to start reacting. This effect is pushed to the extreme with nano-thermites.
The temperature achieved in the reaction in adiabatic conditions, when no heat is lost to the environment, can be estimated using the Hess's law - by calculating the energy produced by the reaction itself (subtracting the enthalpy of the reactants from the enthalpy of the products) and subtracting the energy consumed to heating the products (from their specific heat, when the materials only change their temperature, and their enthalpy of fusion and eventually enthalpy of vaporization, when the materials melt or boil). In real conditions, the reaction loses heat to the environment, the achieved temperature is therefore somewhat lower. The heat transfer rate is finite, so the faster the reaction is, the closer to adiabatic condition it runs and the higher is the achieved temperature.[20]
The most common composition is the iron thermite. The oxidizer used is usually either iron(III) oxide or iron(II,III) oxide. The former produces more heat. The latter is easier to ignite, likely due to the crystal structure of the oxide. Addition of copper or manganese oxides can significantly improve the ease of ignition.
The original mixture, as invented, used iron oxide in the form of mill scale. The composition was very difficult to ignite.[18]
Copper thermite can be prepared using either copper(I) oxide (red) or copper(II) oxide (black). The composition produces less heat per mass than the iron thermite. However, the burn rate tends to be very fast and the copper melting point is relatively low. Therefore the reaction produces a significant amount of molten copper in a very short time. An explosion can occur and send a spray of copper drops to considerable distance.[21]
Copper thermite has industrial uses in e.g. welding of thick copper conductors ("cadwelding"). This kind of welding is being evaluated also for cable splicing on the US Navy fleet, for use in high-current systems, e.g. electric propulsion.[22]
The reaction can be so fast the copper thermite can be considered a type of flash powder.
Thermate composition is a thermite one enriched with a salt-based oxidizer (usually nitrates, e.g. barium nitrate, or peroxides). In contrast with thermites, thermates burn with evolution of flame and gases. The presence of the oxidizer makes the mixture easier to ignite and improves penetration of target by the burning composition, as the evolved gas is projecting the molten slag and providing mechanical agitation.[18] This mechanism makes thermate more suitable than thermite for incendiary purposes and for emergency destruction of sensitive equipment (e.g. cryptographic devices), as thermite's effect is more localized.
Metals are capable of burning under the right conditions, similar to the combustion process of wood or gasoline. In fact, rust is the result of oxidation of steel or iron at very slow rates. A thermite reaction is a process in which the correct mixture of metallic fuels are combined and ignited. Ignition itself requires extremely high temperatures.
Ignition of a thermite reaction normally requires only a simple child's sparkler or easily obtainable magnesium ribbon, but may require persistent efforts, as ignition can be unreliable and unpredictable. These temperatures cannot be reached with conventional black powder fuses, nitrocellulose rods, detonators, pyrotechnic initiators, or other common igniting substances.[13] Even when the thermite is hot enough to glow bright red, it will not ignite as it must be at or near white-hot to initiate the reaction. It is possible to start the reaction using a propane torch if done correctly.[23]
Often, strips of magnesium metal are used as fuses. Because metals burn without releasing cooling gases, they can potentially burn at extremely high temperatures. Reactive metals such as magnesium can easily reach temperatures sufficiently high for thermite ignition. Magnesium ignition remains popular among amateur thermite users, mainly because it can be easily obtained.[13]
The reaction between potassium permanganate and glycerol or ethylene glycol is used as an alternative to the magnesium method.[13] When these two substances mix, a spontaneous reaction will begin, slowly increasing the temperature of the mixture until flames are produced. The heat released by the oxidation of glycerine is sufficient to initiate a thermite reaction.[13]
Apart from magnesium ignition, some amateurs also choose to use sparklers to ignite the thermite mixture.[24] These reach the necessary temperatures and provide enough time before the burning point reaches the sample.[25] However, this can be a dangerous method, as the iron sparks, like the magnesium strips, burn at thousands of degrees and can ignite the thermite even though the sparkler itself is not in contact with it. This is especially dangerous with finely powdered thermite.
Similarly, finely-powdered thermite can be ignited by a regular flint spark lighter, as the sparks are burning metal (in this case, the highly-reactive rare-earth metals lanthanum and cerium). Therefore it is unsafe to strike a lighter close to thermite.
A stoichiometric mixture of finely powdered iron(III) oxide and aluminium may be ignited using ordinary red-tipped book matches by partially embedding one match head in the mixture, and igniting that match head with another match, preferably held with tongs in gloves to prevent flash burns.
Thermite reactions have many uses. Thermite is not an explosive; instead it operates by exposing a very small area of metal to extremely high temperatures. Intense heat focused on a small spot can be used to cut through metal or weld metal components together both by melting metal from the components, and by injecting molten metal from the thermite reaction itself.
Thermite may be used for repair by the welding in-place of thick steel sections such as locomotive axle-frames where the repair can take place without removing the part from its installed location.
Thermite can be used for quickly cutting or welding steel such as rail tracks, without requiring complex or heavy equipment.[26][27] However, defects such as slag inclusions and voids (holes) are often present in such welded junctions and great care is needed to operate the process successfully. Care must also be taken to ensure that the rails remain straight, without resulting in dipped joints, which can cause wear on high speed and heavy axle load lines.[28]
A thermite reaction, when used to purify the ores of some metals, is called the thermite process, or aluminothermic reaction. An adaptation of the reaction, used to obtain pure uranium, was developed as part of the Manhattan Project at Ames Laboratory under the direction of Frank Spedding. It is sometimes called the Ames process.[29]
Copper thermite is used for welding together thick copper wires for the purpose of electrical connections. It is used extensively by the electrical utilities and telecommunications industries (exothermic welded connections).
Thermite hand grenades and charges are typically used by armed forces in both an anti-materiel role and in the partial destruction of equipment; the latter being common when time is not available for safer or more thorough methods.[30][31] For example, thermite can be used for the emergency destruction of cryptographic equipment when there is a danger that it might be captured by enemy troops. Because standard iron-thermite is difficult to ignite, burns with practically no flame and has a small radius of action, standard thermite is rarely used on its own as an incendiary composition. It is more usually employed with other ingredients added to enhance its incendiary effects. Thermate-TH3 is a mixture of thermite and pyrotechnic additives which have been found to be superior to standard thermite for incendiary purposes.[32] Its composition by weight is generally about 68.7% thermite, 29.0% barium nitrate, 2.0% sulfur, and 0.3% of a binder (such as PBAN).[32] The addition of barium nitrate to thermite increases its thermal effect, produces a larger flame, and significantly reduces the ignition temperature.[32] Although the primary purpose of Thermate-TH3 by the armed forces is as an incendiary anti-materiel weapon, it also has uses in welding together metal components.
A classic military use for thermite is disabling artillery pieces, and it has been used for this purpose during and since World War II; such as at Pointe du Hoc, Normandy.[33] Thermite can permanently disable artillery pieces without the use of explosive charges, and therefore thermite can be used when silence is necessary to an operation. There are several ways to do this. By far the most destructive method is to weld the weapon shut by inserting one or more armed thermite grenades into the breech and then quickly closing it. This makes the weapon impossible to be loaded.[34] An alternative method is to insert an armed thermite grenade down the muzzle of the artillery piece, fouling the barrel and making the weapon very dangerous to fire. Yet another method is to use thermite to weld the traversing and elevation mechanism of the weapon, making it impossible to aim properly.
Thermite was also used in both German and Allied incendiary bombs during World War II.[35][36] Incendiary bombs usually consisted of dozens of thin thermite-filled canisters (bomblets) ignited by a magnesium fuse. Incendiary bombs destroyed entire cities due to the raging fires that resulted from their use. Cities that primarily consisted of wooden buildings were especially susceptible. These incendiary bombs were utilized primarily during nighttime air raids. Bombsights could not be used at night, creating the need to use munitions that could destroy targets without the need for precision placement.
Thermite usage is hazardous due to the extremely high temperatures produced and the extreme difficulty in smothering a reaction once initiated. Small streams of molten iron released in the reaction can travel considerable distances and may melt through metal containers, igniting their contents (see images). Additionally, flammable metals with relatively low boiling points such as zinc (with a boiling point of 907 °C (1,665 °F), which is about 1,370 °C (2,500 °F) below the temperature at which thermite burns) could potentially spray superheated boiling metal violently into the air if near a thermite reaction.
Preheating of thermite before ignition can easily be done accidentally, for example by pouring a new pile of thermite over a hot, recently-ignited pile of thermite slag. When ignited, preheated thermite can burn almost instantaneously, releasing light and heat energy at a much higher rate than normal and causing burns and eye damage at what would normally be a reasonably safe distance.
The thermite reaction can take place accidentally in industrial locations where abrasive grinding and cutting wheels are used with ferrous metals. Using aluminium in this situation produces a mixture of oxides which is capable of a violent explosive reaction.[37]
Mixing water with thermite or pouring water onto burning thermite can cause a steam explosion, spraying hot fragments in all directions.
Thermite's main ingredients were also utilized for their individual qualities, specifically reflectivity and heat insulation, in a paint coating or dope for the German zeppelin Hindenburg, possibly contributing to its fiery destruction. This was a theory put forward by the former NASA scientist Addison Bain, and later tested in small scale by the scientific reality-TV show MythBusters with semi-inconclusive results. (It was not proven to be the fault of the thermite reaction, but instead it was conjectured to be a combination of that and the burning of hydrogen gas that filled the body of the Hindenburg).[38] The MythBusters program also tested the veracity of a video found on the Internet, whereby a quantity of thermite was allowed to drop onto a block of ice of similar mass, causing a sudden explosion. They were able to confirm the results, and Jamie Hyneman conjectured this was due to the thermite mixture aerosolizing, perhaps in a cloud of steam, causing it to burn even faster. They found chunks of ice as far as 150 feet (46 m) from the point of explosion. Mr. Hyneman voiced skepticism about another theory explaining the phenomenon: one that the reaction somehow separated the hydrogen and oxygen in the water and then ignited them.