Thermite

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Not to be confused with thermate or Thermalite.
A thermite mixture using iron (III) oxide

Thermite is a pyrotechnic composition of metal powder, fuel and metal oxide. When ignited by heat, thermite undergoes an exothermic oxidation-reduction reaction. Most varieties are not explosive but can create brief bursts of high temperature in a small area. Its form of action is similar to that of other fuel-oxidizer mixtures, such as black powder.

Thermites have diverse compositions. Fuels include aluminium, magnesium, titanium, zinc, silicon, and boron. Aluminium is common because of its high boiling point. Oxidizers include 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,IV) oxide.[1]

Thermites have been used for welding metal parts such as railway rails, in metal refining, demolition of munitions, and in incendiary weapons.

Chemical reactions[edit]

A thermite reaction using iron(III) oxide. The sparks flying outwards are globules of molten iron trailing smoke in their wake.

The aluminium reduces the oxide of another metal, most commonly iron oxide, because aluminium forms stronger, far more stable, bonds with oxygen than iron:

Fe2O3 + 2 Al → 2 Fe + Al2O3

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 (however, it may react violently):

3 CuO + 2 Al → 3 Cu + Al2O3

Some thermite-like mixtures are used as pyrotechnic initiators as in fireworks.

Thermites with nanosized particles are described by a variety of terms, such as metastable intermolecular composites, super-thermite,[3] nano-thermite,[4] and nanocomposite energetic materials.[5][6]

History[edit]

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". 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]

Types[edit]

A thermite reaction taking place on a cast iron skillet

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, quartz in silicon 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;[citation needed]
  • It forms a passivation layer making it safer to handle than many other reactive metals.[15]
  • Its relatively low melting point (660 °C) 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.
  • Its high boiling point (2519 °C) 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 2887 °C and 2582 °C respectively), but is especially unusual among the highly reactive metals (cf. magnesium and sodium which boil at 1090 °C and 883 °C respectively).
  • Further, the low density of the aluminium oxide formed as a result of the reaction tends to cause it to float on the resultant pure metal. This is particularly important for reducing contamination in a 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 2500 °C 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. Even so, thermite is used for welding underwater.[17]

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. 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 a 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]

Iron thermite[edit]

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[edit]

Copper thermite can be prepared using either copper(I) oxide (Cu2O, red) or copper(II) oxide (CuO, black). The burn rate tends to be very fast and the melting point of copper is relatively low so the reaction produces a significant amount of molten copper in a very short time. Copper(II) thermite reactions can be so fast that copper thermite can be considered a type of flash powder. An explosion can occur and send a spray of copper drops to considerable distance.[21]

Copper(I) 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]

Thermates[edit]

Main article: Thermate

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.

Ignition[edit]

A thermite reaction using iron(III) oxide

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 a 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.[citation needed] 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. 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).[26] 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.[citation needed]

Civilian uses[edit]

Thermite reaction proceeding for a railway welding. Shortly after this, the liquid iron flows into the mould around the rail gap
Residues of ceramic molds for thermite welding like these, left by railway workers, can be found along tracks

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.[citation needed]

Thermite can be used for quickly cutting or welding steel such as rail tracks, without requiring complex or heavy equipment.[27][28] 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.[29]

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.[30]

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).

Military uses[edit]

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.[31][32] 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 increase 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.[33] 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).[33] The addition of barium nitrate to thermite increases its thermal effect, produces a larger flame, and significantly reduces the ignition temperature.[33] Although the primary purpose of Thermate-TH3 by the armed forces is as an incendiary anti-material 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 since World War II; such as at Pointe du Hoc, Normandy.[34] 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. This can be done by inserting one or more armed thermite grenades into the breech and then quickly closing it; this welds the breech shut and makes loading the weapon impossible.[35] Alternatively, a thermite grenade discharged inside the barrel of the gun will foul the barrel, making the weapon very dangerous to fire; thermite can also be used to weld the traversing and elevation mechanism of the weapon, making it impossible to aim properly.[citation needed]

Thermite was used in both German and Allied incendiary bombs during World War II.[36][37] Incendiary bombs usually consisted of dozens of thin thermite-filled canisters (bomblets) ignited by a magnesium fuse. Incendiary bombs created massive damage in many cities due to fires started by the thermite. 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.

Hazards[edit]

The violent effects of thermite

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, which is about 1,370 °C below the temperature at which thermite burns) could potentially spray superheated boiling metal violently into the air if near a thermite reaction.[citation needed]

If, for some reason, thermite is contaminated with organics, hydrated oxides and other compounds able to produce gases upon heating or reaction with thermite components, the reaction products may be sprayed. Moreover, if the thermite mixture contains enough empty spaces with air and burns fast enough, the super-heated air also may cause the mixture to spray. For this reason it is preferable to use relatively crude powders, so the reaction rate is moderate and hot gases could escape the reaction zone.

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.[citation needed]

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.[38]

Mixing water with thermite or pouring water onto burning thermite can cause a steam explosion, spraying hot fragments in all directions.[citation needed]

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 proven not to be the fault of the thermite reaction alone, but instead conjectured to be a combination of that and the burning of hydrogen gas that filled the body of the Hindenburg).[39] 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, finding huge chunks of ice as far as 50m from the point of explosion. Co-host Jamie Hyneman conjectured that this was due to the thermite mixture aerosolizing, perhaps in a cloud of steam, causing it to burn even faster. Hyneman also voiced skepticism about another theory explaining the phenomenon: that the reaction somehow separated the hydrogen and oxygen in the ice and then ignited them. A far more likely explanation is that the explosion is due to the reaction of high temperature molten aluminium with water. Aluminium reacts violently with water or steam at high temperatures, releasing hydrogen and oxidizing in the process. The speed of that reaction and the ignition of the resulting hydrogen can easily account for the explosion verified.[40] This process is akin to the explosive reaction caused by dropping metallic potassium into water.

See also[edit]

References[edit]

  1. ^ Kosanke, K; Kosanke, B. J; Von Maltitz, I; Sturman, B; Shimizu, T; Wilson, M. A; Kubota, N; Jennings-White, C; Chapman, D (December 2004). Pyrotechnic Chemistry — Google Books. ISBN 978-1-889526-15-7. Retrieved 2009-09-15. 
  2. ^ "Demo Lab: The Thermite Reaction". Ilpi.com. Retrieved 2011-10-11. 
  3. ^ "Low-Cost Production of Nanostructured Super-Thermites". Navysbir.com. Retrieved 2011-10-12. 
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  7. ^ H. Goldschmidt, "Verfahren zur Herstellung von Metallen oder Metalloiden oder Legierungen derselben" (Process for the production of metals or metalloids or alloys of the same), Deutsche Reichs Patent no. 96317 (13 March 1895).
  8. ^ Goldschmidt, Hans; Vautin, Claude (1898-06-30). "Aluminium as a Heating and Reducing Agent". Journal of the Society of Chemical Industry 6 (17): 543–545. Retrieved 2011-10-12. 
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  10. ^ "Thermite Bombs used to Set Fires". The Milwaukee Journal. 1939-12-01. Retrieved 2011-10-12. 
  11. ^ "what it Means: Thermite Bombing". the Florence Times. 1940-08-31. Retrieved 2011-10-12. 
  12. ^ "Hydrogen May Not Have Caused Hindenburg's Fiery End – Page 3 – New York Times". Nytimes.com. 1997-05-06. Retrieved 2011-10-12. 
  13. ^ a b c d e "Thermite". Amazing Rust.com. 2001-02-07. Retrieved 2011-10-12. 
  14. ^ Koch, Ernst-Christian (2002). "Metal-Fluorocarbon-Pyrolants: III. Development and Application of Magnesium/Teflon/Viton (MTV)". Propellants, Explosives, Pyrotechnics 27 (5): 262. doi:10.1002/1521-4087(200211)27:5<262::AID-PREP262>3.0.CO;2-8. 
  15. ^ Granier, J. J.; Plantier, K. B.; Pantoya, M. L. (2004). "The role of the Al2O3passivation shell surrounding nano-Al particles in the combustion synthesis of NiAl". Journal of Materials Science 39 (21): 6421. Bibcode:2004JMatS..39.6421G. doi:10.1023/B:JMSC.0000044879.63364.b3. 
  16. ^ Wohletz, Kenneth (2002). "Journal of Volcanology and Geothermal Research : Water/magma interaction: some theory and experiments on peperite formation". Journal of Volcanology and Geothermal Research 114: 19. Bibcode:2002JVGR..114...19W. doi:10.1016/S0377-0273(01)00280-3. 
  17. ^ Sarah Lyall (2006-10-27). "Cameras Catch Speeding Britons and Lots of Grief – New York Times". Great Britain: Nytimes.com. Retrieved 2011-10-12. 
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  30. ^ US patent 2830894, Spedding, Frank H.; Wilhelm, Harley A. & Keller, Wayne H., "Production of Uranium", issued 1958, assigned to United States Atomic Energy Commission 
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  33. ^ a b c US patent 5698812, Song, Eugene, "Thermite destructive device", issued 1997, assigned to United States Secretary of the Army 
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Further reading[edit]

  • L. L. Wang, Z. A. Munir and Y. M. Maximov (1993). "Thermite reactions: their utilization in the synthesis and processing of materials". Journal of Materials Science 28 (14): 3693–3708. Bibcode:1993JMatS..28.3693W. doi:10.1007/BF00353167. 
  • M. Beckert (2002). "Hans Goldschmidt and the aluminothermics". Schweissen und Schneiden 54 (9): 522–526. 

External links[edit]