This article needs attention from an expert in Chemicals.(April 2021)
Napalm is an incendiary mixture of a gelling agent and a compatible volatile petrochemical (usually gasoline (petrol), kerosene and diesel fuel). The name is a portmanteau of two of the constituents of the original thickening and gelling agents: aluminium naphthenate and aluminum salts of coconut fatty acids sold by Metasap under the trade name Aluminum "palmitate". Napalm B (Alecto) is the more modern version of napalm (utilizing polystyrene derivatives) and, although distinctly different in its chemical composition, is often referred to simply as "napalm".
The first military-grade thickener based on aluminum soap, X-104 soap, simply called napalm, developed by Fieser's group and Arthur Minich, was composed of a co-precipitated hydroxy-aluminum salts of coconut fatty acids, naphthenic acids and oleic acid, in a weight ratio of 2:1:1. This soap was the only standard thickener used on a large scale in WWII, the Korean War and the Vietnam War, with the minority, during the vietnam war, being composed of Alecto, isooctal (M4), instantgel and Incendagel. The sample 104 was extensively researched and investigated, becoming the 104 series (X-104 series), with each specific soap to be used between X-104-A, X-104-B and X-104-C.
A team led by chemist Louis Fieser originally developed napalm for the United States Chemical Warfare Service in 1942 in a secret laboratory at Harvard University. Of immediate first interest was its viability as an incendiary device to be used in fire bombing campaigns during World War II; its potential to be coherently projected into a solid stream that would carry for distance (instead of the bloomy fireball of pure gasoline) resulted in widespread adoption in infantry flamethrowers as well. Acting as an anti-mist agent, napalm delays the evaporation of non-polar substances (hydrocarbons), extracted from oil.
Napalm burns at temperatures ranging from 800 to 1,200 °C (1,470 to 2,190 °F). In addition, it burns for a greater duration than gasoline, as well as being more easily dispersed and sticking tenaciously to its targets. These traits make it extremely effective (and controversial) in the anti-structure and antipersonnel role. It has been widely used in both the air and ground role, with the largest use to date being via air-dropped bombs in World War II (most notably in the devastating incendiary attacks on Japanese cities in 1945), and later close air support roles in Korea and Vietnam. Napalm also has fueled most of the flamethrowers (tank, ship and infantry-based) used since World War II, giving them much greater range, and was used in this role as a common weapon of urban combat by both the Axis and the Allies in World War II. Multiple nations (including the United States,[contradictory] China, Russia, Iran and North Korea) maintain large stockpiles of napalm-based weapons of various types.
Napalm was used in flamethrowers, bombs and tanks in World War II. It is believed to have been formulated to burn at a specific rate and to adhere to surfaces to increase its stopping power. During combustion, napalm rapidly deoxygenates the available air and generates large amounts of carbon monoxide and carbon dioxide.
Like any other thickener, increasing the concentration of the solute tends to increase the viscosity of the solution. Concentrations of ~4% are the best concentrations used in flamethrowers, concentrations of >4% are used in mechanized flamethrowers and others high kinetic energy systems, which require the use of fracture resistant gel. Depending on the proportion of mixture needed to dissolve the carboxylic salt, the resulting solution could be unfeasible for flamethrowers, but satisfactory for incendiary cluster bombs and mines, due to its high viscosity.
Napalm is packaged in the exact quantity for application to each delivery instrument, with each type receiving its usage design. With three commonly used models. Napalm thickener type A, the X-104-B, being delivered to troops in the form of 5 lbs cans, contained in boxes of 6 to 8 units, to be used in flamethrowers. The Napalm thickener Type B, this thickener is delivered to troops to prepare incendiary oil NP. This thickener is delivered in 100 lbs drums (X-104-A). X-104-C, the napalm type C, disposed at the end of the war, is delivered in 15 lbs drums, suitable for preparing NP-type incendiary oils in the field (12,6% gel).
The designation variations between soaps and types were due to an initial specification, later terminated, of specific soaps for flamethrowers, which were usually delivered in Type A (Napalm Type A) packaging.
Later, another designation that was used, is the US Navy's Napalm Type 1 (M2) thickener, a finely ground Napalm to which an anti-caking agent was added to the thickener type B, with the anti-caking agent that can be added intimately. This type of Napalm was specifically developed for use in the Incendiary Mixer Mk 1 and Mods (Broughton, Geoffrey et al. 1943) .
X-104-B received specification modifications, being disposed in 5-1/4 pound cans, stored in boxes containing 6, readily indicated for making a 4.2% gel, considered preferred for flame throwers fuels.
Initially, the difference between the thickeners was that Napalm Type A had a slow solvation, with Type B being fast. Manufacturers then used variations of X-104, with a higher concentration of oleic acid. These soaps were more susceptible to oxidation compared to the original formula (then X-104), which resulted in a slower solvating soap when oxidized, but the soap had a longer shelf life than type B. When the CWS standardization directive was approved, the Type A solvation time restriction was removed, with the solvation time being the same as Type B. The soap's acidic ratio range turned out to be the same as soap original X-104.
Alternative compositions exist for different types of uses, e.g. triethylaluminium, sodium metal, K.O.F.Q.R. fluid, KS fluid (EWP), flamex and white phosphorus a pyrophoric compound that aids ignition.
Use of fire in warfare has a long history. Greek fire, also described as "sticky fire" (πῦρ κολλητικόν, pýr kolletikón), is believed to have had a petroleum base. The development of napalm was precipitated by the use of jellied gasoline mixtures by the Allied forces during World War II. Latex, used in these early forms of incendiary devices, became scarce, since natural rubber was almost impossible to obtain after the Japanese army captured the rubber plantations in Malaya, Indonesia, Vietnam, and Thailand.
This shortage of natural rubber prompted chemists at US companies such as DuPont and Standard Oil, and researchers at Harvard University, to develop factory-made alternatives—artificial rubber for all uses, including vehicle tires, tank tracks, gaskets, hoses, medical supplies and rain clothing. A team of chemists led by Louis Fieser at Harvard University was the first to develop synthetic napalm, during 1942. "The production of napalm was first entrusted to Nuodex Products, and by the middle of April 1942 they had developed a brown, dry powder that was not sticky by itself, but when mixed with gasoline turned into an extremely sticky and flammable substance." One of Fieser's colleagues suggested adding phosphorus to the mix which increased the "ability to penetrate deeply...into the musculature, where it would continue to burn day after day."
On 4 July 1942, the first test occurred on the football field near the Harvard Business School. Tests under operational conditions were carried out at Jefferson Proving Ground on condemned farm buildings, and subsequently at Dugway Proving Ground on buildings designed and constructed to represent those to be found in German and Japanese towns. This new mixture of chemicals was widely used in the Second World War in incendiary bombs and in flamethrowers.
From 1965 to 1969, the Dow Chemical Company manufactured napalm B for the American armed forces. After news reports of napalm B's deadly and disfiguring effects were published, Dow Chemical experienced boycotts of its products, and its recruiters for new chemists, chemical engineers, etc., graduating from college were subject to campus boycotts and protests. The management of the company decided that its "first obligation was the government." Meanwhile, napalm B became a symbol for the Vietnam War.
Composition and nature of preparation
Napalm-A, colloquially coinciding with Napalm type A (X-104-B), is an impure substance composed of a mixture of fatty acids stabilized by a basic aluminum cation. The interaction of these, with each other, form a compound, a soap, preferably a white granular. Napalm has no definable formula, as it contains coconut fatty acids and naphthenic acid, but it can be condensed to two structures. The Soap initially consisted of a mixture of soaps of different physical states, with aluminum naphthenate tending to a gum and metasap soap being a fluffy white powder.
The experiment was eventually changed and redesigned several times (EXRY). With the original formula showing a low adhesion and undesirable sintering of the soap during manufacture (G. H. Mclntyre et al. 1944.). Gibb's laboratory group developed a version of the original napalm, tested for filling implementation in the field, initially presenting itself as a solvated and extruded solid (napalm polymer), which can be an incendiary solid or not. Depending on the solvator, the solvated took the form of a semi-solid aluminum grease, from white to brownish in color and to brownish solids, in the form of pellets, of various sizes.
The material achieved "satisfactory" results when, under three co-precipitations (X-102, X-103 and X-104), the last mixture, composed by 2 parts coconut fatty acid, 1 part naphthenic acid and 1 part oleic acid (E1R3), has been prepared (G. H. Mclntyre et al. 1944.).
The napalm thickener finally adopted consisted of a coarse powdered aluminum soap composed of naphthenic, oleic and coconut fatty acids. The sodium soap used for aluminum soap precipitation contained 0.10 to 0.15 percent alpha-naphthol, an intimate mixture. The recommended formula of the organic acids used in the manufacture of the napalm thickener was the original X-104.
Napalm is classically prepared in two steps. (I) The reactants, readily mixed, are alkalized by an excess of base, forming the sodium salts of naphthenic acids, total coconut fatty acids and oleic acid.
(II) A concentrated alum solution is then dropped into the reactor until coagulation occurs, after the end of the metathesis reaction. The aluminum content of the finished thickener ranges from 5.4 to 5.8 percent and the moisture content from 0.4 to 0.8 percent. Three processes have been used successfully for the manufacture of napalm during the second world war. All are based on the equations below, but the mechanical details for combining the materials differ.
The method employed as an attempt at standardization was called the batch method 1. In this process, the total amount of caustic soda required is added to the mixed acids, and alum is then added until precipitation is complete. This is the method used by the largest number of manufacturers and was selected as recommended based on the fact that there is more information available about it than about any other process.
The stoichiometric and reaction mixture tends not to coagulate the product, necessitating the use of an excess of alum. The excess varies from 15% to 30% of the 100%. With the excess varying from the notions employed in the procedure, ranging from ~0% to 100%, with the stoichiometric excess being 30%. The precipitation temperature, mainly of water, will dictate the physical state of the product. The higher of temperature, the greater the density of the product, however, at a certain point, the product sinters. The temperature chosen is based on the entropy of the fatty acid.
Naphthenic acids have a tendency to precipitate out of a viscous granular material into a paste. Oleic acid precipitates into a less viscous granular material than naphthenic acid, but can sinter completely at room temperature, forming a gum. Coconut fatty acid precipitates in the form of a fragrant granular material, showing great resistance to high temperatures and oxidation, being pulverized into a fine powder, easily carried by air.
Soap concentration also affects physicochemical properties, as well as speed and type of agitation. The concentration of the reagents itself also dictates the soap's physicochemical properties .With the standard concentration used by manufacturers being 13% soap with caustic excess and 15% alum. The stoichiometric equation describes the use being a 6:1 molar concentration for soap with caustic and alum excess, respectively, with the standard process using a 6x higher concentration of Alum, an equimolar concentration. Drip of a half molar concentration alum solution tends to produce a soap rich in aluminum-dihydroxylated (2:1).
The alum concentration will depend on the agitation speed, the hydrodynamics of the system. Low and very high equimolar concentrations tend to pre-sinter the soap, by different mechanisms.
With the supernatant formed, the reactor contents are diluted and poured into a centrifuge or in filtered under suction, with centrifugation being more preferred by manufacturers. The coagulate is then dehydrated, forming a cake.
Due to the slowing down of filtration and the often deficient filtration scale, it is often necessary for the product formed with acidic aqueous mother liquor to remain for a long time, which ends up degrading the product by hydrolysis, with the fully digested material contaminating the product.
The cake is pulverized and then dried in trays, in a rotating tunnel, under heat and ventilation, or it is boiled under vacuum, with an inclined rotating barrel. The centrifugation and drying process are essential steps in the final property of the soap. The structure of the particulate will dictate the most convenient drying process, and some particulates will not be satisfactory for filtration under suction, due to the large contact area, requiring greater work, also favoring sintering. The type of spin and the speed of rotation tend to change the properties of the aluminum soaps. A strong centrifugation tends to pre-sinter the soap or sinter it completely, turning the material, a powder, into a sticky material.
At very high temperatures sintering the material early on, turning the powder into a crystalline sand-like material and oxidizing it under induction, making the material potentially explosive when sprayed onto a flame. A number of antioxidant compounds had been tested. With α-naphthol prolonging the induction time. Tray, mat, plate, and other static oxidation methods occur immediately after a sinter rearrangement.
The material undergoes a slight decrease in viscosity, which favors drying, increasing its melting point. The mass then behaves as a single compound and oxidizes evenly, starting with the material in contact with the tray. The breakage of the pre-induced cake, which did not undergo oxidation, made the material more resistant to oxidation. However, increasing density decreased the spontaneity of dissolution. Induction appears to occur only in soaps rich in unsaturated acids. Coconut soap did not go into induction, at the oxidation temperature of unsaturated soaps.
The vacuum distillation process, or the presence of an inert atmosphere, tends to eliminate the oxidation process. Drying, under agitation, delays the induction process, eliminating the need for the additive. The drying process generally uses a speed (FPM) and a temperature below the occurrence of metastable rearrangement (sintering). Hot air drying tends to oxidize the material from the outside. Static oxidation comes from the inside out. Hot air drying oxidizes the material immediately.
Maximum thickening for napalm was achieved using a caustic excess of 60%. But the manufacturers generally employed something ranging from 51~55%. The ≥50% caustic excess value is standard for spontaneous thickening soaps such as M1 (M2), M3, M4, M5, bogol, camgel, OP-2 and HK, lastol (EAZ-92-01-series, codename "locost"), linool (EAZ-92-02) and others. With the value being below ≤50%, for Steolate, F.R.A.S., napalm of low av, W and metalex, soaps with no thickening at <15 degrees Celsius.
The alum used by the manufacturers could be of different degrees of hydration, but aluminum sulfate trihydrate, called the Victory grade, was preferred. The salt aluminizing process could employ other water-soluble aluminum salts as well as other forms of aluminum sulfate. This aluminum salt must contain an inert, monovalent or bi-valent cation. The additional amount of alum applied by the suppliers in the coagulation of napalm was based on dividing the molar value of free caustic.
The precipitation process employed by each napalm manufacturer varied considerably, from the machinery to the notions applied in the process. The widely adopted process was the batch process No. 1, more suitable for the production of napalm, due to its simplicity.
The other notable process was the "two-stream", which gave a product with a thickening power up to 30% greater than the conventional process. The scale process, called "continuous process", was the most desirable from the point of view of engineering, with the material being able to be produced in less than 1 hour, continuously and on a large scale. The batch method-2, which uses a neutral sodium soap, with sodium ash being added to the alum solution, forming the "tempered" alum. Which is subsequently dripped into the neutral soap, this process produces a better soap than the standard process. The batch method-2 is considerably less energetic and is most recommended for manufacturers with more sensitive machinery.
Batch process no. 2 was applied by the British of A. Boake Roberts, in the manufacture of F.R.A.S., with the addition of a protective colloid, which uniformed the product's dissolution and reduced the probability of product digestion. Process batch type 1 and colloid polymer are used in the manufacture of Instantgel. The total replacement of alkali hydroxides has its advantages and disadvantages arising from their properties. Other commonly used bases are sodium or potassium carbonate, aqueous ammonia solution, calcium and magnesium hydroxide.
Thickening mechanism and properties
Aluminum soaps are denoted as mono, di-acid and "tri-acid" aluminum salts, having one to two free hydroxy groups, with each structure being more satisfactory for thickening, depending on the enthalpy of dissolution of the coupled fatty acid. The aluminum element has shown, since the first attempts to isolate it, the behavior of acting chemically opposite to the electrical affinity of the medium, being a base in an acidic medium and acid in a basic medium, resulting in substances with a structure dependent on the pH of the medium.
This characteristic was also manifested in its compounds, with aluminum oxide acting as a base in an acidic medium and as an acid in a basic medium. With aluminum reacted in an acidic medium, presenting an electrophilic character.
Napalm, and other hydroxy-aluminum soaps, is an example of an ampholyte, having only one free hydroxyl group, acting as a nucleophile, and three acid groups, composed of two carboxylic groups and a trivalent cationic aluminum group, acting as electrophiles.
This property served as the basis for Fowkes, who suggested that the gelling mechanism of aluminum soaps was due to the amphoteric cascade effect, stabilized by the solvation of lipophilic groups, forming pseudopolymeric structures, which spontaneously broke and reformed. With this structure aging to a point, forming a pseudopolymer of size that forced the precipitation of the colloidal complex, in the form of gel, jelly and sol.
This assumption proved to be satisfactory and applicable in other studies for a long time, however, Wang and Rackaitis, using viscosity measurements and high resolution electron microscopy, revealed that the gelling mechanism is due to the rearrangement of soap molecules in micelles of spherical structure, which congest in uniform size.
The micellar formation mechanism of monohydroxylated aluminum soaps is due to micellar inversion of the coagulate, with this step occurring in the sintered product. The lipophilic groups of the low molecular-mass organic gelator attract, capture and immobilize the lipophilic solvent and the hydrophilic groups are repelled by the solvent, spontaneously forming a stable configuration, resulting in a spheroid structure, a reverse micelle, with subsequent nucleophilic action of hydroxyl radicals. Then the exposed nonpolar micelle groups coalesce by immobilizing the surrounding solvent, the continuous phase (preferably low molecular weight hydrocarbon), resulting in a material with solid properties, from a precipitate to a coagulate.
Depending on the quality of the napalm, is not able to digest fuel, resulting in a precipitate only. Gels obtained by endothermic thickening tend to have a tendency to behave as a precipitate, due to syneresis.
Because the thickened product is a thixotropic agent, when stirred, when it is disseminated by explosives, heated or set on fire, its viscosity decreases, as the movement of its constituent entities increases due to the decrease in intermolecular forces. The decrease in viscosity in thickened gasoline is commonly generated by endothermic medium, the heat of explosions and the heat of combustion, commonly caused by the combustion of the igniter and high speed of digestion of surrounding oxygen.
Napalm was first employed in incendiary bombs and went on to be used as fuel for flamethrowers.
The first recorded strategic use of napalm incendiary bombs occurred in an attack by the US Army Air Force on Berlin on 6 March 1944, using American AN-M76 incendiary bombs with PT-1 (Pyrogel) filler. The first known tactical use by the USAAF was by the 368th Fighter Group, Ninth Air Force Northeast of Compiègne, France 27 May 1944 and the British De Havilland Mosquito FB Mk.VIs of No. 140 Wing RAF, Second Tactical Air Force on 14 July 1944, which also employed the AN-M76 incendiary in a reprisal attack on the 17th SS Panzergrenadier Division "Götz von Berlichingen" in Bonneuil-Matours. Soldiers of this Waffen SS unit had captured and then killed a British SAS prisoner-of-war, Lt. Tomos Stephens, taking part in Operation Bulbasket, and seven local Resistance fighters. Although it was not known at the time of the air strike, 31 other POWs from the same SAS unit, and an American airman who had joined up with the SAS unit, had also been executed.
Further use of napalm by American forces occurred in the Pacific theater of operations, where in 1944 and 1945, napalm was used as a tactical weapon against Japanese bunkers, pillboxes, tunnels, and other fortifications, especially on Saipan, Iwo Jima, the Philippines, and Okinawa, where deeply dug-in Japanese troops refused to surrender. Napalm bombs were dropped by aviators of the U.S. Navy, the United States Army Air Forces, and the U.S. Marine Corps in support of ground troops. The M69 incendiary was specifically designed to destroy Japanese civilian houses. Those bombs were widely used against civilians, including the Bombing of Tokyo. Over 40,000 tons of AN-M69s were dropped on Japanese cities during the war.
When the U.S. Army Air Forces on the Marianas Islands ran out of conventional thermite incendiary bombs for their B-29 Superfortresses to drop on large Japanese cities, its top commanders, such as General Curtis LeMay, used napalm bombs to continue with fire raids.
In the European Theater of Operations napalm was used by American forces in the siege of La Rochelle in April 1945 against German soldiers (and inadvertently French civilians in Royan) – about two weeks before the end of the war.
In its first known post-WWII use, U.S.-supplied napalm was used in the Greek Civil War by the Greek National Army as part of Operation Coronis against the Democratic Army of Greece (DSE) – the military branch of the Communist Party of Greece (KKE).
Napalm was also widely used by the United States during the Korean War. The ground forces in North Korea holding defensive positions were often outnumbered by Chinese and North Koreans, but U.S. Air Force and Navy aviators had control of the air over nearly all of the Korean Peninsula. Hence, the American and other U.N. aviators used napalm B for close air support of the ground troops along the border between North Korea and South Korea, and also for attacks in North Korea. Napalm was used most notably during the battle "Outpost Harry" in South Korea during the night of 10–11 June 1953. Eighth Army chemical officer Donald Bode reported that on an "average good day" UN pilots used 70,000 gallons of napalm, with approximately 60,000 gallons of this thrown by US forces. The New York Herald Tribune hailed "Napalm, the No. 1 Weapon in Korea". Winston Churchill, among others, criticized American use of napalm in Korea, calling it "very cruel", as the US/UN forces, he said, were "splashing it all over the civilian population", "tortur[ing] great masses of people". The American official who took this statement declined to publicize it.
At the same time the French Air Force regularly used napalm for close air support of ground operations in the First Indochina War (1946–1954). At first the canisters were simply pushed out the side doors of Ju-52 planes that had been captured in Germany, later mostly B-26 bombers were used.
Napalm became an intrinsic element of U.S. military action during the Vietnam War as forces made increasing use of it for its tactical and psychological effects. Reportedly about 388,000 tons of U.S. napalm bombs were dropped in the region between 1963 and 1973, compared to 32,357 tons used over three years in the Korean War, and 16,500 tons dropped on Japan in 1945. The U.S. Air Force and U.S. Navy used napalm with great effect against all kinds of targets, such as troops, tanks, buildings, jungles, and even railroad tunnels. The effect was not always purely physical as napalm had psychological effects on the enemy as well.
A variant of napalm was produced in Rhodesia for a type of ordnance known as Frantan between 1968 and 1978 and was deployed extensively by the Rhodesian Air Force during the bush war. In May 1978, Herbert Ushewokunze, minister of health for the Zimbabwe African National Union (ZANU) produced photographic evidence of purported civilian victims of Rhodesian napalm strikes, which he circulated during a tour of the US. The government of Mozambique and the Zimbabwe African People's Union (ZAPU) also issued claims at around the same time that napalm strikes against guerrilla targets had become a common feature in Rhodesian military operations both at home and abroad.
Other instances of napalm's use include: France during the Algerian War (1954–1962); the Portuguese Colonial War (1961–1974); Turkey (1964) dropped napalm bombs in the Republic of Cyprus on civilians; the Six-Day War by Israel (1967); in Nigeria (1969); in India and Pakistan (1965 and 1971); Egypt (1973); by Turkey (1974) against civilians in the Turkish Invasion of Cyprus; by Morocco during the Western Sahara War (1975–1991); by Argentina (1982); by Iran (1980–88); by Iraq (1980–88, 1991); by IPKF (Indian Peace keeping force) in 1987 against Tamils (LTTE) in Sri Lanka; by Angola during the Angolan Civil War; and Yugoslavia (1991–1996). In 2018, Turkey was accused of using napalm in its war against Kurdish militias over Afrin. Turkey's General Staff, however, denies this.
When used as a part of an incendiary weapon, napalm can cause severe burns (ranging from superficial to subdermal), asphyxiation, unconsciousness, and death. In this implementation, napalm fires can create an atmosphere of greater than 20% carbon monoxide and firestorms with self-perpetuating winds of up to 70 miles per hour (110 km/h).
Napalm is effective against dug-in enemy personnel. The burning incendiary composition flows into foxholes, trenches and bunkers, and drainage and irrigation ditches and other improvised troop shelters. Even people in undamaged shelters can be killed by hyperthermia, radiant heat, dehydration, asphyxiation, smoke exposure, or carbon monoxide poisoning.
One firebomb released from a low-flying plane can damage an area of 2,500 square yards (2,100 m2).
International law does not specifically prohibit the use of napalm or other incendiaries against military targets, but use against civilian populations was banned by the United Nations (UN) Convention on Certain Conventional Weapons (CCW) in 1980. Protocol III of the CCW restricts the use of all incendiary weapons, but a number of countries have not acceded to all of the protocols of the CCW. According to the Stockholm International Peace Research Institute (SIPRI), countries are considered a party to the convention, which entered into force as international law in December 1983, as long as they ratify at least two of the five protocols. Approximately 25 years after the General Assembly adopted it, it was reported that the United States signed it on 21 January 2009, President Barack Obama's first full day in office. Its ratification, however, is subject to a reservation that says that the treaty can be ignored if it would save civilian lives. Despite this allegation, the United States government had eliminated napalm from U.S. military arsenals in February 1995. The UN has also acknowledged that the United States had ratified the CCW in March 1995, 13 years after the country became a signatory to it.
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- Flame fougasse
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- M-69 Incendiary cluster bomb
- Mark 77 bomb
- Molotov cocktail
- Phan Thi Kim Phuc, a Vietnamese child injured by a napalm attack
- White phosphorus munitions
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