History of gunpowder

Gunpowder was the first chemical explosive and propellant. Prior to the invention of gunpowder, many incendiary and burning devices had been used, including Greek fire. Gunpowder stood alone as an energetic material until as late as 1799 with the discovery and investigation of mercury (II) fulminate by Edward Charles Howard. The invention of gunpowder is usually attributed to Chinese alchemy, and is popularly listed as one of the "Four Great Inventions" of China. The invention was made perhaps as early as during the Tang Dynasty (9th century), but certainly by the Song Dynasty (11th century). Knowledge of gunpowder spread throughout the Old World as a result of the Mongol conquests of the 13th century. It was employed in warfare to some effect from at least the 14th century, although the development of effective artillery took place during the 15th century, and firearms came to dominate Early Modern warfare in Europe by the 17th century.

Original development


The prevailing academic consensus is that gunpowder was formulated in the 9th century by Chinese alchemists searching for an elixir of immortality. By the time the Song Dynasty treatise, Wujing Zongyao (武经总要), was written by Zeng Gongliang, Ding Du, and Yang Weide in 1044 AD, the various Chinese formulas for gunpowder held levels of nitrate in the range of 27% to 50%.

China
As early as 492, Chinese alchemists had noted that saltpeter burns with a purple flame, allowing for practical efforts at purifying the substance, one of the most important ingredients in gunpowder. The first reference to gunpowder in China occurs in a Daoist work from the mid-9th century, the Zhenyuan miaodao yaolüe. However, the earliest surviving chemical formula date to 1044 in the Wujing Zongyao, a Chinese collection of military information. At this point the formulae contained too little saltpeter (about 50%) to be explosive, but the mixture was highly flammable. A silk banner slightly predating the Wujing Zongyao depicts a gunpowder-fueled flamethrower.

Fireworks were invented in ancient China in the 10th century to scare away evil spirits.

In AD 1280, the bomb store of the large gunpowder arsenal at Weiyang accidentally caught fire, which produced such a massive explosion that a team of Chinese inspectors at the site a week later deduced that some 100 guards had been killed instantly, with wooden beams and pillars blown sky high and landing at a distance of over 10 li (~2 mi. or ~3.2 km) away from the explosion.

By the time of Jiao Yu and his Huolongjing (a book written by Jiao Yu that describes military applications of gunpowder in great detail) in the mid 14th century, the explosive potential of gunpowder was perfected, as the level of nitrate in gunpowder formulas had risen to a range of 12% to 91%, with at least 6 different formulas in use that are considered to have maximum explosive potential for gunpowder. By that time, the Chinese had discovered how to create explosive round shot by packing their hollow shells with this nitrate-enhanced gunpowder.

A medieval European work describing the powerful weapons that had been built by the Chinese, had been suggested by historian Kenneth Warren Chase to be referring to the Chinese invention of Gunpowder.

According to modern historians genuine firearms appeared to have been invented first in China in the 13th century. The Chinese developed fire arrows in 989 tipped with explosives, along with flame throwers by 1000. Another weapon was called the huo-yao pien-chien, meaning "gunpowder-whip-arrow".

A gunpowder weapon from China, the huo p'ao, was described in the Sung Shih. It was suggested that this huo p'ao was related to a weapon which appeared in 1232, the chen t'ien lei. Lou Ch'ien-hsia and his troops used it in 1277. The passage stated that "He lit it and a clap of thunder was heard, the walls crumbled, and smoke covered the sky. Many soldiers outside died of fright. When the fire went out, they went inside and failed to find even the ashes of the 250 defenders; they had disappeared without trace."

The "t'u huo ch'iang" was a bamboo tube which shot out multiple pellets when fired.

The Mongols used gunpowder during Ogdai Khan's invasion of Europe. "Fire catapults", "p'ao", and "naphtha-shooters" were used.

Islamic world


The Arabs acquired knowledge of gunpowder some time after 1240, but before 1280, by which time Hasan al-Rammah had written, in Arabic, recipes for gunpowder, instructions for the purification of saltpeter, and descriptions of gunpowder incendiaries. However, because al-Rammah attributes his material to "his father and forefathers", al-Hassan argues that gunpowder became prevalent in Syria and Egypt by "the end of the twelfth century or the beginning of the thirteenth".

During the invasion of Transoxania in 1219, along with the main Mongol force, Genghis Khan used a Chinese specialist catapult unit in battle, they were used again in 1220 in Transoxania, and during the 1239–1240 invasion of the Caucasus. The Chinese may have used the catapults to hurl gunpowder bombs, since they already had them by this time. While Genghis Khan was conquering Transoxania and Persia, several Chinese who were familiar with gunpowder were serving with Genghis's army. Historians have suggested that the Mongol invasion had brought Chinese gunpowder weapons to Central Asia. One of these was the huochong, a Chinese mortar.

Al-Baytar, an Arab from Spain who had immigrated to Egypt, wrote in Arabic that "snow of China" was the name used to describe saltpeter. Al-Baytar died in 1248.

C. F. Temler interprets Peter, Bishop of Leon, as reporting the use of cannon in Seville in 1248. Al-Hassan claims that "the first cannon in history" was used by the Mamluks against the Mongols at the Battle of Ain Jalut in 1260; Khan claims that it was invading Mongols who introduced gunpowder to the Islamic world and cites Mamluk antagonism towards early riflemen in their infantry as an example of how gunpowder weapons were not always met with open acceptance in the Middle East. Similarly, the refusal of their Qizilbash forces to use firearms contributed to the Safavid rout at Chaldiran in 1514.

Hasan al-Rammah included 107 gunpowder recipes in his al-furusiyyah wa al-manasib al-harbiyya (The Book of Military Horsemanship and Ingenious War Devices), 22 of which are for rockets. If one takes the median of 17 of these 22 compositions for rockets (75% nitrates, 9.06% sulphur and 15.94% carbon), it is almost identical with the reported ideal recipe (75% potassium nitrate, 10% sulphur, and 15% carbon).

Hasan al-Rammah also describes the purifying of saltpeter using the chemical processes of solution and crystallization. This was the first clear method for the purification of saltpeter. The earliest torpedo was also first described in 1270 by Hasan al-Rammah in The Book of Military Horsemanship and Ingenious War Devices, which illustrated a torpedo running with a rocket system filled with explosive materials and having three firing points.

The earliest surviving documentary evidence for the use of the hand cannon, considered the oldest type of portable firearm and a forerunner of the handgun, are from several Arabic manuscripts dated to the 14th century. Al-Hassan argues that these are based on earlier originals and that they report hand-held cannons being used by the Mamluks at the Battle of Ain Jalut in 1260.

India
Chinese gunpowder technology is believed to have arrived in India by the mid-14th century, but could have been introduced much earlier by the Mongols, who had conquered both China and India, perhaps as early as the mid-13th century. The unification of a large single Mongol Empire resulted in the free transmission of previously top-secret Chinese technology into a Mongol conquered India. Regardless, it is believed that the Mongols used Chinese gunpowder weapons during their invasion and subsequent conquest of India.

It was written in the Tarikh-i Firishta (1606–1607) that the envoy of the Mongol ruler Hulegu Khan was presented with a dazzling pyrotechnics display upon his arrival in Delhi in 1258 AD. As a part of an embassy to India by Timurid leader Shah Rukh (1405–1447), 'Abd al-Razzaq mentioned naphtha-throwers mounted on elephants and a variety of pyrotechnics put on display. Firearms known as top-o-tufak also existed in the Vijayanagara Empire of India by as early as 1366 AD. From then on the employment of gunpowder warfare in India was prevalent, with events such as the siege of Belgaum in 1473 AD by the Sultan Muhammad Shah Bahmani.

Roger Pauly has written that "while gunpowder was primarily a Chinese innovation," the saltpeter that led to the invention of gunpowder may have arrived from India, although it is also likely that it originates indigenously in China.

Europe
One theory of how gunpowder came to Europe is that it made its way along the Silk Road through the Middle East; another is that it was brought to Europe during the Mongol invasion in the first half of the 13th century, or during the subsequent diplomatic and military contacts (see Franco-Mongol alliance). William of Rubruck, an ambassador to the Mongols in 1254–1255 and a personal friend of Roger Bacon, is also often designated as a possible intermediary in the transmission of gunpowder know-how between the East and the West.

Several sources mention Chinese firearms and gunpowder weapons being deployed by the Mongols against European forces at the Battle of Mohi in 1241. Professor Kenneth Warren Chase credits the Mongols for introducing into Europe gunpowder and its associated weaponry.

One of the earliest European references to gunpowder is found in Roger Bacon's Epistola de secretis operibus artiis et naturae from 1267. The oldest written recipes for gunpowder in Europe were recorded under the name Marcus Graecus or Mark the Greek between 1280 and 1300. However, the very first time gunpowder was used in the Western world for military purposes was in 1262, when king Alfonso X of Castile set siege to the city of Niebla in Spain whose Spanish-Arab inhabitants used some sort of primitive gun against the Spaniards.

In 1250 the Norwegian Konungs skuggsjá mentions, in its military chapter, the use of "coal and sulphur" as the best weapon for ship-to-ship combat.

Mixtures of coal and sulphur are not explosive, but can produce a slow-burning effect.

In 1326 the earliest known European picture of a gun appeared in a manuscript by Walter de Milemete. On 11 February of that same year, the Signoria of Florence appointed two officers to obtain canones de mettallo and ammunition for the town's defense. A reference from 1331 describes an attack mounted by two Germanic knights on Cividale del Friuli, using gunpowder weapons of some sort. The French raiding party that sacked and burned Southampton in 1338 brought with them a ribaudequin and 48 bolts (but only 3 pounds of gunpowder). The Battle of Crécy in 1346 was one of the first in Europe where cannons were used. In 1350, only four years later, Petrarch wrote that the presence of cannons on the battlefield was 'as common and familiar as other kinds of arms'.



Before the musket were made, arquebus was used in Spanish empire, Ottoman empire, Portugal and in Japan. References to gunnis cum telar (guns with handles) were recorded in 1350 and by 1411 it was recorded that John the Good, Duke of Burgundy, had 4000 handguns stored in his armory. However, musketeers and musket-wielding infantrymen were despised in society by the traditional feudal knights, even until the time of Cervantes (1547–1616 AD). At first even Christian authorities made vehement remarks against the use of gunpowder weapons, calling them blasphemous and part of the 'Black Arts'. By the mid-14th century, however, even the army of the Pope would be armed with artillery and gunpowder weapons.

Around the late 14th century European powdermakers began adding liquid to the constituents of gunpowder which reduced dust, and with it the risk of explosion during manufacture. The powdermakers would then shape the resulting paste of moistened gunpowder—known as mill cake—into "corns" or granules to allow it to dry. Not only did "corned" powder keep better, because of its reduced surface area, but gunners also found that it was more powerful and easier to load into guns. The main advantage of corning is that the flame lights all the granules when the gunpowder is lit, spreading between them before significant gas expansion has occurred. Without corning much of the powder, away from the initial flame, would be blown out of the barrel before it burnt. The size of the granules varied for different types of gun. Prior to corning, gunpowder would gradually demix into its constitutive components and was too unreliable for effective use in guns. The same granulation process is used nowadays in the pharmaceutical industry to ensure that each tablet contains the same proportion of active ingredient. Before long, powdermakers standardized the process by forcing mill cake through sieves instead of corning powder by hand.



Early Modern history
The 15th through 17th century saw widespread development in gunpowder technology throughout the Old World. During the 15th and 16th centuries, these developments were more advanced in India and Persia than in Europe, but by the 17th century, technological progress in Europe led to application of gunpowder on a scale and to an effect unprecedented anywhere else, both in warfare and in civil engineering. Gunpowder remained of central importance throughout the Early Modern period, and throughout the Napoleonic era, and was only replaced by more advanced explosives beginning in the 1860s.

Mughal India


By the 16th century, Indians were manufacturing a diverse variety of firearms; large guns in particular, became visible in Tanjore, Dacca, Bijapur and Murshidabad. Guns made of bronze were recovered from Calicut (1504) and Diu (1533). Gujarāt supplied Europe saltpeter for use in gunpowder warfare during the 17th century. Bengal and Mālwa participated in saltpeter production. The Dutch, French, Portuguese, and English used Chāpra as a center of saltpeter refining.

Fathullah Shirazi (c. 1582), who worked for Akbar the Great as a mechanical engineer, developed an early multi gun shot. As opposed to the polybolos and repeating crossbows used earlier in ancient Greece and China, respectively, Shirazi's rapid-firing gun had multiple gun barrels that fired hand cannons loaded with gunpowder.

In Encyclopædia Britannica (2008), Stephen Oliver Fought & John F. Guilmartin, Jr. describe the gunpowder technology in 18th century India, with reference to the rocket artillery used by the Kingdom of Mysore (as described in the Fathul Mujahidin) and its influence on the Congreve rocket:

Hyder Ali, prince of Mysore, developed war bombs with an important change: the use of metal pips to contain the combustion powder. Although the hammered soft iron he used was crude, the bursting strength of the container of black powder was much higher than the earlier paper construction. Thus a greater internal pressure was possible, with a resultant greater thrust of the propulsive jet. The rocket body was lashed with leather thongs to a long bamboo stick. Range was perhaps up to three-quarters of a mile (more than a kilometer). Although individually these rockets were not accurate, dispersion error became less important when large numbers were fired rapidly in mass attacks. They were particularly effective against cavalry and were hurled into the air, after lighting, or skimmed along the hard dry ground. Hyder Ali's son, Tippu Sultan, continued to develop and expand the use of rocket weapons, reportedly increasing the number of rocket troops from 1,200 to a corps of 5,000. In battles at Seringapatam in 1792 and 1799 these rockets were used with considerable effect against the British.

The news of the successful use of rockets spread through Europe. In England Sir William Congreve began to experiment privately. First, he experimented with a number of black-powder formulas and set down standard specifications of composition. He also standardized construction details and used improved production techniques. Also, his designs made it possible to choose either an explosive (ball charge) or incendiary warhead.

In A History of Greek Fire and Gunpowder, James Riddick Partington describes Indian rockets, mines and other means of gunpowder warfare:

"The Indian war rockets were formidable weapons before such rockets were used in Europe. They had bam-boo rods, a rocket-body lashed to the rod, and iron points. They were directed at the target and fired by lighting the fuse, but the trajectory was rather erratic. The use of mines and counter-mines with explosive charges of gunpowder is mentioned for the times of Akbar and Jahāngir."

Military
Advances in metallurgy led to portable weapons and the development of hand-held firearms such as muskets. Cannon technology in Europe gradually outpaced that of China and these technological improvements were then transferred back to China through Jesuit missionaries who were put in charge of cannon manufacture by the late Ming and early Qing emperors.



Shot and gunpowder for military purposes were made by skilled military tradesmen, who were later called firemakers, who were also required to make fireworks for celebrations of victory or peace. During the Renaissance two European schools of pyrotechnic thought emerged, one in Italy and the other at Nürnberg, Germany. The Italian school of pyrotechnics emphasized elaborate fireworks, the German school stressed scientific advancement. Both schools added significantly to the further development of pyrotechnics and, by the mid-17th century, fireworks were used for entertainment on an unprecedented scale in Europe——being popular even at resorts and public gardens. At the same time some military men were disguising gray in their beards by dusting them with gunpowder, the antiquary John Aubrey noted in his memoranda.

Mining
Until the invention of explosives, large rocks could only be broken up by hard labor or by heating with large fires followed by rapid quenching. Black powder was used in civil engineering and mining as early as the 15th century. The earliest surviving record for the use of gunpowder in mines comes from Hungary in 1627. It was introduced to Britain in 1638 by German miners, after which records are numerous. Until the invention of the safety fuse by William Bickford in 1831, the practice was extremely dangerous. Another reason for danger were the dense fumes given off and the risk of igniting flammable gas when used in coal mines.

Canals
The first time gunpowder was used on a large scale in civil engineering was in the construction of the Canal du Midi in Southern France. It was completed in 1681 and linked the Mediterranean sea with the Atlantic with 240 km of canal and 100 locks. Another noteworthy consumer of black powder was the Erie canal in New York, which was 585 km long and took eight years to complete, starting in 1817.

Tunnel construction
Black powder was also extensively used in railway construction. At first railways followed the contours of the land, or crossed low ground by means of bridges and viaducts, but later railways made extensive use of cuttings and tunnels. One 2400-ft stretch of the 5.4 mi Box Tunnel on the Great Western Railway line between London and Bristol consumed a ton of gunpowder per week for over two years. The 12.9 km long Mont Cenis Tunnel was completed in 13 years starting in 1857 but, even with black powder, progress was only 25 cm a day until the invention of pneumatic drills sped up the work.

The latter half of the 19th century saw the invention of nitroglycerin, nitrocellulose and smokeless powders which soon replaced black powder in many applications.

Later improvements
Gunpowder as a gun propellant suffered from several weaknesses inherent to its composition. It was subject to passivation by moisture and was awkward to load and ignite in a weapon. Sulfur oxides and moisture produced corrosion on metal gun components and the smoke gave away the position of the shooter. The development of cartridges and explosive primers were a major improvement in the use of gunpowders in the field.

From the earliest period, gunpowder has been composed of a nitrate salt, sulfur, and carbonaceous matter. The Nitrate component is the Oxidizing agent, Sulfur is a low melting Reducing agent and serves to aid in the transfer of heat through the gunpowder mass, and Carbon is a reducing component producing hot, high pressure gas. The utility of gunpowder lies in its ability to accelerate a projectile by the explosive expansion of gas. The development of new explosive materials in the 19th century naturally lead to improvements in the rate and magnitude of pressure rise as well as new means for ignition of the charge.

Nitroester compositions nitrocellulose and nitroglycerin were developed by Henri Braconnot in 1832 and Ascanio Sobrero in 1846, respectively. The development of smokeless powder stemmed from efforts by numerous workers to produce an improved gun propellant providing better resistance to moisture, greater muzzle velocity, and generally greater reliability. By the end of the 19th century, nitroester compositions Poudre B, Ballistite, and Cordite were the major smokeless propellants. Significantly, many nitroesters were capable of detonation without confinement. The classic gunpowder composition was only capable of Deflagration in the open.

The process of aromatic nitration to afford picric acid from the trinitration of phenol was performed in the early 19th century, though it is possible that Johann Rudolf Glauber may have reported it much earlier. Nitroesters would find use in gun propellant formulation. Nitroaromatics like picric acid eventually found use in explosive cannon shells owing to their ability to withstand the severe shock of firing.