2008年10月12日星期日

History of ferrous metallurgy 2

Medieval Islamic world
During the Islamic Golden Age and Muslim Agricultural Revolution, Muslim chemists, inventors and engineers were making significant advances in metallurgy.
Theories on metals
In the 7th century, Khalid ibn Yazid (Calid, d. 709) used potassium nitrate as a flux in metallurgical operations.[36] In the 8th century, Ja'far al-Sadiq refuted the theory of the four classical elements and hypothesized that each one is made up of different chemical elements. He argued that earth is not an element, but that each "metal, which is in the earth, is an element."[37]
Al-Sadiq's student, the alchemist Geber (Jabir ibn Hayyan), discussed metals extensively as he was interested in the transmutation of metals, one of the principle goals of alchemy. He analyzed each classical element in terms of four basic qualities of hotness, coldness, dryness, and moistness.[38] According to Geber, in each metal two of these qualities were interior and two were exterior. For example, lead was externally cold and dry, while gold was hot and moist. Thus, Jabir theorized, by rearranging the qualities of one metal, a different metal would result.[39] By this reasoning, the search for the philosopher's stone was introduced to Western alchemy.[40][41]
Geber also provided a sound theory on the geologic formation of metals, stating that the six metals differ essentially because of different proportions of sulfur and mercury in them. He also prepared various metallic substances, such as basic lead carbonatic, arsenic and antimony from their sulfides.[42] The elemental system used in medieval alchemy was also developed by Geber. His original system consisted of seven elements, which included the five classical elements (aether, air, earth, fire and water), in addition to two chemical elements representing the metals: sulphur, ‘the stone which burns’, which characterized the principle of combustibility, and mercury, which contained the idealized principle of metallic properties. He was thus the first to recognize the metal mercury as an 'element'.[43] He was also the first to classify all seven classical metals: gold, silver, tin, lead, mercury, iron and copper.
In the 9th century, Al-Kindi (Alkindus) was the first to refute the theory of the transmutation of metals into more precious metals such as gold or silver.[45] Abū Rayhān al-Bīrūnī,[46] Avicenna[47] and Ibn Khaldun were also refuted the theory of the transmutation of metals.
In the 10th century, Muhammad ibn Zakarīya Rāzi (Rhazes) classified all seven fusible metals: gold, silver, copper, iron, tin, lead, and mercury.[48] In the 11th century, Abū Rayhān al-Bīrūnī accurately measured the specific weights of many gemstones and their corresponding metals, which are very close to modern measurements.[49]
Metal production
Muslim engineers invented the first stamp mills and steel mills. By the 11th century, every province throughout the Islamic world had these industrial mills in operation, from al-Andalus and North Africa to the Middle East and Central Asia.[50] The first geared gristmills[51] were invented by Muslim engineers for many industrial uses such as crushing metalic ores before extraction. In order to adapt water wheels for gristmilling purposes, cams were used for raising and releasing trip hammers to fall on a material.[52] The first wind-powered gristmills driven by windmills were built in what are now Afghanistan, Pakistan and Iran in the 9th and 10th centuries.[53] The first forge to be driven by a hydropowered watermill rather than manual labour, also known as a finery forge, was invented in 12th century Islamic Spain.[53] The first factory milling installations were also built by Muslim engineers throughout every city and urban community in the Islamic world, particularly Baghdad, since the 10th century.[54] The first large milling installations in Europe were built in 12th century Islamic Spain.[53]
One of the most famous steels produced in the medieval Near East was Damascus steel used for swordmaking, and mostly produced in Damascus, Syria, in the period from 900 to 1750. This was produced using the crucible steel method, based on the earlier Indian wootz steel. This process was further refined[citation needed] in the Middle East using locally produced steels. The exact process remains unknown, but allowed carbides to precipitate out as micro particles arranged in sheets or bands within the body of a blade. The carbides are far harder than the surrounding low carbon steel, allowing the swordsmith to make an edge which would cut hard materials with the precipitated carbides, while the bands of softer steel allowed the sword as a whole to remain tough and flexible. A team of researchers based at the Technical University of Dresden that uses x-rays and electron microscopy to examine Damascus steel discovered the presence of cementite nanowires[55] and carbon nanotubes.[56] Peter Paufler, a member of the Dresden team, says that these nanostructures give Damascus steel its distinctive properties[57] and are a result of the forging process.[58] [57]
Muslim chemists and engineers invented the cucurbit and aludel, and they produced the equipment needed for melting metals such as furnaces and crucibles.[44] Lead and tin were also first purified and clearly differentiated from one another by Arabic chemists and alchemists.[59] In 1206, Al-Jazari introduced the method of casting metals in closed mould boxes with green sand.
In the 10th century, Muhammad ibn Zakarīya Rāzi (Rhazes) wrote that he and his Muslim predecessors (Calid, Geber and al-Kindi) invented the following derivative and artificial metals: lead(II) oxide (PbO), red lead (Pb3O4), tin(II) oxide (Isfidaj), copper acetate (Zaniar), copper(II) oxide (CuO), lead sulfide, zinc oxide, bismuth oxide, antimony oxide, iron rust, iron acetate, Daws (a contituent of steel), cinnabar (HgS), arsenic trioxide (As2O3), alkali (al-Qili), sodium hydroxide (caustic soda), and Qalimiya (anything that separates from metals during their purification). He also wrote that Muslim alchemists were able to produce alkali metals from the ashes of the Ushnan plant, and he described a stone called daws, a constituent of iron and steel.[48] He also described a method of converting a substance into a fusible alloy.[62]
In Islamic pottery, the Hispano-Moresque style of pottery introduced the ceramic technique of painting in metallic lusters from the 8th century.[63] In 827, Caliph al-Mamun had a silver and golden tree in his palace in Baghdad which had a metal bird automaton singing automatically on the swinging branches of this tree.[64][65] In printing, after woodblock printing appeared in the Islamic world, which may have been adopted from China, a unique type of block printing was invented in Islamic Egypt during the 9th-10th centuries: print blocks made from metals such as tin, lead and cast iron.[66] In circa 1000, the Muslim ophthalmologist Ammar ibn Ali of Mosul invented a hollow metallic syringe hypodermic needle.[67] The use of an iron case and metal cylinder in rocket artillery was introduced by Tipu Sultan and his father Hyder Ali in India during the 1780s.[68][69]
One of the most remarkable feats in metallurgy was the seamless celestial globe, invented in Kashmir by Ali Kashmiri ibn Luqman in 998 AH (1589-1590 CE), and twenty other such globes were later produced in Lahore and Kashmir during the Mughal Empire. Before they were rediscovered in the 1980s, it was believed by modern metallurgists to be technically impossible to produce metal globes without any seams, even with modern technology. These Mughal metallurgists pioneered the method of lost-wax casting while producing these seamless globes.[70]
Medieval to modern Europe

Ironmaking described in "The Popular Encyclopedia" vol.VII, published 1894
There was no fundamental change in the technology of iron production in Europe for many centuries. Iron continued to be made in bloomeries. However there were two separate developments in the Medieval period. One was the application of water power to the bloomery process in various places (as outlined above). The other was the first European production in cast iron.
Development of Water-powered bloomeries
Sometime in the medieval period, water power was applied to the bloomery process. It is possible that this was at the Cistercian Abbey of Clairvaux as early as 1135, but it was certainly in use in France by the early 13th century there and in Sweden.[71] In England, the first clear documentary evidence for this is the accounts of a forge of the Bishop of Durham, near Bedburn in 1408,[72] but that was certainly not the first such ironworks. In the Furness district of England, powered bloomeries were in use into the beginning of the 18th century, and near Garstang until about 1770.
The Catalan Forge was a variety of powered bloomery. Bloomeries with hot blast were used in upstate New York in the mid 19th century.
The first blast furnaces in Europe
Cast iron development lagged in Europe, as the smelters could only achieve temperatures of about 1000 C; or perhaps they did not want hotter temperatures, as they were seeking to produce blooms as a precursor of wrought iron, not cast iron. Through a good portion of the Middle Ages, in Western Europe, iron was thus still being made by the working of iron blooms into wrought iron. Some of the earliest casting of iron in Europe occurred in Sweden, in two sites, Lapphyttan and Vinarhyttan, between 1150 and 1350 CE. Some scholars have speculated the practice followed the Mongols across Russia to these sites, but there is no clear proof of this hypothesis, and it would certainly not explain the pre-mongol datings of many of these iron-production centres. In any event, by the late fourteenth century, a market for cast iron goods began to form, as a demand developed for cast iron cannonballs.
Osmond iron
Iron from furnaces such as Lapphyttan was refined into wrought iron by the osmond process. The pig iron from the furnace was melted in front of a blast of air and the droplets caught on a staff (which was spun). This formed a ball of iron, known as an osmond. This was probably a traded commodity by c.1200.
Finery process
An alternative method of decarburising pig iron seems to have been devised in the region around Namur in the 15th century. This Walloon process spread by the end of that century to the Pay de Bray on the eastern boundary of Normandy before the end of that century, and to then to England, where it became the main method of making wrought iron by 1600. It was introduced to Sweden by Louis de Geer in the early 17th century and was used to make the oregrounds iron favoured by English steelmakers.
A variation on this was the German process. This became the main method of producing bar iron in Sweden.
Steelmaking in early modern Europe
In the early 17th century, ironworkers in Western Europe had found a means (called cementation) to carburize wrought iron. Wrought iron bars and charcoal were packed into stone boxes, then held at a red heat for up to a week. During this time, carbon diffused into the iron, producing a product called cement steel or blister steel (see cementation process). One of the earliest places where this was used in England was at Coalbrookdale, where Sir Basil Brooke had two cementation furnaces (recently excavated). For a time in the 1610s, he owned a patent on the process, but had to surrender this in 1619. He probably used Forest of Dean iron as his raw material, but it was soon found that oregrounds iron was more suitable.
The quality of the steel could be improved by faggoting, producing shear steel. However in the 1740s, Benjamin Huntsman found a means of melting blister steel, made by the cementation process in crucibles; this was cast usually as ingots as crucible steel. This is more homogeneous than blister steel.
The transition to coke in England
Beginnings
Early iron smelting used charcoal as both the heat source and the reducing agent. By the 18th century, the availability of wood for making charcoal was limiting the expansion of iron production, so that England became increasingly dependent for a considerable part of the iron required by its industry, on Sweden (from the mid 17th century) and then from about 1725 also on Russia.[73]
Smelting with coal (or its derivative coke) was a long sought objective. The production of pig iron with coke was probably achieved by Dud Dudley in the 1620s, and with a mixed fuel made from coal and wood again in the 1670s. However this was probably only a technological rather than a commercial success. Shadrach Fox may have smelted iron with coke at Coalbrookdale in Shropshire in the 1690s, but only to make cannon balls and other cast iron products such as shells. However, in the peace after the Nine Years War, there was no demand for these.[74]
Abraham Darby and his successors
In 1707, Abraham Darby patented a method of making cast iron pots. His pots were thinner and hence cheaper than those of his rivals. Needing a larger supply of pig iron he leased the blast furnace at Coalbrookdale in 1709. There, he made iron using coke, thus establishing the first successful business in Europe to do so. His products were all of cast iron, though his immediate successors attempted (with little commercial success) to fine this to bar iron.[75]
Bar iron thus continued normally to be made with charcoal pig iron until the mid 1750s. In 1755 Abraham Darby II (with partners) opened a new coke-using furnace at Horsehay in Shropshire, and this was followed by others. These supplied coke pig iron to finery forges of the traditional kind for the production of bar iron. The reason for the delay remains controversial.[76]
New forge processes

Schematic drawing of a puddling furnace.
It was only after this that economically viable means of converting pig iron to bar iron began to be devised. A process known as potting and stamping was devised in the 1760s and improved in the 1770s, and seems to have been widely adopted in the West Midlands from about 1785. However, this was largely replaced by Henry Cort's puddling process, patented in 1784, but probably only made to work with grey pig iron in about 1790. These processes permitted the great expansion in the production of iron that constitutes the Industrial Revolution for the iron industry.[77]
In the early 19th century, Hall discovered that the addition of iron oxide to the charge of the puddling furnace caused a violent reaction, in which the pig iron was decarburised, this became known as 'wet puddling'. It was also found possible to produce steel by stopping the puddling process before decarburisation was complete.
Hot blast
The efficiency of the blast furnace was improved by the change to hot blast, patented by James Beaumont Neilson in Scotland in 1828. This further reduced production costs. Within a few decades, the practice was to have a 'stove' as large as the furnace next to it into which the waste gas (containing CO) from the furnace was directed and burnt. The resultant heat was used to preheat the air blown into the furnace.[78]
Industrial steelmaking

Schematic drawing of a Bessemer converter
Apart from some production of puddled steel, English steel continued to be made by the cementation process, sometimes followed by remelting to produce crucible steel. These were batch-based processes whose raw material was bar iron, particularly Swedish oregrounds iron.
The problem of mass-producing cheap steel was solved in 1855 by Henry Bessemer, with the introduction of the Bessemer converter at his steelworks in Sheffield, England. (An early converter can still be seen at the city's Kelham Island Museum). In the Bessemer process, molten pig iron from the blast furnace was charged into a large crucible, and then air was blown through the molten iron from below, igniting the dissolved carbon from the coke. As the carbon burned off, the melting point of the mixture increased, but the heat from the burning carbon provided the extra energy needed to keep the mixture molten. After the carbon content in the melt had dropped to the desired level, the air draft was cut off: a typical Bessemer converter could convert a 25-ton batch of pig iron to steel in half an hour.
Finally, the basic oxygen process was introduced at the Voest-Alpine works in 1952; a modification of the basic Bessemer process, it lances oxygen from above the steel (instead of bubbling air from below), reducing the amount of nitrogen uptake into the steel. The basic oxygen process is used in all modern steelworks; the last Bessemer converter in the U.S. was retired in 1968. Furthermore, the last three decades have seen a massive increase in the mini-mill business, where scrap steel only is melted with an electric arc furnace. These mills only produced bar products at first, but have since expanded into flat and heavy products, once the exclusive domain of the integrated steelworks.
Until these 19th century developments, steel was an expensive commodity and only used for a limited number of purposes where a particularly hard or flexible metal was needed, as in the cutting edges of tools and springs. The widespread availability of inexpensive steel powered the Second Industrial Revolution and modern society as we know it. Mild steel ultimately replaced wrought iron for almost all purposes, and wrought iron is no longer commercially produced. With minor exceptions, alloy steels only began to be made in the late 19th century. Stainless steel was developed on the eve of the First World War and was not widely used until the 1920s.

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