Grantville Gazette Volume 25

by editor Paula Goodlett

  Absent that fortuitous breakthrough, exploitation of molybdenum will require prospecting, by individuals armed with good descriptions of the mineral, and sent to the right vicinity. We know to look for molybdenite in a few European locales (notably, at Slangsvold near Raade in Norway, EB11/molybdenite), but if those fail, our best bet is probably once European civilization reaches Colorado (EA). I have no idea how many years that will take.

  Curiously, there are fourteenth century samurai swords which are rich in molybdenum, no doubt as a result of the use of native molybdenite at some point in the forging process.(Emsley 266).

  Tungsten

  Tungsten is probably best known to the average up-timer as the filament of the electric light bulb. It's also used, less obviously, to make alloys with iron and aluminum, and in high temperature processing. Josh Modi told magnate De Geer that "tungsten would allow you to make a steel close to what was called 'hi-speed tool steel.'" Mackey, "The Essen Chronicles, Part 3: Trip to Paris" (Grantville Gazette 9). The cemented carbide tools which Larry Wild broke (Cresswell and Washburn, "When the Chips are Down," Ring of Fire) are sintered composites of tungsten carbide in a cobalt matrix.

  Tungsten's principal ores are scheelite (calcium tungstate) and wolframite (iron-manganese tungstate), which can accumulate in placer deposits. Josh also declared that, according to the encyclopedias, tungsten can be obtained from the tailings of tin mines. Mackey, "Essen Steel, Part 1: Crucibellus" (Grantville Gazette 7). EB11/Wolframite confirms that wolframite is "commonly associated with tin ores." However, this should not inspire a false sense of confidence. "This element is far less widely distributed than tin . . . it is probable that on the whole tungsten is not more than one-hundredth as abundant in Cornwall as tin . . . there may be tin without tungsten, but not tungsten without tin." (Collins 333-4). The principal European source is actually Portugal (EA).

  Wolframite does occur with cassiterite in the Erzgebirge (Mineral Industry of the British Empire and Foreign Countries, 24, 1921) and indeed it's believed to have gotten its name from German tin miners (they thought the wolframite devoured tin) (Emsley 470) So we will be able to produce tungsten . . . just in limited quantities.

  To complicate matters further, the standard methods of extracting tungsten are reduction of tungstic acid with aluminum or heating tungsten oxide with carbon in an electric furnace. So you either need aluminum, or lots of electricity.

  Group 7 Metals

  Manganese

  The principal ore of manganese is pyrolusite (manganese dioxide), and it has been used since ancient times to decolorize soda lime glass (which otherwise has a greenish cast) or to instead give it a purple tint (Emsley 250-1). It can be (and probably already is) mined at Ilmenau and elsewhere in Thuringia (EB11/pyrolusite). Another ore is rhodochrosite (manganese carbonate), which is associated with silver.

  The alloy ferromanganese (introduced 1839) is used in steelmaking to remove oxygen and sulfur impurities; indeed, it was a key component (1856) in the perfected Bessemer process. Manganese also serves as an alloying element. EA says, somewhat cryptically, "Ferromanganese is produced from manganese ore in blast furnaces in somewhat the same manner as pig iron." I take this to mean that a mixture of hematite (iron oxide) and pyrolusite (manganese oxide) is reduced by the combination of heat and carbon.

  The metal can be obtained from the oxide by reduction with aluminum, or by heating the carbonate with carbon. (EB11).Another option, which I am not sure is documented in Grantville, is to electrolyze magnesium sulfate (Emsley 251). The sulfate, in turn, can be derived from manganese dioxide and concentrated sulfuric acid (EB11).

  Manganese dioxide is also useful as an oxygen source in a common dry cell (EA) and in the production of chlorine gas by reaction with HCl (Emsley 251).

  The manganates are made by fusion of manganese dioxide with the metal hydroxide in presence of an oxidizing agent. In turn, adding carbon dioxide or chlorine to a manganate should yield the permanganate. Potassium permanganate is an important oxidizing agent. Historically, potassium manganate and permanganate were both prepared by Glauber in 1659.

  It seems to me that the down-timers had everything they needed to make ferromanganese and potassium permanganate, all they lacked was knowledge of the underlying chemistry (so they would know what to do with the pyrolusite) and of the uses for these materials (so they would have the motivation).

  I figure that until the end of the Baltic War, there will be reluctance to fiddle around with new alloys; the emphasis will be on producing as much basic steel as possible. However, by late 1634, there may well be some ferromanganese production. And I think that the alchemists will be experimenting with potassium permanganate even earlier, perhaps in 1633. After all, there is a connection between strong oxidizing agents and things that go BOOM!

  Technetium, Rhenium

  Ignored.

  "Platinum Group" Metals

  These are ruthenium, rhodium, paladium, osmium, iridium and platinum, which are group 8, 9 and 10 elements which tend to occur together, because of their high density and similar chemical properties, in the same deposits. However, the same is true, to a lesser degree, of iron (group 8), cobalt (9) and nickel (10).

  Group 8 Metals

  Iron

  Iron, of course, is extremely well known to the down-timers, and methods of using it to make steel are discussed in Boatright, "Iron" (Grantville Gazette 3). Iron forms both ferrous (+2 valence) and ferric (+3) compounds; EA gives uses for ferrous sulfate, sulfide, phosphide, chloride, and ferric sulfate, sulfide (pyrite), chloride, hydroxide, oxide (hematite) and bromide. All of these compounds can be made by disclosed reactions (EA, EB11) of iron, or iron compounds, with reagents such as sulfuric acid, sulfur, phosphorus, hydrochloric acid, chlorine, ammonia and bromine. Chlorine is available in NTL 1633, and most of the others even sooner. The only question mark is bromine.

  Some iron compounds are known to down-timers. Green vitriol (vitriol of Mars) is ferrous sulfate heptahydrate. The down-timers use it in the manufacture of iron gall ink, and as a mordant. In the nineteenth century it was used as a developer in the collodion process. Yellow ochre is hydrated ferric oxide. Colcothar is a red iron oxide made by roasting green vitriol.

  Ruthenium

  Ignored.

  Osmium

  Osmium metal is associated with other platinum group metals, and was first discovered in "the residue left when crude platinum was dissolved by aqua regia." (EB11). Nowadays, it's a byproduct of nickel refining. It's useful as a catalyst (it was one of the first good catalysts for the Haber process) and in specialized applications requiring extreme hardness (nibs for ultra-expensive fountain pens). Still, the demand for it is minute. (<100 kg 2000: Emsley 295).

  The most intriguing osmium compound is the tetroxide, which is used to detect fingerprints. (EA) EB11 says that it forms "when osmium compounds are heated in air, or with aqua regia, or fused with caustic alkali and nitre."

  Even though it was discovered at a surprisingly early date (1803), Osmium is not likely to be seen commercially in our time frame.

  Group 9 Metals

  Cobalt

  Cobalt is a peculiar case. Cobalt compounds have been used since the days of the Pyramids to make blue glasses and ceramics. This usage appears to have been forgotten in Europe after the fall of Rome as, when medieval miners in Saxony and Bohemia encountered cobalt ores (smaltite, cobalt arsenide) in Saxony and Bohemia, they didn't consider them to be of value (Emsley 116). In this regard, cobalt's rather like nickel. However, it appears that "smalt" was rediscovered by the Bohemian glass makers in 1540-60 (Gettens, 158).

  At some point in the seventeenth century, it was discovered that if a cobalt ore were dissolved in aqua regia, it formed an "invisible ink" which was revealed by heat. (Emsley 119).

  Cobalt is used principally as an alloying element, to impart temperature resistance. Cobalt arsenides are associated with nickel, silver and gold, and other cobalt ores with copper. (EA). Cobalt is mostly produ
ced as a byproduct of nickel refining (Emsley 117) and EA warns that extraction is usually "complicated . . . because of the presence of numerous contaminating elements."

  Rhodium

  Rhodium, discovered in 1803, is used as an alloying element, in electroplating other metals, as a reflective coating for mirrors, and as a catalyst (in particular, in catalytic converters of cars). It's a byproduct of platinum mining. (EA; Emsley, 362).

  Iridium

  Iridium, discovered in 1802, is perhaps the most corrosion-resistant of the metals, and is used in electrical contacts and pen points (EA). While found in a platinum ore (EB11), it's usually a byproduct of nickel refining (Emsley 202).

  Group 10 Metals

  Nickel

  The European down-timers have encountered nickel, but without realizing what they were dealing with. The nickel ore niccolite (nickel arsenide) is found with cobalt, silver and copper in Saxon mines (EB11/Niccolite). The miners called it kupfernickel (St. Nick's copper), because they deemed it a demonic imitation of copper. Lolly Aossi tells Father Smithson in July 1634 that nickel has been found in tailings from more than one mine." Runkle, "Sunday Driver" (Grantville Gazette 13).

  The up-time interest in nickel is likely to be mostly in the metal itself, which can be used as a catalyst, as a metal plating agent, or in alloys with other metals, such as iron (Stainless steel), copper (Monel) or chromium (Nichrome).

  Palladium

  Palladium is associated with platinum (and nickel) ores, and with certain placer deposits of gold and silver. It's used mainly as a catalyst, and, in that guise, can be found in the catalytic converters of cars manufactured shortly before the RoF (older converters used platinum).

  It will probably not be sought out independently, but those refining the associated metals may keep an eye out for it.

  Platinum

  EA says that "platinum was known and used by pre-Columbian Indians in South America," and this is confirmed by archaeological evidence. Even before RoF, a few Europeans were aware of platinum's existence: "In 1557, an Italian scholar, Julius Scaliger, wrote of a metal from Spanish Central America that could not be made to melt and this must have been platinum [MP 1772°C]." Serious European investigation did not begin until the early eighteenth century. Even then, the authorities initially considered platinum to be detrimental (it could be used to adulterate gold), and banned it for decades. (Emsley 319).

  If the up-time texts excite Spanish interest in mining platinum, then they can probably find Indians who know where the Columbian deposits are located. It appears that sometime after October 1633, Antonio ("Catalina") de Erauso went to Cartagena to begin a search for platinum. Mackey, "Land of Ice and Sun" (Grantville Gazette 11).

  There are three commercial forms of platinum: powder ("platinum black"), spongy and compact. Both the powder (made by reduction of platinum chloride) and the spongy form (made from ammonium chlorplatinate) are used as catalysts, whereas the compact platinum is formed into jewelry. Platinum is also used in many applications in which heat or corrosion resistance are important.

  Ammonium chlorplatinate is obtained by dissolving platinum ore in aqua regia, and then precipitating the desired salt by adding acidified ammonium chloride. Platinum chloride is recovered if you heat chlorplatinic acid in dry chlorine or dry hydrogen chloride. (EB11).

  Platinum dioxide, which is also a catalyst, is made by fusing chlorplatinic acid with sodium nitrate (EA) or caustic soda (EB11).

  Group 11 Metals

  The elements of this group are all available pre-RoF as both the elemental metals, and in several salts.

  Copper

  Copper carbonate occurs naturally as malachite and azurite, copper sulfide as chalcocite, chalcopyrite and bornite, and copper oxide as cuprite.

  Copper hydroxide, a pigment, was made down-time by reacting sodium hydroxide (lye) with copper sulfate (blue vitriol). It can also be made electrochemically. (Analogous reactions are used to make iron hydroxide.)

  The alchemists' "blue vitriol" ("blue copperas") is copper sulfate pentahydrate. Its modern use is as a pesticide and analytical reagent.

  Copper sulfate and nitrate are made by reacting copper (or copper salts) with sulfuric or nitric acid, respectively. The hydroxide and chloride are also easy to make. (EB11). The chloride ("resin of copper") was reportedly made by Robert Boyle in 1664 (Levity).

  Silver

  Silver nitrate, the most important (and least expensive) silver compound even today, was known to the alchemists as "lunar caustic," "magisterium argenti," "crystalli dianae," or "lapis infernalis." It was first prepared by the eighth century Geber, and came into medical use in the seventeenth century (Sadtler, 402). Beginning in the nineteenth century, it was placed in newborns' eyes to prevent eye infections (EA), and used to silver mirrors by the Liebig method. It is made by reacting the metal with nitric acid.

  Silver chloride is the alchemists' lac argenti (milk of silver) or luna cornea, which occurs in nature as the mineral cerargyrite (horn silver) and in that form was described by Oswald Croll in 1608. Since it is insoluble, it can also be obtained by reacting a soluble chloride with a soluble silver salt (such as the nitrate). Silver bromide and iodide are obtained analogously. These three insoluble silver halides darken on exposure to light, which explains why they are useful in photography. Silver iodide has also been used to seed clouds.

  Fulminating silver (silver nitride) is an explosive, and was also known to the alchemists. EB11 says that it can be set off by the touch of a feather.

  Silver carbonate and silver chromate are used in organic synthesis. Silver carbonate is made readily from sodium carbonate and silver nitrate. The bottleneck in producing silver chromate will be obtaining a chromate salt; potassium will do.

  Silver salts have been used to sterilize drinking water. (Emsley 396).

  Gold

  Gold is ductile, a good electrical conductor, and resistant to corrosion. Gold coatings are occasionally used in industrial chemical equipment to protect surfaces from corrosive fluids. But because of gold's unreactiveness, preparation of gold salts isn't easy.

  Gold chloride may be made by dissolving gold in aqua regia, a mixture of nitric and hydrochloric acids. Gold chloride is the secret ingredient of the ruby glass of Bohemia, which would have been invented by Johann Kunkel (1630-1703) but for the RoF.

  If gold chloride is reacted with stannous chloride, you obtain Purple of Cassius, which is a mixture of colloidal gold (tiny gold particles) and tin oxide (EA). It was first made by Andrea Cassius in 1685, and it was used to impart a ruby color to glass, or purple to porcelain. (Emsley 167).

  Another interesting compound is gold hydrazide ("fulminating gold"). It has been called the world's first high explosive, and it was probably made inadvertently by alchemists when they fiddled around with gold chloride (EB11). We know that both Robert Hooke and Johann Glauber experimented with it during the seventeenth century. (Lateral Science)

  Since gold is readily available, but expensive, the commercial appearance of gold compounds is going to be "demand-driven."

  Group 12 Metals

  Zinc

  Brass, a zinc-copper alloy, has been used since antiquity, but the ancients thought of it as simply being a form of copper. Elemental zinc was produced in medieval India (hence the name "Malabar Lead" or "Indian Lead"), and zinc smelting technology was transmitted to China by the sixteenth century. In 1597, Libavius received a sample of Indian zinc, but he took it to be a "peculiar kind of tin." I strongly suspect that the "Japanese zinc" mentioned in 1634: The Galileo Affair (Chapter 33) is actually Chinese.

  After the RoF, zinc is in high demand. Chad Jenkins complains in May 1632 that zinc is not available for galvanization at a reasonable price. Rittgers, "Von Grantville" (Grantville Gazette 7). In April-July 1633, the recycling crew carefully strips zinc off any unusable galvanized steel, and "later date American pennies" (mostly zinc) have been pulled out of circulation. Schillawski and Rigby, "Recycling" (Grantville Gazette 6). N
onetheless, in 1634, Lewis Bartolli has arsenic-free rods of zinc metal. Cooper, "Arsenic and Old Italians" (Grantville Gazette 22).

  Nowadays, the principal ore of zinc is sphalerite (zinc sulfide), which is found in the Harz. However, prior to the RoF, it was calamine (a zinc carbonate, with some zinc silicate) which was most likely to be used by Europeans to make brass. Indeed, Beckmann (78) asserts that by the mid-sixteenth century, there was isolated use of "furnace calamine" (a calcined zinc) from the Rammelsberg mine in alloying, under the guidance of Erasmus Ebener. Clark, "The Secret Book of Zink" (Grantville Gazette 2) explains how zinc can be extracted from calamine and used to galvanize iron, or to make zinc oxide or zinc chloride.

  Nonetheless, Dr. Phil ordered a large quantity of sphalerite in December 1633. He received about five tons worth, in fact, and figured out how to recover, not only the zinc, but various potentially salable byproducts, notably sulfur and sulfuric acid. Offord, "Dr. Phil Zinkens A Bundle" (Grantville Gazette 7). Nonetheless, in April 1634, Sharon Nichols orders two hundred tons "Japanese zinc" from her Venetian connections, and expects delivery by June 1635.

  In the twentieth century, the single most important use of metallic zinc was in galvanizing steel, but it's still used to make brass (and other alloys). Because of its reactivity, it's useful as an anode in certain batteries, and it can be used as an oxidizing agent in chemistry.