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History and Production of Nickel and Nickel Alloys

1.1 Origin and Abundance of Nickel

The story of nickel, like other natural elements, began billions of years ago with the origin of the universe and our solar system. According to the standard model, as the temperature decreased after the Big Bang, stable atoms of hydrogen and helium formed. It is presumed that local differences in the concentration of these nuclides resulted in gravitational clumping and initiated fusion reactions involving hydrogen and helium, resulting in the formation of stars. The exhaustion of hydrogen and helium fuels in the center of stars resulted in gravitational collapse, and other fusion reactions occurred involving successively heavier nuclides - carbon, neon, oxygen, and silicon. A form of stellar explosion, called a Type IA supernova, resulted in the nuclear fusion of carbon and oxygen, which produced the transition series elements with stable atomic numbers, such as Fe, Ni, Co, V, Cr, and Mn. The explosion of Type IA supernova is believed to have injected these elements into nearby gas clouds [1]. As the stars became unstable and exploded, the interstellar space began to be enriched in heavy elements. Local gravitational clumping of interstellar gas resulted in spinning disks that are the forerunners of planetary systems, such as our own. The relative abundances of various elements in the solar system have been measured by many investigators, which have yielded consistent results [2]. The abundances of elements in the solar system are usually reported on a logarithmic scale as atoms relative to a million Si atoms. The abundances are usually derived from the spectroscopy of solar and stellar emissions, from analyses of lunar soils where the deposition of elements from solar winds may have occurred, and from analyses of meteorites and comets. The abundances show a general decrease with an increase in atomic number, with some local maxima for stable nuclides, such as iron and nickel. Doubtless, this stellar history will be revised as more data are gathered, but the abundance of these elements in the universe appears to be reasonably well established.

Figure 1.1 Abundance ratio of selected elements with respect to silicon (atoms of the element per million atoms of Si) in the continental crust.

Although the Earth's crust has a relatively low concentration of nickel [3] (Figure 1.1), it is believed, from density considerations and the analysis of some meteorites, that the Earth's core is made up entirely of iron with about 8% of nickel and some cobalt.

It has been hypothesized that a certain Ni-Fe metallic mineral, called Josephinite after its discovery in Josephine Creek in Oregon [4], originated from the core-mantle boundary and was transported to the lithosphere by deep-mantle plumes and then emplaced in the crust through various hydrothermal processes [4-6]. Further discussion of the Ni-Fe alloy will be presented in a later chapter under natural analogs of long-term corrosion processes. It is possible that some early uses of high Ni artifacts could have arisen from accidental finds of Ni-Fe meteorites.

1.2 Ancient History of Nickel Usage

Archeologists believe that the deliberate extraction of metal from its ores occurred sometime in the fifth millennium Before Common (Current) Era (BCE) in Mesopotamia in a region spanning the current-day southern Turkey and northern Iraq [7]. Although metal objects dated from the 7250 to 6750 BCE period have been found in the Çayönü site in Turkey, they are believed to originate from native copper, not copper smelted from ores [8]. Rapp [9] analyzed over 1000 native copper deposits and came to the conclusion that only 1 out of 851 samples contained Ni content greater than 0.63% and that any copper artifact with less than 0.7% Ni is likely to be native copper. These are imprecise markers for smelted vs. native copper. For example, the copper objects found at the Çayönü site contained 0.875% Ni [8] but are believed to be native copper in origin. Using a combination of elements present in the metal objects excavated from a chalcolithic site in India, it has been suggested that these objects were smelted rather than native copper [9]. In chalcolithic sites in modern-day Syria, Iraq, Pakistan, and India, nickel content as high as 3.5% has been found. Further, the nickel content varied significantly depending on the type of object, suggesting deliberate additions of nickel by the early metallurgists [9]. Alloys of copper and nickel, called paktong or white metal, were produced in ancient China by smelting complex sulfide ores. In later periods, zinc was added to increase the malleability of paktong, perhaps paving the way for latter-day "German silver" or nickel brass [10]. Perhaps, the oldest example of human-made copper-nickel alloys existing today is a coin containing 78% copper and 20% nickel, dating to about 235 BCE from Bactria (an area in modern Afghanistan). It is improbable that the ancient metallurgists recognized nickel as a separate metallic element, but it is likely that some arsenical ores found in association with malachite (basic copper carbonate) in these areas, for example annabergite ((Ni,Co)3(AsO4)2.8H2O), were deliberately used in the smelting process to achieve certain desired properties.

1.3 History of Industrial Usage of Nickel and Its Alloying Elements

The isolation of elemental nickel was performed first by Kronstedt in 1751 and was confirmed by Bergmann in 1755 CE [11]. Richter produced the first malleable nickel in 1804, which was commercialized in 1865 by Joseph Wharton [10] through a refinery built in Camden, New Jersey. Chromium, molybdenum, tungsten, and cobalt are among the most useful alloying elements for corrosion- and wear-resistant Ni-based alloys. Although chromium is found in almost equal abundance as nickel in the Earth's crust, its discovery as a metal occurred later because of its strong tendency to form oxy-compounds. As early as 1770, chemists who analyzed the mineral crocoite in Ural mines assumed that it was essentially lead with impurities. Little did they realize that crocoite was essentially lead chromate. However, the French chemist Louis Nicolas Vauquelin in 1797 conducted a systematic study of crocoite by boiling it with potassium carbonate and reacting the resulting residue with various salts. The resulting diverse color changes made him realize that he is dealing with a new element, and he named it "chromium" from the Greek word "chroma," meaning colors. The name molybdenum originated from the Greek name "Molybdena" for a lead mineral. Carl Scheele first separated molybdenum oxide from the mineral molybdenite in 1778. He suspected that the oxide was that of a new element but did not perform conclusive experiments. He left the reduction of molybdenum oxide to his friend, P. Hjelm, who performed the reduction using carbon, producing a highly impure molybdenum. The pure form of Mo was obtained by Berzelius in 1817 using hydrogen reduction. The origin of the name wolfram for tungsten is perhaps apocryphal. Early smelters of tin ores discovered that part of the metal was lost in one of the minerals and considered that mineral to have devoured tin like a wolf does sheep and called it wolframite. It was also known as tungsten or "heavy stone." In 1781, Carl Scheele treated wolframite with nitric acid and discovered a white substance that he showed was different from molybdic acid. In 1783, two Spanish chemists, the brothers Juan Jose and Fausto Elhuyar, succeeded in extracting metallic tungsten from tungstic acid. Cobalt [11] perhaps owes its name to a mineral "Kobold," so named by Saxony miners after the evil spirit that was assumed to inhabit the mineral. The mineral, which looked like silver, resisted all efforts to extract silver. Cobalt was first extracted by Brandt in 1735 but was not recognized until much later as a separate element.

Although all these elements were known in the 18th century, it took almost another century to realize the benefits of their alloying with iron and nickel. Nickel alloys were first produced in 1830 in Birmingham under the names of "Merry Plate" and "Merry Metal Blanc." The early efforts to start a nickel industry in Canada received significant impetus by the order of $1 million worth of nickel by the U.S. government for the production of armor plates. The development of stainless steels and nickel-based corrosion-resistant alloys occurred in several overlapping cycles and in several countries at the same time [12]. Pollack (Chapter 1 in Ref. [12]) characterized the development stages as "alloy technology driven," "production technology driven," and "application technology driven." In the first stage, the effects of various alloying elements were explored in many different alloys, mainly in the form of castings and high-carbon stainless steels. In the second stage, new melting technologies capable of manufacturing low-carbon alloys were developed, significantly enhancing the application potential of the Ni-based alloys. In the third stage, new alloys tailored to specific application niches were developed.

The development of Ni-based alloys is intertwined with the development of stainless steels. Harry Brearley in the United Kingdom pioneered the...