What is nickel?
Ni is the chemical symbol of nickel in the VIIIB group of the periodic table and its atomic number is 28. Its density is 8.908 g/cm³. The melting and boiling points of nickel are 1728K (1455 °C, 2651 °F) and 3186 K, (2913 °C, 5275 °F) respectively. Pure nickel is a silvery grey metal. When it is exposed to air, a layer of the basic oxide surface is formed to protect nickel from further oxidation. Therefore, the nickel we see is usually grey white. Nickel is hard, malleable, ductile and can be highly polished. It is the fifth most common element on Earth, usually existing in the form of its compounds. With good properties, nickel is often made into stainless steel, structural alloy steels and other kinds of steel, high nickel base alloys and batteries. Nickel is widely used in military industrial manufacturing, civil machinery manufacturing and the electroplating industry.
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- Nickel: discovery and development
- Classification of nickel alloys
- Nickel: uses
- Nickel: smelting
- Nickel: industry standards
- Nickel: resource and production
- Nickel: recycling
- Nickel: health effects
Before nickel’s actual discovery and isolation, it had been used unintentionally by human beings for centuries. It had been mistaken by ancients for silver, copper and steel. Traced back to 3500 BC, Syrian bronzes contained a small amount of nickel. Between 1700 BC and 1400 BC, manuscripts from China suggested white copper (cupronickel) was used. In 235 BC, coins in China were made of nickel. And in the 17th century nickel was exported to Britain but the nickel content of cupronickel was not discovered until 1822. Also in the 17th century, German miners discovered a red-colored ore which they believed contained copper. However, analysis proved there was no copper but a useless, smelly material was actually present. Finally in 1751, Swedish scientist Baron Axel Frederich Cronstedt isolated nickel from an ore closely resembling kupfernickel. Therefore, he named this new element after the traditional mineral.
Since the mid-19th century, nickel has been a component of coins in the United States, India, Switzerland and Canada. Coins of nearly pure nickel were first used in 1881 in Switzerland and more notably 99.9% nickel five-cent coins were struck in Canada (the world’s largest nickel producer at the time). Gradually, considering the cost of nickel, the material in coins was replaced by using substitutes, with only a few countries using the metallized coating.
Along with developments in society, the nickel industry worldwide has itself developed rapidly since 1974, and nickel plays an important role in the stainless steel industry, battery industry and certain other industries. Gradually, with the development of the above industries, nickel consumption across the world increased greatly between 1974 and 2011.
However, as the stainless steel industry has moved into maturity in most developed nations, current consumption has tended to be stable in those countries. While production in recent years has been steadily increasing, at the same time, affected by global recessions, nickel oversupply has been a direct cause of its declining price. Meanwhile, taking environmental protection and energy conservation into consideration, nickel applications within the battery industry -such as nickel/metal-hydride (Ni/MH) batteries for electric vehicles (EVs) and hybrid electric vehicles (HEVs) – have been developed and gone into mass-production in developed countries. In addition, the nickel recycling industry is developing fast. Therefore, with improving technology, the worldwide nickel industry will have much room to develop.
Nickel alloys are designated by various designation systems however the alloys are usually identified according to their trade names. There are four main groups of nickel alloys: commercially pure nickel alloys, nickel- copper alloys, non-heat-treatable nickel-chromium-iron alloys and heat-treatable nickel-chromium-iron alloys.
Commercially pure nickel alloys
These alloys contain not less than 99% nickel.
Three-digit numbers (2xx, 3xx) are used as trade names of commercial nickel.
The alloys are characterized by very good corrosion resistance and high ductility.
These alloys contain about 30% copper, which forms a solid solution with nickel.
The accepted trade name of Nickel-Copper Alloys is Monel.
Nickel-Copper Alloy, containing aluminum and titanium as additional alloying elements (Monel K-500), is heat-treatable and may be strengthened by precipitation hardening.
Non-heat-treatable nickel-chromium-iron alloys
The major alloying elements of these alloys (15-22% chromium and up to 46% iron) form a solid solution with nickel.
The alloys may be hardened by cold work.
The non-heat-treatable Nickel-Chromium-Iron Alloys are identified according to their trade names: Inconel, Incoloy and Hastelloy.
Heat-treatable nickel-chromium-iron alloys
These alloys may be strengthened by precipitation hardening due to the presence of additional alloying elements: aluminum, titanium, silicon.
Nimonic, Inconel X-750, Udimet, Waspaloy, Rene, and Astroloy are some of the trade names of heat-treatable Nickel-Chromium-Iron Alloys.
Uses of nickel
Nickel-containing products play an important role in our daily lives. Compared with other materials, nickel-containing products possess better corrosion resistance, greater toughness, more strength at high and low temperatures, and a range of special magnetic and electronic properties. Therefore, most nickel production is used for alloying elements, coatings, batteries, and some other uses, such as kitchen wares, mobile phones, medical equipment, transport, buildings, power generation and jewellery.
The use of nickel is dominated by the production of ferronickel for stainless steel (66%). However, it is also used in the production of non-ferrous alloys (12%), alloy steels (5%), plating (7%), foundry (3%) and batteries (2%).
Nickel can alloy with steels, irons, coppers, chromium, aluminum, lead, cobalt, silver, gold and other elements to make stainless steels, cast irons, inconel, incoloy, monel, nimonic and other alloys. Detailed alloys’ classifications are as follows:
Ferrous alloys include stainless steels, low alloy steels, cast irons and some specialty steels. The products are used in gas turbines, some chemical plants, coinage and marine engineering.
The most widely used non-ferrous alloys are copper alloys such as monel, nickel brasses and bronzes. The products include propellers, crankshafts and hulls of premium tugboats, fishing boats and other working boats.
Nickel-base alloys include Ni-base superalloy, Ni-base corrosion resistant alloy, Ni-base wear-resistant alloy, Ni-based precision alloy, Ni-base shape memory alloy and Hydrogen storing alloy. The above alloys are widely used in aviation, shipbuilding, the chemical industry, electronics, medicine and the energy industry.
Nickel powder is used for powder metallurgy (P/M) alloys.
Nickel coatings primarily refer to electroplated nickel, which is used to provide hard-wearing decorative and engineering coatings as ‘nickel-plating’, ‘electroless nickel coating’ or ‘electroforming’. When used with a top layer of chromium, it is popularly known as ‘chrome-plating’. When done in combination with silicon carbide it is known as composite plating, such as in the coating of coins.
Nickel is a key part of several rechargeable battery systems used in electronics, power tools, transport and emergency power supply. The most important application is nickel-metal hydride (NiMH).
Catalyst: key to several important reactions, including the hydrogenation of vegetable oils, reforming of hydrocarbons, and the production of fertilizers, pesticides, and fungicides. Moreover nickel is used for filters, binders and some other uses.
Extraction and purification
Nickel is recovered through extractive metallurgy: it is extracted from its ores by conventional roasting and reduction processes that yield a metal of greater than 75% purity. In many stainless steel applications, 75% pure nickel can be used without further purification, depending on the composition of the impurities.
Most sulfide ores have traditionally been processed using pyrometallurgical techniques to produce a matte for further refining. Recent advances in hydrometallurgical techniques have resulted in significant nickel purification using these processes. Most sulfide deposits have traditionally been processed by concentration through a froth flotation process followed by pyrometallurgical extraction. In hydrometallurgical processes, nickel sulfide ores undergo flotation (differential flotation if Ni/Fe ratio is too low) and then smelted. After producing the nickel matte, further processing is done via the Sherritt-Gordon process. First, copper is removed by adding hydrogen sulfide, leaving a concentrate of only cobalt and nickel. Then, solvent extraction is used to separate the cobalt and nickel, with the final nickel concentration greater than 99%.
A second common form of further refining involves the leaching of the metal matte into a nickel salt solution, followed by the electro-winning of the nickel from solution by plating it onto a cathode as electrolytic nickel.
Purification of nickel oxides to obtain the purest metal is performed via the Mond process, which increases the nickel concentrate to greater than 99.99% purity. This process was patented by Ludwig Mond and has been in industrial use since before the beginning of the 20th century. In the process, nickel is reacted with carbon monoxide at around 40–80 °C to form nickel carbonyl in the presence of a sulfur catalyst. Iron gives iron pentacarbonyl, too, but this reaction is slow. If necessary, the nickel may be separated by distillation. Dicobalt octacarbonyl is also formed in nickel distillation as a by-product, but it decomposes to tetracobalt dodecacarbonyl at the reaction temperature to give a non-volatile solid.
Nickel is re-obtained from the nickel carbonyl by one of two processes. It may be passed through a large chamber at high temperatures in which tens of thousands of nickel spheres, called pellets, are constantly stirred. It then decomposes, depositing pure nickel onto the nickel spheres. Alternatively, the nickel carbonyl may be decomposed in a smaller chamber at 230 °C to create a fine nickel powder. The resultant carbon monoxide is re-circulated and reused through the process. The highly pure nickel produced by this process is known as “carbonyl nickel”.
Hydrometallurgy of Nickel
The high temperature (~250°C) acid pressure leaching of nickeliferous laterite ore has been practised commercially since the late 1950’s. The acid pressure leach solution is treated using hydrogen sulphide to produce a high grade sulphide containing at least 50% nickel. This mixed sulphide is then pressure leached to give a high purity concentrated nickel-cobalt solution, suitable for solvent extraction to separate the valuable metals. The nickel and cobalt are separately reduced to metal products.
The flow-sheet below shows the unit operations used in the process.
Source: Acid Leach Process-METMOC
The main source of the world’s nickel is from copper-nickel sulphide ores with those mined at Sudbury, Ontario being by far the most extensive. The principle nickel sulphide is pentlandite (NiFeS2), which is usually associated with chalcopyrite and iron sulphides. International Nickel (INCO) and Sherritt Gordon use a bulk Cu/Ni float pictured below, followed by selective flotation of the two elements into separate concentrates. Other Canadian producers leave separation to the smelters.
Flotation of a Copper/Nickel Ore Containing Pyrrhotite is as follows:
Generalized Flowsheet of the INCO Matte Separation Process is as follows:
Nickel flash smelting
Outotec® Nickel Flash Smelting Process is a benchmark nickel-smelting method and a clear global leader in the world’s primary nickel production from sulfide raw materials. Efficiency and improved environmental and in-plant hygiene have been the guiding principles in developing the process.
Flash smelting (Finnish: Liekkisulatus) is a smelting process for sulfur-containing ores including chalcopyrite. The process was developed by Outokumpu in Finland and first applied at the Harjavalta plant in 1949 for smelting copper ore. It has also been adapted for nickel and lead production.
A second flash smelting system was developed by the International Nickel Company (‘INCO’) and has a different concentrate feed design compared to the Outokumpu flash furnace. The Inco flash furnace has end-wall concentrate injection burners and a central waste gas off-take, while the Outokumpu flash furnace has a water-cooled reaction shaft at one end of the vessel and a waste gas off-take at the other end. While the INCO flash furnace at Sudbury was the first commercial use of oxygen flash smelting, fewer smelters use the INCO flash furnace than the Outokumpu flash furnace. The reactions in the flash smelting furnaces produce copper matte, iron oxides and sulfur dioxide. The reacted particles fall into a bath at the bottom of the furnace, where the iron oxides react with fluxes, such as silica and limestone, to form a slag.
Outotec, formerly the technology division on Outokumpu now holds Outokumpu’s patents to the technology and licenses it worldwide. (INCO was acquired by Brazil’s Vale in 2006.)
Source: Flash smelting-WIKIPEDIA
Niihama Nickel Refinery
The Niihama Nickel Refinery is the only refinery that produces electrolytic nickel and electrolytic cobalt in Japan. The Niihama Nickel Refinery started production of electrolytic nickel in 1939. Since that time, it has undergone 2 major production changes, and now produces electrolytic nickel using the MCLE (Matte Chlorine Leach Electrowinning) method. This MCLE method process is highly evaluated as an excellent industrial manufacturing technology, making the refinery highly efficient even from a worldwide standard.
Nickel matte with a 70% nickel grade, procured from mines and smelters that we have a stake in, and mixed sulfide with a 60% nickel grade produced in Coral Bay, using the HPAL (High Pressure Acid Leach) process is used as raw material.
Production Process of Electrolytic Nickel
ISO 11876:2010 Hardmetals — Determination of calcium, copper, iron, potassium, magnesium, manganese, sodium, nickel and zinc in cobalt metal powders — Flame atomic absorption spectrometric method
ISO 11790:2010 Copper, lead, zinc and nickel concentrates — Guidelines for the inspection of mechanical sampling systems
ISO 12153:2011 Welding consumables — Tubular cored electrodes for gas shielded and non-gas shielded metal arc welding of nickel and nickel alloys–Classification
ISO 11435:2011 Nickel alloys — Determination of molybdenum content — Inductively coupled plasma/atomic emission spectrometric method
ISO 12932:2013 Welding — Laser-arc hybrid welding of steels, nickel and nickel alloys — Quality levels for imperfections
ISO 22033:2011 Nickel alloys — Determination of niobium — Inductively coupled plasma/atomic emission spectrometric method
ISO/TS 24348:2014 Ophthalmic optics — Spectacle frames — Method for the simulation of wear and detection of nickel release from metal and combination spectacle frames
ISO 5817:2014 Welding — Fusion-welded joints in steel, nickel, titanium and their alloys (beam welding excluded) — Quality levels for imperfections
ASTM A494 / A494M – 14 Standard Specification for Castings, Nickel and Nickel Alloy
ASTM B626 – 14 Standard Specification for Welded Nickel and Nickel-Cobalt Alloy Tube
ASTM A265 – 12 Standard Specification for Nickel and Nickel-Base Alloy-Clad Steel Plate
ASTM B619 – 10e2 Standard Specification for Welded Nickel and Nickel-Cobalt Alloy Pipe
ASTM B343 – 92a(2009) Standard Practice for Preparation of Nickel for Electroplating with Nickel
ASTM B474 – 03(2009) Standard Specification for Electric Fusion Welded Nickel and Nickel Alloy Pipe
ASTM B366 – 10a Standard Specification for Factory-Made Wrought Nickel and Nickel Alloy Fittings
ASTM B622 – 10e1 Standard Specification for Seamless Nickel and Nickel-Cobalt Alloy Pipe and Tube
ASTM B775 – 13 Standard Specification for General Requirements for Nickel and Nickel Alloy Welded Pipe
ASTM B751 – 08(2013) Standard Specification for General Requirements for Nickel and Nickel Alloy Welded Tube
ASTM B906 – 02(2012) Standard Specification for General Requirements for Flat-Rolled Nickel and Nickel Alloys Plate, Sheet, and Strip
ASTM B730 – 08(2013) Standard Specification for Welded Nickel (UNS N02200/UNS N02201) and Nickel Copper Alloy (UNS N04400) Tube
ASTM B151 / B151M – 13 Standard Specification for Copper-Nickel-Zinc Alloy (Nickel Silver) and Copper-Nickel Rod and Bar
ASTM B206 / B206M – 12 Standard Specification for Copper-Nickel-Zinc (Nickel Silver) Wire and Copper-Nickel Alloy Wire
International Standards and Testing Applicable to Batteries—(Nickel Metal Hydride Batteries, Nickel Cadmium Batteries)
World Resources: Identified land-based resources averaging 1% nickel or greater contain at least 130 million tons of nickel. About 60% is in laterites and 40% is in sulfide deposits. Extensive resources of nickel are also found in manganese crusts and nodules covering large areas of the ocean floor.
Source: Nickel-U.S. Geological Survey, Mineral Commodity Summaries, February 2014
Distribution according to region
Laterite-nickel ore: New Caledonia in the south Pacific Ocean; Moluccas and Sulawesi in Indonesia; Palawan in the Philippines; Queensland in Australia; Minas Gerais and Goias in Brazil; Oriente in Cuba; Banan in Dominica; the Central Euboea area, Neo Kokkino area of Viotia, and Kastoria area in Greece; and some other areas in Russia and Albania, etc.
Nickel sulphide ore: Jinchuan, Gansu Province and Panshi, Jilin Province in China; Sudbury, Ontario Province and Lynn Lake-Thompson, Manitoba Province in Canada; Kola Peninsula and Norilsk, Siberia, in Russia; Kambalda in Australia; Selebi Phikwe in Botswana; Kotalahti in Finland.
Distribution according to country
Laterite-Nickel Ore: Cuba, New Caledonia, Indonesia, Philippines, Burma, Vietnam and Brazil.
Nickel Sulphide ore: Canada, Russia, Australia, China and South Africa, etc.
Major nickel producing countries: Indonesia, Russia, China, Canada, Cuba, Australia, Philippines, New Caledonia.
The figures of nickel reserves reported by the United States Geological Survey (USGS) in 2014 were as follows:
Source: Nickel- U.S. Geological Survey, Mineral Commodity Summaries, February 2014
Production and consumption
The figures of nickel mine production reported by the United States Geological Survey (USGS) in 2014 were as follows:
Source: Nickel- U.S. Geological Survey, Mineral Commodity Summaries, February 2014
Nickel consumption by country and industry, 2011 were as follows:
In 2012, the slowdown in demand for nickel was especially apparent compared with other base metals, thanks mainly to the moderation in stainless steel production, which accounts for about two-thirds of global usage. Consumption is forecast to have slowed from a 7 percent growth rate in 2011 to 2 percent in 2012, and to increase 4 percent in 2013, underpinned by the recovery in demand from the EU, South Korea, and India. The medium-term consumption outlook is still promising considering emerging markets’ low per capita nickel consumption and ongoing industrialization and urbanization. Consumption in China, however, is expected to moderate significantly from the annual growth rate of 21 percent during 2006-10; the focus of its steel industry is shifting from expanding capacity to improving quality and product range.
Source: Nickel Consumption by Country and Industry-MAPI
Leading nickel consumers in 2011 were as follows:
Metals are recycled because they are valued and because most of them share the inherent quality of recyclability. This is especially true of non-ferrous metals, a group that includes nickel. Nickel is amongst the most valuable of the common non-ferrous metals and the world’s most highly recycled substance. In contrast to the rapid development within the nickel industry, growing consumption of nickel, and proliferation of waste materials, the level of nickel resources is declining.
Industry experts estimate that nickel bearing scrap totaling 4.4-4.6 million tonnes per year is collected and recycled. This scrap is estimated to contain almost 350,000t of nickel (or one-quarter of the total demand) annually which is mainly used by the stainless steel industry. The nickel scrap processing industry consists of four or five major companies operating on an international level to ensure that nickel bearing scrap is collected from every corner of the globe. Moreover, batteries contain a variety of materials that can be reused as a secondary raw material. There are well-established methods and techniques for the recycling of most batteries containing lead, nickel-cadmium, nickel hydride and mercury. For some, such as newer nickel-hydride and lithium systems, recycling methods are still in the early stages. With huge opportunity for development, it follows that nickel collecting and recycling will become of great importance for the nickel industry.
As we all know, nickel is widely used in many areas in our daily life, for example coins, jewellery, mobile phones, magnets, electronics, glasses and kitchen wares. With its excellent properties, it is of great importance in people’s lives. However, for human beings, it may also present significant health hazards. The hazard level depends on the amount of inhalation and the duration of inhalation. For example, it is one of the most common allergenic metals. The following Q&As may give you more information about the effect of nickel on human health.
How can nickel affect my health?
Nickel is one of the essential biological elements for human beings. However, it is also one of the most common allergenic metals, and about 10%-20% of people are allergic to nickel ion. More women are sensitive to nickel than men. This difference between men and women is thought to be a result of greater exposure of women to nickel through jewellery and other metal items containing nickel. Once a person is sensitized to nickel, further contact with the metal may cause a reaction. The most common reaction is a skin rash at the site of contact. For some sensitized people, dermatitis (a type of skin rash) may develop in an area of the skin that is away from the site of contact. Some workers exposed to nickel by inhalation can become sensitized and have asthma attacks, but this is rare. People who are sensitive to nickel have reactions when nickel comes into prolonged contact with the skin. Some sensitized individuals react when they eat nickel in food or water or breathe dust containing nickel.
People who are not sensitive to nickel would have to eat very large amounts of nickel to suffer harmful health effects. Workers who accidentally drank light-green water containing 250 ppm of nickel from a contaminated drinking fountain had stomach aches and suffered adverse effects in their blood (increased red blood cells) and kidneys (increased protein in the urine). This concentration of nickel is more than 100,000 times greater than the amount usually found in drinking water.
The most serious harmful health effects from exposure to nickel, such as chronic bronchitis, reduced lung function and cancer of the lung and nasal sinus, have occurred in people who have breathed dust containing certain nickel compounds while working in nickel refineries or nickel-processing plants. The levels of nickel in these workplaces were much higher than usual (background) levels in the environment.
How might I be exposed to nickel?
Normally nickel comes into contact with the human through food (the major source), water, air, soil, sediment and some hazardous waste sites–as well as through smoking tobacco. Also some products used in our daily lives contain nickel, including stainless steels and nickel alloys used in jewellery, coins, kitchen wares, mobile phones and some medical artificial body parts. Usually, the nickel content of the above sources is low. You may be exposed to higher levels of nickel if you work in industries that process or use nickel. Exposure of unborn children to nickel occurs through the transfer of nickel from the mother’s blood to fetal blood. Likewise, nursing infants are exposed to nickel through the transfer of nickel from the mother’s breast milk.
How can nickel enter and leave my body?
Nickel can enter your body by breathing air, drinking water, eating food and wearing jewellery which contains nickel. It depends on the size of the nickel particles, whether the nickel element reaches your lungs and your blood. If the particles are large, they stay in your nose; if the particles are small, they enter deep into your lungs. Some of these nickel particles can leave the lungs with mucus that you spit out or swallow. More nickel will pass into your body through your stomach and intestines if you drink water containing nickel than if you eat food containing the same amount of nickel. A small amount of nickel can enter your bloodstream from skin contact. After nickel gets into your body, it can go to all organs, but it mainly goes to the kidneys. The nickel that gets into your bloodstream leaves in the urine. After nickel is eaten, most of it leaves quickly in the feces, and the small amount that gets into your blood leaves in the urine.
How can families reduce the risk of exposure to nickel?
For the whole family, it is better to eat food and drink water with no nickel, and keep away from the nickel industries and plants and similar places .
Avoid wearing jewellery and some other items containing nickel.
Visit the doctor to check whether you, your children or other family members have been exposed to substantial amounts of nickel regularly.
Refrain from smoking.
Be careful when choosing the kitchen wares.
What recommendations has the federal government made to protect human health?
The federal government develops regulations and recommendations to protect public health. Regulations can be enforced by law. The EPA, the Occupational Safety and Health Administration (OSHA), and the Food and Drug Administration (FDA) are some federal agencies that develop regulations for toxic substances. Recommendations provide valuable guidelines to protect public health, but cannot be enforced by law. The Agency for Toxic Substances and Disease Registry (ATSDR) and the National Institute for Occupational Safety and Health (NIOSH) are two federal organizations that develop recommendations for toxic substances.
Regulations and recommendations can be expressed as “not-to-exceed” levels, that is, levels of a toxic substance in air, water, soil, or food that do not exceed a critical value that is usually based on levels that affect animals; they are then adjusted to levels that will help protect humans. Sometimes these not-to-exceed levels differ among federal organizations because they use different exposure times (an 8-hour working day or a 24-hour day), different animal studies, or other factors.
Recommendations and regulations are also updated periodically as more information becomes available. For the most current information, check with the federal agency or organization that provides it. Some regulations and recommendations for nickel include the following:
OSHA has set an enforceable limit of 1.0 mg nickel/m³ for metallic nickel and nickel compounds in workroom air to protect workers during an 8-hour shift over a 40-hour working week. EPA recommends that drinking water levels for nickel should not be more than 0.1 mg per litre.
Source: China Nickel Alloy Pipe Fittings Manufacturer – Yaang Pipe Industry (www.steeljrv.com)
(Yaang Pipe Industry is a leading manufacturer and supplier of nickel alloy and stainless steel products, including Super Duplex Stainless Steel Flanges, Stainless Steel Flanges, Stainless Steel Pipe Fittings, Stainless Steel Pipe. Yaang products are widely used in Shipbuilding, Nuclear power, Marine engineering, Petroleum, Chemical, Mining, Sewage treatment, Natural gas and Pressure vessels and other industries.)
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