The rare-earth elements (rare-earth metals), or the lanthanides are 17 soft, heavy metals. These metals tarnish slowly in air and react slowly with water to form hydroxides. They can form oxides and ignite spontaneously above 400 °C. They have diverse applications in electronic components, lasers, glass, magnetic materials and industrial processes.
The history of rare earth elements?
The first rare-earth element was ytterbite, discovered by Arrhenius in 1787, in Ytterby, Sweden. Arrhenius’s ytterbite reached Gadolin, a professor at the Royal Academy of Turku. He yielded an oxide that he called yttria. Ekeberg, proceeded to isolate beryllium from the gadolinite.
After this discovery in 1794, a mineral from Bastnäs, Sweden, was re-examined by Berzelius and Hisinger and they observed a white oxide, naming it ceria. The new elements, yttrium and cerium were the only discoveries of rare earth elements for the next 30 years.
In 1839 Mosander heated the nitrate and dissolved it in nitric acid, leading to an oxide he later named lanthana. 3 years later he separated the lanthana into didymia and pure lanthana. In 1842 Mosander also separated the yttria into three oxides: pure yttria, terbia and erbia. The earth giving pink salts he called terbium and the yellow ones, erbium. The six verified elements by 1842 were; yttrium, cerium, lanthanum, didymium, erbium and terbium.
Discovery and characterisation of the last rare earth elements
In 1879 Delafontaine benefitted from a newly discovered process, flame spectroscopy, leading to several new optical lines within didymia. In the same year, samarium was also isolated by Lecoq de Boisbaudran. Further research of samaria, yttria, and samarskite, showed the existence of an unknown element, later revealing europium. In 1839 a mineral from Miass in the Ural Mountains was documented by Rose and later Blomstrand, Galissard de Marignac. Rose found tantalum and niobium.
The use of X-ray spectra, through X-ray crystallography made it possible to assign atomic numbers. Hafnium sits in the periodic table below zirconium and they are very similar in their chemical and physical properties.
Spedding and others in the United States, as part of the Manhattan Project in the 1940’s, developed chemical ion-exchange procedures for separating the rare-earth elements. This was used for separating plutonium-239 and neptunium from uranium, thorium, actinium.
Rare-earth elements are derived from bastnäsite, monazite, and loparite. Rare-earth minerals are difficult to extract and mine, relative to the transition metals, this makes industrial extraction very expensive. Ion exchange, fractional crystallisation and liquid–liquid extraction has optimised the extraction process and made their use more readily available.
Rare earth metals – Lithium in Cornwall
Cornish Lithium, pioneering the UK industry for battery rare earth metals, continue ongoing drilling work in Cornwall, UK. The company is aiming to pursue lithium from hot water brines, which sit within the historic tin and copper mines. Additionally, the company is chasing lithium extraction from hard rock, believing that it was mined on the surface during World War II.
Cornish Lithium will also explore lithium and other rare minerals. This valuable data being recorded via contemporary imaging 3D techniques, highlights a fresh understanding of the geological potential of the region’s deposits.
List and applications of rare earth metals
Rare earth elements are widely used in low carbon technologies. China produces >95% of the World’s supply but has been steadily reducing supply. The restrictions to the UK economy is currently limited but as the UK drives new green initiatives and technology becomes ever more prominent a future strategy and its economic importance to the UK has to be focused upon. The US and Australia are ramping up supply to offset the slowing Chinese market. Below are applications in today’s global marketplace for each of the rare earth metals:
Scandium alloys for the aerospace industry
Yttrium phosphors, ceramics, metal alloys
Lanthanum batteries, catalysts for refining
Cerium catalysts, polishing
Praseodymium magnet corrosion resistance
Neodymium powerful magnets for laptops, lasers
Promethium beta radiation source
Samarium high temperature magnets, reactor control rods
Europium liquid crystal displays
Gadolinium magnetic resonance imaging contrast agent
Terbium phosphors for lighting
Dysprosium high power magnets, lasers
Holmium the most powerful magnets
Thulium ceramic magnetic materials
Ytterbium fibre optic technology, solar panels
Lutetium X-ray phosphors
Rare earth elements used in magnets
Neodymium and samarium cobalt magnets are the main types. These are split into a variation of grades which exhibit different properties. Samarium cobalt magnets are made from an alloy of samarium, cobalt, iron, copper, hafnium, zirconium and praseodymium. They have very high maximum operating temperatures and are extremely resistant to corrosion.
Neodymium magnets, discovered in 1982 by GM and Sumitomo Special Metals became the strongest permanent magnets. They are constructed from an alloy containing neodymium, iron and boron. Middle range neodymium magnets exhibit less tolerance to corrosion.
Rare earth metals China
China announced regulations on exports and a crackdown on smuggling. In 2010, China Daily, citing an unnamed Ministry of Commerce official, reported that China will “further reduce quotas for rare earth exports by 30 percent to protect the precious metals from over-exploitation.” At the end of 2010, China announced that the first round of export quotas in 2011 for rare earths would be a 35% decrease from the previous first round of quotas. In September 2011, China announced the halt in production of three of its eight major rare-earth mines. In March 2012, the US, EU, and Japan confronted China at WTO about these export and production restrictions. In August 2012, China announced a further 20% reduction in production. The United States, Japan, and the European Union filed a joint lawsuit with the World Trade Organisation, arguing that China should not be able to deny such important exports.
In response to the opening of new mines in other countries (Australia and the United States), prices of rare earths dropped. On August 29, 2014, the WTO ruled that China had broken free-trade agreements, and the WTO said in the summary of key findings that “the overall effect of the foreign and domestic restrictions is to encourage domestic extraction and secure preferential use of those materials by Chinese manufacturers.”
Rare earth metals in your mobile phone batteries…
Rare earth elements make-up your glass backlit display, magnets in speakers, to the motors, making it vibrate. Beyond mobile devices, they are found in electric cars, solar cells, and batteries. The irony is that the components they create are part of the new, renewable energy drive. A hybrid Toyota Prius, for example, uses >10kg of rare earths in its main floor battery. This is just one of many hybrid and electric vehicles.
Rare earth elements and the environment
They are found in very minute concentrations in the Earth’s crust. Rare earth elements can be absorbed into plants and consumed by humans and animals. Mining sites see the concentrations rise above the normal background expectations. Once in the environment they can leach into the soil where they travel by numerous means like ground erosion, pH, precipitation and ground water.
Extraction rely’s on the production of phosphorus fertilisers which contribute to contamination. Strong acids are also used during this process, which can then leach out in to the environment. Additionally, cerium oxide which is produced during the combustion of diesel as an exhaust particulate, contributes to soil contamination. Refining, and recycling have serious environmental consequences. Radioactive tailings resulting from the occurrence of thorium and uranium in rare-earth element ores present a potential hazard leading to extensive environmental damage. An example is the large-scale operation in Baotou, in Inner Mongolia, where much of the world’s supply is refined, has caused major environmental damage.
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