Bismuth metal has been known since ancient times. Before modern analytical methods bismuth's metallurgical similarities to lead andtin often led it to be confused with those metals. The etymology of "bismuth" is uncertain. The name may come from mid-sixteenth-centuryNeo-Latin translations of the German wordsweiße Masse orWismuth, meaning 'white mass', which were rendered asbisemutum orbisemutium.
Bismuth compounds account for about half the global production of bismuth. They are used in cosmetics;pigments; and a few pharmaceuticals, notablybismuth subsalicylate, used to treatdiarrhea.[12] Bismuth's unusual propensity to expand as it solidifies is responsible for some of its uses, as in the casting of printing type.[12] Bismuth, when in its elemental form, has unusually lowtoxicity for aheavy metal.[12] As thetoxicity of lead and the cost of itsenvironmental remediation became more apparent during the 20th century, suitable bismuthalloys have gained popularity as replacements for lead. Presently, around a third of global bismuth production is dedicated to needs formerly met by lead.
Bismuth metal has been known since ancient times. It was one of the first 10 metals to have been discovered. The namebismuth dates to around 1665 and is of uncertain etymology. The name possibly comes from obsolete GermanBismuth,Wismut,Wissmuth (early 16th century), perhaps related toOld High Germanhwiz ("white").[13] TheNeo-Latinbisemutium (coined byGeorgius Agricola, who Latinized many German mining and technical words) is from the GermanWismuth, itself perhaps fromweiße Masse, meaning "white mass".[14][15]
The element was confused in early times with tin and lead because of its resemblance to those elements. Because bismuth has been known since ancient times, no one person is credited with its discovery.Agricola (1546) states that bismuth is a distinct metal in a family of metals including tin and lead. This was based on observation of the metals and their physical properties.[16] Miners in the age of alchemy also gave bismuth the nametectum argenti, or "silver being made" in the sense of silver still in the process of being formed within the Earth.[17][18][19] Bismuth was also known to theIncas and used (along with the usual copper and tin) in a specialbronze alloy for knives.[20]
Left: A bismuthhopper crystal exhibiting the stairstep crystal structure andiridescent colors, which are produced byinterference of light within the oxide film on its surface. Right: a 1 cm3 cube of unoxidised bismuth metal
Pressure-temperature phase diagram of bismuth.TC refers to the superconducting transition temperature
Bismuth is a brittle metal with a dark, silver-pink hue, often with aniridescentoxide tarnish showing many colors from yellow to blue. The spiral, stair-stepped structure of bismuth crystals is the result of a higher growth rate around the outside edges than on the inside edges. The variations in the thickness of the oxide layer that forms on the surface of the crystal cause different wavelengths of light to interfere upon reflection, thus displaying a rainbow of colors. Whenburned inoxygen, bismuth burns with a blueflame andits oxide forms yellowfumes.[22] Itstoxicity is much lower than that of its neighbors in theperiodic table, such as lead andantimony.[24]
Though virtually unseen in nature, high-purity bismuth can form distinctive, colorfulhopper crystals. It is relatively nontoxic and has a low melting point just above 271 °C (520 °F), so crystals may be grown using a household stove, although the resulting crystals will tend to be of lower quality than lab-grown crystals.[32]
At ambient conditions, bismuth shares the same layered structure as the metallic forms ofarsenic andantimony,[28]: 767 crystallizing in therhombohedral lattice.[25]: 172 When compressed at room temperature, this Bi–I structure changes first to themonoclinic Bi-II at 2.55 GPa, then to thetetragonal Bi-III at 2.7 GPa, and finally to thebody-centered cubic Bi-V at 7.7 GPa. The corresponding transitions can be monitored via changes in electrical conductivity; they are rather reproducible and abrupt and are therefore used for calibration of high-pressure equipment.[33][34]
Bismuth is stable to both dry and moist air at ordinary temperatures. At sufficiently high temperatures, it can react with water vapor to make bismuth(III) oxide.[35]: 8
2 Bi + 3 H2O → Bi2O3 + 3 H2
It reacts withfluorine to formbismuth(V) fluoride at 500 °C (932 °F) orbismuth(III) fluoride at lower temperatures (typically from Bi melts); with otherhalogens it yields only bismuth(III) halides.[28]: 769–70 [36]: 559–61 [25]: 185 The trihalides are corrosive and easily react with moisture, formingoxyhalides with the formula BiOX.[35]: 9
The only primordialisotope of bismuth,bismuth-209, had long been regarded as the heaviest stable nuclide, but was suspected[39] on theoretical grounds to be unstable toalpha decay. This was finally demonstrated in 2003, when researchers at theInstitut d'astrophysique spatiale inOrsay, France, detected this decay; the best value of the half-life is now2.01×1019 years (3Bq/t),[40][41] over109 times longer than the estimatedage of the universe.[12] Due to its hugely long half-life, for all known medical and industrial applications, bismuth can be treated as stable. The radioactivity is of academic interest because bismuth is one of a few elements whose radioactivity was suspected and theoretically predicted before being detected in the laboratory.[12] Bismuth has the longest known α-decay half-life, thoughtellurium-128 has the longest known by any mode:double beta decay at about2.25×1024 years.[10]
Six isotopes of bismuth with short half-lives (210–215 inclusive, but not 210m) occur in the natural radioactivedecay chains ofactinium,radium,thorium, andneptunium; and more have been synthesized. (Though all primordial237Np has long since decayed, it is continually regenerated by (n,2n) knockout reactions on natural238U.)[42][43]
For medical use, bismuth-213 can be produced, as the parent isotopeactinium-225, by bombardingradium withbremsstrahlung photons from alinear particle accelerator. In 1997, an antibody conjugate with bismuth-213 (half-life 45.6 minutes, emitsalpha particles) was used to treat leukemia patients, and it has been used in other cancer treatment, for example, in thetargeted alpha therapy (TAT) experimental program.[44][45]
Chemically, bismuth resemblesarsenic andantimony, but is much less toxic.[24] In almost all known compounds, bismuth hasoxidation state +3; a few have states +5 or −3.
Thetrioxide[28]: 768 [36]: 553 andtrisulfide can both be made from the elements,[46][36]: 559–61 although the trioxide is extremely corrosive at high temperatures.[25]: 185 The pentoxide is not stable at room temperature, and will evolveO2 gas if heated.[47] Both oxides formcomplex anions,[48] andNaBiO3 is a strong oxidising agent.[36]: 578 The trisulfide is common in bismuthore.[46]
Similarly, bismuth forms all possible trihalides, but the only pentahalide isBiF5. All areLewis acids.[35]: 8 Bismuth forms several formally-BiI halides; these are complex salts with unusually structured polyatomic cations and anions.[48][49]
Bismuth oxychloride (BiOCl) structure (mineralbismoclite). Bismuth atoms are shown as grey, oxygen red, chlorine green.
In strongly acidicaqueous solution, theBi3+ ion solvates to formBi(H2O)3+8.[50] As pH increases, the cations polymerize until the octahedralbismuthyl complex[Bi6O4(OH)4]6+,[51] often abbreviatedBiO+. Althoughbismuth oxychloride andbismuth oxynitrate have stoichiometries suggesting the ion, they aredouble salts instead.[25]: 184 Bismuth nitrate hydrolysys in water, forming oxynitrate.
The reported abundance of bismuth in the Earth's crust varies significantly by source from 180ppb (similar to that of silver) to 8ppb (twice as common as gold). The most importantores of bismuth arebismuthinite andbismite.[22]Native bismuth is known from Australia, Bolivia, and China.[55][25]: 172–3
According to theUnited States Geological Survey (USGS), 10,200tonnes of bismuth were produced worldwide by mining and 17,100 tonnes by refining in 2016. Since then, USGS does not provide mining data for bismuth, considering them unreliable. Globally, bismuth is mostly produced by refining, as a byproduct of extraction of other metals such as lead, copper,tin,molybdenum andtungsten, though the refining-to-mining ratio depends on the country.[25]: 173 [58][59][60]
Bismuth travels in crude lead bullion (which can contain up to 10% bismuth) through several stages of refining, until it is removed by theKroll-Betterton process which separates the impurities as slag, or the electrolyticBetts process. Bismuth will behave similarly with another of its major metals, copper.[58] The raw bismuth metal from both processes contains still considerable amounts of other metals, foremost lead. By reacting the molten mixture with chlorine gas the metals are converted to their chlorides while bismuth remains unchanged. Impurities can also be removed by various other methods for example with fluxes and treatments yielding high-purity bismuth metal (over 99% Bi).[61]
World mine production and annual averages of bismuth price (New York, not adjusted for inflation).[62]
The price for pure bismuth metal was relatively stable through most of the 20th century, except for a spike in the 1970s. Bismuth has always been produced mainly as a byproduct of lead refining, and thus the price usually reflected the cost of recovery and the balance between production and demand.[62]
Before World War II, demand for bismuth was small and mainly pharmaceutical—bismuth compounds were used to treat such conditions as digestive disorders,sexually transmitted diseases and burns. Minor amounts of bismuth metal were consumed in fusible alloys forfire sprinkler systems andfuse wire. During World War II bismuth was considered astrategic material, used for solders, fusible alloys, medications and atomic research. To stabilize the market, the producers set the price at $1.25 per pound ($2.75 /kg) during the war and at $2.25 per pound ($4.96 /kg) from 1950 until 1964.[62]
In the early 1970s, the price rose rapidly due to increasing demand for bismuth as a metallurgical additive to aluminium, iron and steel. This was followed by a decline owing to increased world production, stabilized consumption, and the recessions of 1980 and 1981–1982. In 1984, the price began to climb as consumption increased worldwide, especially in the United States and Japan. In the early 1990s, research began on the evaluation of bismuth as a nontoxic replacement for lead in ceramic glazes, fishing sinkers, food-processing equipment, free-machiningbrasses for plumbing applications, lubricating greases, and shot forwaterfowl hunting.[35]: 14 Growth in these areas remained slow during the middle 1990s, in spite of the backing of lead replacement by the United States federal government, but intensified around 2005. This resulted in a rapid and continuing increase in price.[62]
Most bismuth is produced as a byproduct of other metal-extraction processes including the smelting of lead, and also of tungsten and copper. Itssustainability is dependent on increased recycling, which is problematic.[63]
It was once believed that bismuth could be practically recycled from the soldered joints in electronic equipment. Recent efficiencies in solder application in electronics mean there is substantially less solder deposited, and thus less to recycle. While recovering the silver from silver-bearing solder may remain economic, recovering bismuth is substantially less so.[64]
18th-century engraving of bismuth processing. During this era, bismuth was used to treat some digestive complaints.
Bismuth has few commercial applications, and those applications that use it generally require small quantities relative to other raw materials. In the United States, for example, 733 tonnes of bismuth were consumed in 2016, of which 70% went into chemicals (including pharmaceuticals, pigments, and cosmetics) and 11% into bismuth alloys.[61]
In the early 1990s, researchers began to evaluate bismuth as a nontoxic replacement for lead in various applications.[61]
Bismuth compounds (including sodium bismuth tartrate) were formerly used to treat syphilis.[72][73]Arsenic combined with either bismuth or mercury was a mainstay of syphilis treatment from the 1920s until the advent of penicillin in 1943.[74]
Bismuth oxychloride (BiOCl) is sometimes used in cosmetics, as a pigment in paint for eye shadows, hair sprays and nail polishes.[12][25]: 184 [76][77] This compound is found as the mineral bismoclite and in crystal form contains layers of atoms (see figure above) that refract light chromatically, resulting in aniridescent appearance similar tonacre of pearl. It was used as a cosmetic inancient Egypt and in many places since.Bismuth white (also "Spanish white") can refer to either bismuth oxychloride orbismuth oxynitrate (BiONO3), when used as a white pigment.[78]Bismuth vanadate is used as a light-stable non-reactive paint pigment (particularly for artists' paints), often as a replacement for the more toxic cadmium sulfide yellow and orange-yellow pigments. The most common variety in artists' paints is a lemon yellow, visually indistinguishable from its cadmium-containing alternative.[79]
Bismuth-basedtransistors have been claimed to enable smaller, faster, and more energy-efficient transistors than traditionalsilicon. Bismuth offers a small bandgap and high electron mobility. It hastopological insulator states, conducting along its surface/edges while still insulating internally.Two-dimensional semiconductor materials can be produced from it, enabling thinner and higher-performance devices. Such 2D bismuth materials support sub-nanometer channel lengths, surpassing silicon's practical limits. However, bismuth's anisotropic heat transport can complicate chip design.[80]
Bismuth telluride (Bi2Te3) has been investigated for use in thermoelectric transistors that use temperature gradients (e.g., via laser illumination) to generate electricity, yielding0.7093 μW in experimental setups. They operate by leveraging theSeebeck effect, using a temperature difference to drive charge carrier movement.[81]
Bismuth oxyselenide (Bi2O2Se andBi2SeO5) have been investigated for use infield-effect transistors (FETs). These 2D materials exhibit highelectron mobility (e.g.,10–15 cm2/(V·s)) and stability in air. One study reported that these materials enabled transistors that were 40% faster and 10% more efficient thanIntel's3 nm chips.[82][83]
Bismuth can reduce contact resistance when paired with 2D semiconductors such asMoS2. This eliminates the Schottky barrier—a common efficiency issue in metal-semiconductor interfaces.[84]
Bismuth is used in alloys with other metals such as tin and lead.Wood's metal, an alloy of bismuth, lead, tin, and cadmium, is used in automatic sprinkler systems for fires. It forms the largest part (50%) ofRose's metal, afusible alloy, which also contains 25–28% lead and 22–25% tin. It was also used to makebismuth bronze, which was used during theBronze Age, having been found in Inca knives atMachu Picchu.[85]
The density difference between lead (11.32 g/cm3) and bismuth (9.78 g/cm3) is small enough that for manyballistics and weighting applications, bismuth can substitute for lead. For example, it can replace lead as a dense material infishing sinkers. It has been used as a replacement for lead inshot, bullets andless-lethalriot gun ammunition. The Netherlands, Denmark, England, Wales, the United States, and many other countries now prohibit the use of lead shot for the hunting of wetland birds, as many birds are prone tolead poisoning owing to mistaken ingestion of lead (instead of small stones and grit) to aid digestion, or even prohibit the use of lead for all hunting, such as in the Netherlands. Bismuth-tin alloy shot is one alternative that provides similar ballistic performance to lead.[61]
Bismuth, as a dense element of high atomic weight, is used in bismuth-impregnated latex shields to shield from X-ray in medical examinations, such asCTs, mostly as it is considered non-toxic.[86]
The European Union'sRestriction of Hazardous Substances Directive (RoHS) for reduction of lead has broadened bismuth's use in electronics as a component of low-melting point solders, as a replacement for traditional tin-lead solders.[61] Its low toxicity will be especially important for solders to be used in food processing equipment and copper water pipes, although it can also be used in other applications including those in the automobile industry, in the European Union, for example.[87]
Bismuth has been evaluated as a replacement for lead in free-machiningbrasses for plumbing applications,[88] although it does not equal the performance of leaded steels.[87]
Many bismuthalloys have lowmelting points and are found in specialty applications such assolders. Many automatic sprinklers, electric fuses, and safety devices in fire detection and suppression systems contain the eutecticIn19.1-Cd5.3-Pb22.6-Sn8.3-Bi44.7 alloy that melts at 47 °C (117 °F)[22] This is a convenient temperature since it is unlikely to be exceeded in normal living conditions. Low-melting alloys, such as Bi-Cd-Pb-Sn alloy which melts at 70 °C (158 °F), are also used in automotive and aviation industries. Before deforming a thin-walled metal part, it is filled with a melt or covered with a thin layer of the alloy to reduce the chance of breaking. Then the alloy is removed by submerging the part in boiling water.[25]: 183
Bismuth is used to makefree-machining steels and free-machining aluminium alloys for precision machining properties. It has similar effect to lead and improves the chip breaking during machining. The shrinking on solidification in lead and the expansion of bismuth compensate each other and therefore lead and bismuth are often used in similar quantities.[89][90] Similarly, alloys containing comparable parts of bismuth and lead exhibit a very small change (on the order 0.01%) upon melting, solidification or aging. Such alloys are used in high-precision casting, e.g. in dentistry, to create models and molds.[25]: 183 Bismuth is also used as an alloying agent in production of malleable irons[61] and as athermocouple material.[22]
Bismuth is also used in aluminium-silicon cast alloys to refine silicon morphology. However, it indicated a poisoning effect on modification ofstrontium.[91][92] Some bismuth alloys, such asBi35-Pb37-Sn25, are combined with non-sticking materials such asmica, glass andenamels because they easily wet them allowing to make joints to other parts. Addition of bismuth to caesium enhances the quantum yield of caesium cathodes.[25]: 184 Sintering of bismuth and manganese powders at 300 °C (572 °F) produces a permanent magnet andmagnetostrictive material, which is used in ultrasonic generators and receivers working in the10–100 kHz range and in magnetic andholographic memory devices.[35]: 15
Bismuth is included inBSCCO (bismuth strontium calcium copper oxide), which is a group of similar superconducting compounds discovered in 1988 that exhibit the highest superconducting transition temperatures.[93]
Bismuth oxide, in its delta form, is a solid electrolyte for oxygen. This form normally breaks down below a high-temperature threshold, but can be electrodeposited well below this temperature in a highly alkaline solution.[95]
Bismuth germanate is a scintillator, widely used in X-ray and gamma ray detectors.[96]
Bismuth vanadate is an opaque yellow pigment used by some artists' oil,acrylic, and watercolor paint companies, primarily as a replacement for the more toxiccadmium sulfide yellows in the greenish-yellow (lemon) to orange-toned yellow range. It performs practically identically to the cadmium pigments, such as in terms of resistance to degradation from UV exposure, opacity, tinting strength, and lack of reactivity when mixed with other pigments. The most commonly used variety by artists' paint makers is lemon in color. In addition to being a replacement for several cadmium yellows, it also serves as a non-toxic visual replacement for the older chromate pigments made with zinc, lead, and strontium. If a green pigment and barium sulfate (for increased transparency) are added it can also serve as a replacement forbarium chromate, which possesses a more greenish cast than the others. In comparison withlead chromate, it does not blacken due tohydrogen sulfide in the air (a process accelerated by UV exposure) and possesses a particularly brighter color than them, especially the lemon, which is the most translucent, dull, and fastest to blacken due to the higher percentage of lead sulfate required to produce that shade. It is also used, on a limited basis due to its cost, as a vehicle paint pigment.[97][98] Bismuth vanadate can also be used as electrocatalyst for hydrogen peroxide synthesis.[99]
Bismuth tungstate can be used as photocatalyst for removal of phenolic compounds[100] as well as for hydrogen generation.[101]
Bismuth molybdate is a catalyst for propylene oxidation[102] as well as photocatalyst.[103]
As catalyst for the fluorination of arylboronic pinacol esters through a Bi(III)/Bi(V) catalytic cycle, mimicking transition metals in electrophilic fluorination.[108]
See alsobismuthia, a rare dermatological condition that results from the prolonged use of bismuth.
Scientific literature indicates that some of the compounds of bismuth are less toxic to humans via ingestion than other heavy metals (lead, arsenic, antimony, etc.)[12] presumably due to the comparatively low solubility of bismuth salts.[109] Itsbiological half-life for whole-body retention is reported to be 5 days but it can remain in the kidney for years in people treated with bismuth compounds.[110]
Bismuth poisoning can occur and has according to some reports been common in relatively recent times.[109][111] As with lead, bismuth poisoning can result in the formation of a black deposit on thegingiva, known as a bismuth line.[112][113][25]: 187–8 Poisoning may be treated withdimercaprol; however, evidence for benefit is unclear.[114][115]
Bismuth's environmental impacts are not well known; it may be less likely to bioaccumulate than some other heavy metals, and this is an area of active research.[116][117]
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