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Amorphous metal

An amorphous metal (also known as metallic glass or glassy metal) is a solid


metallic material, usually an alloy, with a disordered atomic-scale structure. Most
metals are crystalline in their solid state, which means they have a highly ordered
arrangement of atoms. Amorphous metals are non-crystalline, and have a glass-like
structure. But unlike common glasses, such as window glass, which are typically
electrical insulators, amorphous metals have good electrical conductivity. There are
several ways in which amorphous metals can be produced, includingextremely rapid
cooling, physical vapor deposition, solid-state reaction, ion irradiation, and
mechanical alloying.[1][2]
Samples of amorphous metal, with
millimeter scale
In the past, small batches of amorphous metals have been produced through a variety
of quick-cooling methods. For instance, amorphous metal ribbons have been
produced by sputtering molten metal onto a spinning metal disk (melt spinning). The rapid cooling, on the order of millions of
degrees a second, is too fast for crystals to form and the material is "locked" in a glassy state. More recently a number of alloys with
critical cooling rates low enough to allow formation of amorphous structure in thick layers (over 1 millimeter) have been produced;
these are known as bulk metallic glasses (BMG). More recently, batches of amorphous steel with three times the strength of
conventional steel alloys have been produced.

Contents
History
Properties
Applications
Modeling and theory
See also
References
External links

History
The first reported metallic glass was an alloy (Au75Si25) produced at Caltech by W. Klement (Jr.), Willens and Duwez in 1960.[3]
This and other early glass-forming alloys had to be cooled extremely rapidly (on the order of one megakelvin per second, 108 K/s) to
avoid crystallization. An important consequence of this was that metallic glasses could only be produced in a limited number of
forms (typically ribbons, foils, or wires) in which one dimension was small so that heat could be extracted quickly enough to achieve
the necessary cooling rate. As a result, metallic glass specimens (with a few exceptions) were limited to thicknesses of less than one
hundred micrometers.

In 1969, an alloy of 77.5% palladium, 6% copper, and 16.5% silicon was found to have critical cooling rate between 100 and 1000
K/s.

In 1976, H. Liebermann and C. Graham developed a new method of manufacturing thin ribbons of amorphous metal on a
supercooled fast-spinning wheel.[4] This was an alloy of iron, nickel, phosphorus and boron. The material, known as Metglas, was
commercialized in the early 1980s and is used for low-loss power distribution transformers (Amorphous metal transformer). Metglas-
2605 is composed of 80% iron and 20% boron, has Curie temperature of 373 °C and a room temperature saturation magnetization of
1.56 teslas.[5]

In the early 1980s, glassy ingots with 5 mm diameter were produced from the alloy of 55% palladium, 22.5% lead, and 22.5%
antimony, by surface etching followed with heating-cooling cycles. Usingboron oxide flux, the achievable thickness was increased to
a centimeter.

Research in Tohoku University[6] and Caltech yielded multicomponent alloys based on lanthanum, magnesium, zirconium,
palladium, iron, copper, and titanium, with critical cooling rate between 1 K/s to 100 K/s, compara
ble to oxide glasses.

In 1988, alloys of lanthanum, aluminium, and copper ore were found to be highly glass-forming. Al-based metallic glasses containing
[7]
Scandium exhibited a record-type tensile mechanical strength of about 1500 MPa.

In the 1990s new alloys were developed that form glasses at cooling rates as low as one kelvin per second. These cooling rates can be
achieved by simple casting into metallic molds. These "bulk" amorphous alloys can be cast into parts of up to several centimeters in
thickness (the maximum thickness depending on the alloy) while retaining an amorphous structure. The best glass-forming alloys are
based on zirconium and palladium, but alloys based on iron, titanium, copper, magnesium, and other metals are also known. Many
amorphous alloys are formed by exploiting a phenomenon called the "confusion" effect. Such alloys contain so many different
elements (often four or more) that upon cooling at sufficiently fast rates, the constituent atoms simply cannot coordinate themselves
into the equilibrium crystalline state before their mobility is stopped. In this way, the random disordered state of the atoms is "locked
in".

In 1992, the commercial amorphous alloy, Vitreloy 1 (41.2% Zr, 13.8% Ti, 12.5% Cu, 10% Ni, and 22.5% Be), was developed at
Caltech, as a part of Department of Energy and NASA research of new aerospace materials. More variants followed.

In 2004, bulk amorphous steel (actually rather cast iron owing to high C content) was successfully produced by two groups: one at
Oak Ridge National Laboratory, who refers to their product as "glassy steel", and the other at the University of Virginia, calling theirs
"DARVA-Glass 101".[8][9] The product is non-magnetic at room temperature and significantly stronger than conventional steel,
[10][11]
though a long research and development process remains before the introduction of the material into public or military use.

In 2018 a team at SLAC National Accelerator Laboratory, the National Institute of Standards and Technology (NIST) and
Northwestern University reported the use of artificial intelligence to predict and evaluate samples of 20,000 different likely metallic
[12][13]
glass alloys in a year. Their methods promise to speed up research and time to market for new amorphous metals alloys..

Properties
Amorphous metal is usually analloy rather than a pure metal. The alloys contain atoms of significantly different sizes, leading to low
free volume (and therefore up to orders of magnitude higher viscosity than other metals and alloys) in molten state. The viscosity
prevents the atoms moving enough to form an ordered lattice. The material structure also results in low shrinkage during cooling, and
resistance to plastic deformation. The absence ofgrain boundaries, the weak spots of crystalline materials, leads to better resistance to
wear[14] and corrosion. Amorphous metals, while technically glasses, are also much tougher and less brittle than oxide glasses and
ceramics.

Thermal conductivity of amorphous materials is lower than that of crystalline metal. As formation of amorphous structure relies on
fast cooling, this limits the maximum achievable thickness of amorphous structures.

To achieve formation of amorphous structure even during slower cooling, the alloy has to be made of three or more components,
leading to complex crystal units with higher potential energy and lower chance of formation. The atomic radius of the components
has to be significantly different (over 12%), to achieve high packing density and low free volume. The combination of components
should have negative heat of mixing, inhibiting crystal nucleation and prolonging the time the molten metal stays in supercooled
state.
The alloys of boron, silicon, phosphorus, and other glass formers with magnetic metals (iron, cobalt, nickel) have high magnetic
susceptibility, with low coercivity and high electrical resistance. Usually the conductivity of a metallic glass is of the same low order
of magnitude as of a molten metal just above the melting point. The high resistance leads to low losses by eddy currents when
subjected to alternating magnetic fields, a property useful for e.g.transformer magnetic cores. Their low coercivity also contributes to
low loss.

Amorphous metals have higher tensile yield strengths and higher elastic strain limits than polycrystalline metal alloys, but their
ductilities and fatigue strengths are lower.[15] Amorphous alloys have a variety of potentially useful properties. In particular, they
tend to be stronger than crystalline alloys of similar chemical composition, and they can sustain larger reversible ("elastic")
deformations than crystalline alloys. Amorphous metals derive their strength directly from their non-crystalline structure, which does
not have any of the defects (such asdislocations) that limit the strength of crystalline alloys. One modern amorphous metal, known as
Vitreloy, has a tensile strength that is almost twice that of high-grade titanium. However, metallic glasses at room temperature are not
ductile and tend to fail suddenly when loaded in tension, which limits the material applicability in reliability-critical applications, as
the impending failure is not evident. Therefore, there is considerable interest in producing metal matrix composites consisting of a
metallic glass matrix containing dendritic particles or fibers of a ductile crystalline metal.

Perhaps the most useful property of bulk amorphous alloys is that they are true glasses, which means that they soften and flow upon
heating. This allows for easy processing, such as by injection molding, in much the same way as polymers. As a result, amorphous
alloys have been commercialized for use in sports equipment, medical devices, and as cases for electronic equipment.

Thin films of amorphous metals can be deposited viahigh velocity oxygen fueltechnique as protective coatings.

Applications
Currently the most important application is due to the special magnetic properties of some ferromagnetic metallic glasses. The low
magnetization loss is used in high efficiency transformers (amorphous metal transformer) at line frequency and some higher
frequency transformers. Amorphous steel is a very brittle material which makes it difficult to punch into motor laminations.[16] Also
electronic article surveillance(such as theft control passive ID tags,) often uses metallic glasses because of these magnetic properties.

Amorphous metals exhibit unique softening behavior above their glass transition and this softening has been increasingly explored
for thermoplastic forming of metallic glasses.[17] Such low softening temperature allows for developing simple methods for making
composites of nanoparticles (e.g. carbon nanotubes) and BMGs. It has been shown that metallic glasses can be patterned on
[18] This may solve the problems ofnanoimprint lithography
extremely small length scales ranging from 10 nm to several millimeters.
where expensive nano-molds made of silicon break easily. Nano-molds made from metallic glasses are easy to fabricate and more
durable than silicon molds. The superior electronic, thermal and mechanical properties of BMGs compared to polymers make them a
field electron emissiondevices.[19]
good option for developing nanocomposites for electronic application such as

Ti40Cu36Pd14Zr10 is believed to be noncarcinogenic, is about three times stronger than titanium, and its elastic modulus nearly
matches bones. It has a high wear resistance and does not produce abrasion powder. The alloy does not undergo shrinkage on
solidification. A surface structure can be generated that is biologically attachable by surface modification using laser pulses, allowing
better joining with bone.[20]

Mg60Zn35Ca5, rapidly cooled to achieve amorphous structure, is being investigated, at Lehigh University, as a biomaterial for
implantation into bones as screws, pins, or plates, to fix fractures. Unlike traditional steel or titanium, this material dissolves in
organisms at a rate of roughly 1 millimeter per month and is replaced with bone tissue. This speed can be adjusted by varying the
content of zinc.[21]

Modeling and theory


Bulk metallic glasses (BMGs) have now been modeled using atomic scale simulations (within the density functional theory
framework) in a similar manner to high entropy alloys.[22][23] This has allowed predictions to be made about their behavior, stability
and many more properties. As such, new BMG systems can be tested, and tailored systems; fit for a specific purpose (e.g. bone
replacement or aero-engine component) without as muchempirical searching of the phase space and experimental trial and error.

See also
Bioabsorbable metallic glass
Glass-ceramic-to-metal seals
Liquidmetal
Materials science
Structure of liquids and glasses
Amorphous brazing foil

References
1. Some scientists only consider amorphous metals produced by rapid cooling from a liquid state to be glasses.
However, materials scientists commonly consider a glass to be any solid non-crystalline material, regardless of how
it is produced.
2. Ojovan, M. I.; Lee, W. B. E. (2010). "Connectivity and glass transition in disordered oxide systems".Journal of Non-
Crystalline Solids. 356 (44–49): 2534. Bibcode:2010JNCS..356.2534O(http://adsabs.harvard.edu/abs/2010JNCS..3
56.2534O). doi:10.1016/j.jnoncrysol.2010.05.012(https://doi.org/10.1016%2Fj.jnoncrysol.2010.05.012) .
3. Klement, W.; Willens, R. H.; Duwez, POL (1960). "Non-crystalline Structure in Solidified Gold-Silicon Alloys".Nature.
187 (4740): 869–870. Bibcode:1960Natur.187..869K (http://adsabs.harvard.edu/abs/1960Natur .187..869K).
doi:10.1038/187869b0 (https://doi.org/10.1038%2F187869b0).
4. Libermann H. & Graham C. (1976)."Production Of Amorphous Alloy Ribbons And Ef fects Of Apparatus Parameters
On Ribbon Dimensions"(http://ieeexplore.ieee.org/xpls/abs_all.jsp?isnumber=22822&arnumber=1059201&count=15
8&index=111). IEEE Transactions on Magnetics. 12 (6): 921. Bibcode:1976ITM....12..921L (http://adsabs.harvard.ed
u/abs/1976ITM....12..921L). doi:10.1109/TMAG.1976.1059201(https://doi.org/10.1109%2FTMAG.1976.1059201) .
5. Roya, R & Majumdara, A.K. (1981). "Thermomagnetic and transport properties of metglas 2605 SC and 2605".
Journal of Magnetism and Magnetic Materials
. 25: 83–89. Bibcode:1981JMMM...25...83R (http://adsabs.harvard.ed
u/abs/1981JMMM...25...83R). doi:10.1016/0304-8853(81)90150-5(https://doi.org/10.1016%2F0304-8853%2881%2
990150-5).
6. Inoue, A. (2000). "Stabilization of metallic supercooled liquid and bulk amorphous alloys".
Acta Materialia. 48: 279–
306. doi:10.1016/S1359-6454(99)00300-6(https://doi.org/10.1016%2FS1359-6454%2899%2900300-6) .
7. Inoue, A.; Sobu, S.; Louzguine, D. V.; Kimura, H.; Sasamori, K. (2011). "Ultrahigh strength Al-based amorphous
alloys containing Sc". Journal of Materials Research. 19 (5): 1539. Bibcode:2004JMatR..19.1539I (http://adsabs.harv
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8. U.Va. News Service, "University Of Virginia Scientists Discover Amorphous Steel Material is three times stronger
than conventional steel and non-magnetic"(http://www.virginia.edu/topnews/releases2004/poon-july-2-2004.html),
U.Va. News Services, 7/2/2004
9. Google Patents listing for Patent WO 2006091875 A2,"Patent WO 2006091875 A2 - Amorphous steel composites
with enhanced strengths, elastic properties and ductilities (Also published as US20090025834, WO2006091875A3)"
(http://www.google.com/patents/WO2006091875A2?cl=en), Joseph S Poon, Gary J Shiflet, Univ Virginia, 8/31/2006
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11. Ponnambalam, V.; Poon, S. J.; Shiflet, G. J. (2011). "Fe-based bulk metallic glasses with diameter thickness larger
than one centimeter". Journal of Materials Research. 19 (5): 1320. Bibcode:2004JMatR..19.1320P (http://adsabs.har
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covery-metallic-glass.html). Physorg. April 13, 2018. Retrieved 2018-04-14.
13. Ren, Fang; Ward, Logan; Williams, Travis; Laws, Kevin J.; Wolverton, Christopher; Hattrick-Simpers, Jason; Mehta,
Apurva (2018-04-01). "Accelerated discovery of metallic glasses through iteration of machine learning and high-
throughput experiments"(http://advances.sciencemag.org/content/4/4/eaaq1566) . Science Advances. 4 (4):
eaaq1566. doi:10.1126/sciadv.aaq1566 (https://doi.org/10.1126%2Fsciadv.aaq1566). ISSN 2375-2548 (https://www.
worldcat.org/issn/2375-2548). PMID 29662953 (https://www.ncbi.nlm.nih.gov/pubmed/29662953).
14. Gloriant, Thierry (2003)."Microhardness and abrasive wear resistance of metallic glasses and nanostructured
composite materials" (https://doi.org/10.1016/S0022-3093(02)01941-5)
. Journal of Non-Crystalline Solids. 316 (1):
96–103. Bibcode:2003JNCS..316...96G (http://adsabs.harvard.edu/abs/2003JNCS..316...96G) . doi:10.1016/s0022-
3093(02)01941-5 (https://doi.org/10.1016%2Fs0022-3093%2802%2901941-5) .
15. Russell, Alan & Lee, Kok Loong (2005).Structure-Property Relations in Nonferrous Metals(https://books.google.co
m/books?id=fIu58uZTE-gC). John Wiley & Sons. p. 92. ISBN 9780471708537.
16. Ning, S. R.; Gao, J.; Wang, Y. G. (2010). "Review on Applications of Low Loss Amorphous Metals in Motors".
Advanced Materials Research. 129-131: 1366. doi:10.4028/www.scientific.net/AMR.129-131.1366 (https://doi.org/10.
4028%2Fwww.scientific.net%2FAMR.129-131.1366).
17. Saotome, Y.; Iwazaki, H. (2000). "Superplastic extrusion of microgear shaft of 10 μm in module".
Microsystem
Technologies. 6 (4): 126. doi:10.1007/s005420050180(https://doi.org/10.1007%2Fs005420050180).
18. Kumar, G.; Tang, H. X.; Schroers, J. (2009). "Nanomoulding with amorphous metals".Nature. 457 (7231): 868–872.
Bibcode:2009Natur.457..868K (http://adsabs.harvard.edu/abs/2009Natur .457..868K). doi:10.1038/nature07718 (http
s://doi.org/10.1038%2Fnature07718). PMID 19212407 (https://www.ncbi.nlm.nih.gov/pubmed/19212407).
19. Hojati-Talemi, Pejman (2011). "High performance bulk metallic glass/carbon nanotube composite cathodes for
electron field emission".Applied Physics Letters. 99 (19): 194104. Bibcode:2011ApPhL..99s4104H(http://adsabs.ha
rvard.edu/abs/2011ApPhL..99s4104H). doi:10.1063/1.3659898 (https://doi.org/10.1063%2F1.3659898).
20. Maruyama, Masaaki (June 11, 2009)."Japanese Universities Develop Ti-based Metallic Glass for Artificial Finger
Joint" (http://techon.nikkeibp.co.jp/english/NEWS_EN/20090610/171551/?P=1)
. Tech-on.
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. Institute of Physics. October
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22. King, D.M.; Middleburgh, S.C.; Liu, A.C.Y.; Tahini, H.A.; Lumpkin, G.R.; Cortie, M. (January 2014). "Formation and
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External links
Liquidmetal Design Guide
"Metallic glass: a drop of the hard stuff" at New Scientist
Glass-Like Metal Performs Better Under StressPhysical Review Focus, June 9, 2005
"Overview of metallic glasses"
New Computational Method Developed By Carnegie Mellon University Physicist Could Speed Design andesting
T of
Metallic Glass (2004) (the alloy database developed by Marek Mihalkovic, Michael Widom, and others)
Materials Today: The case for bulk metallic glass
New tungsten-tantalum-copper amorphous alloy developed at the Korea Advanced Institute of Science and
Technology [1]
Amorphous Metals in Electric-Power Distribution Applications
Amorphous and Nanocrystalline Soft Magnets
glass transition temperatures of bulk metallic glasses
"New metallic glass material created by starving it of nuclei"
. newatlas.com. Retrieved 2017-12-09.

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