Amorphous metal
An amorphous metal (also known as metallic glass, glassy metal, or shiny metal) is a solid metallic material, usually an alloy, with 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 and can show metallic luster.
There are several ways in which amorphous metals can be produced, including extremely rapid cooling, physical vapor deposition, solid-state reaction, ion irradiation, and mechanical alloying.
History
The first reported metallic glass was an alloy (Au75Si25) produced at Caltech by W. Klement (Jr.), Willens and Duwez in 1960.
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.
In the early 1980s, glassy ingots with a diameter of 5 mm (0.20 in) were produced from the alloy of 55% palladium, 22.5% lead, and 22.5% antimony, by surface etching followed with heating-cooling cycles. Using boron oxide flux, the achievable thickness was increased to a centimeter.
In 1982, a study on amorphous metal structural relaxation indicated a relationship between the specific heat and temperature of (Fe0.5Ni0.5)83P17. As the material was heated up, the properties developed a negative relationship starting at 375 K, which was due to the change in relaxed amorphous states. When the material was annealed for periods from 1 to 48 hours , the properties developed a positive relationship starting at 475 K for all annealing periods, since the annealing induced structure disappears at that temperature.
In 1988, alloys of lanthanum, aluminium, and copper ore were found to be highly glass-forming. Al-based metallic glasses containing Scandium exhibited a record-type tensile mechanical strength of about 1,500 MPa (220 ksi).
Before new techniques were found in 1990, bulk amorphous alloys of several millimeters in thickness were rare, except for a few exceptions, Pd-based amorphous alloys had been formed into rods with a 2 mm (0.079 in) diameter by quenching,
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.
By 2000, research in Tohoku University
In 2004, bulk amorphous steel 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".
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 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 an alloy 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 of grain boundaries, the weak spots of crystalline materials, leads to better resistance to wear
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.
As temperatures change, the electrical resistivity of amorphous metals behaves very different than that of regular metals. While the resistivity in regular metals generally increases with temperature, following the Matthiessen's rule, the resistivity in a large number of amorphous metals is found to decrease with increasing temperature. This is effect can be observed in amorphous metals of high resistivities between 150 and 300 microohm-centimeters.
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 electrical 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.
The superconductivity of amorphous metal thin films was discovered experimentally in the early 1950s by Buckel and Hilsch.
Amorphous metals have higher tensile yield strengths and higher elastic strain limits than polycrystalline metal alloys, but their ductilities and fatigue strengths are lower.
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,
Thin films of amorphous metals can be deposited via high velocity oxygen fuel technique as protective coatings.
Applications
Commercial
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.
A 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.
Ti-based metallic glass, when made into thin pipes, have a high tensile strength of 2,100 MPa (300 ksi), elastic elongation of 2% and high corrosion resistance.
Zr-Al-Ni-Cu based metallic glass can be shaped into 2.2 to 5 by 4 mm (0.087 to 0.197 by 0.157 in) pressure sensors for automobile and other industries, and these sensors are smaller, more sensitive, and possess greater pressure endurance compared to conventional stainless steel made from cold working. Additionally, this alloy was used to make the world's smallest geared motor with diameter 1.5 and 9.9 mm (0.059 and 0.390 in) to be produced and sold at the time.
Potential
Amorphous metals exhibit unique softening behavior above their glass transition and this softening has been increasingly explored for thermoplastic forming of metallic glasses.
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.
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.
Bulk metallic glasses also seem to exhibit superior properties like SAM2X5-630 which has the highest recorded elastic limit for any steel alloy, according to the researcher, essentially it has the highest threshold limit at which a material can withstand an impact without deforming permanently(plasticity). The alloy can withstand pressure and stress of up to 12.5 GPa (123,000 atm) without undergoing any permanent deformation, this is the highest impact resistance of any bulk metallic glass ever recorded (as of 2016) .This makes it as an attractive option for Armour material and other applications which requires high stress tolerance.
Additive manufacturing
One challenge when synthesising a metallic glass is that the techniques often only produce very small samples, due to the need for high cooling rates. 3D-printing methods have been suggested as a method to create larger bulk samples. Selective laser melting (SLM) is one example of an additive manufacturing method that has been used to make iron based metallic glasses.
Modeling and theory
Bulk metallic glasses have been modeled using atomic scale simulations (within the density functional theory framework) in a similar manner to high entropy alloys.