Amorphous metal

Samples of amorphous metal, with millimeter scale

An amorphous metal is a metallic material with a disordered atomic-scale structure. In contrast to most metals, which are crystalline and therefore have a highly ordered arrangement of atoms, amorphous alloys are non-crystalline. Materials in which such a disordered structure is produced directly from the liquid state during cooling are called "glasses", and so amorphous metals are commonly referred to as "metallic glasses" or "glassy metals". However, there are several ways besides extremely rapid cooling in which amorphous metals can be produced, including physical vapor deposition, solid-state reaction, ion irradiation, and mechanical alloying. Some scientists do not consider amorphous metals produced by these techniques to be glasses. However, materials scientists commonly consider amorphous alloys to be a single class of materials, regardless of how they are prepared.

In the past, small batches of amorphous metals have been produced through a variety of quick-cooling methods. For instance, amorphous metal wires 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) had been produced; these are known as bulk metallic glasses (BMG). Liquidmetal sells a number of titanium-based BMGs, developed in studies originally carried out at Caltech. More recently, batches of amorphous steel have been produced that demonstrate strengths much greater than conventional steel alloys.

History

The first reported metallic glass was an alloy (Au₇₅Si₂₅) produced at Caltech by W. Klement (Jr.), Willens and Duwez in 1960.^[1] This and other early glass-forming alloys had to be cooled extremely rapidly (on the order of one megakelvin per second, 10⁶ 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 to 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.^[2] This was an alloy of iron, nickel, phosphorus and boron. The material, known as Metglas, was commercialized in early 1980s and 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.^[3]

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. Using boron oxide flux, the achievable thickness was increased to a centimeter.

The research in Tohoku University 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, comparable to oxide glasses.

In 1988, alloys of lanthanum, aluminium, and copper ore were found to be highly glass-forming.

In the 1990s, however, 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 first 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.^{[citation needed]}

In 2004, two groups succeeded in producing bulk amorphous steel, one at Oak Ridge National Laboratory, the other at University of Virginia. The Oak Ridge group refers to their product as "glassy steel". The product is non-magnetic at room temperature and significantly stronger than conventional steel, though a long research and development process remains before the introduction of the material into public or military use.^[4][5]

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 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 crystals. 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 prolongs 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) are magnetic, with low coercivity and high electrical resistance. 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.

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 as dislocations) 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 composite materials 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 via high velocity oxygen fuel technique as protective coatings.

Applications

Amorphous metals (metallic glasses) exhibit unique softening behavior above their glass transition and this softening has been increasingly explored for thermoplastic forming of metallic glasses.

It has been shown that metallic glasses can be patterned on extremely small length scales ranging from 10 nm to several millimeters.^[6] It has been suggested that this may solve the problems of nanoimprint lithography 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.

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.^[7]

Mg₆₀Zn₃₅Ca₅, rapidly cooled to achieve amorphous structure, is being investigated 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.^[8]

Currently the most important application is due to the special magnetic properties of some amorphous glasses. The low magnetization loss is used in high efficiency transformers (Amorphous metal transformer) at line frequency and some higher frequency transformers. Also Electronic article surveillance often use metallic glasses.

References

1. ^ Klement, W.; Willens, R. H.; Duwez, POL (1960). "Non-crystalline Structure in Solidified Gold-Silicon Alloys". Nature 187 (4740): 869–870. doi:10.1038/187869b0. 
2. ^ Libermann H. and Graham C. (1976). "Production Of Amorphous Alloy Ribbons And Effects Of Apparatus Parameters On Ribbon Dimensions". IEEE Transactions on Magnetics 12 (6): 921. doi:10.1109/TMAG.1976.1059201. http://ieeexplore.ieee.org/xpls/abs_all.jsp?isnumber=22822&arnumber=1059201&count=158&index=111. 
3. ^ Roya, R and A.K. Majumdara (1981). "Thermomagnetic and transport properties of metglas 2605 SC and 2605". Journal of Magnetism and Magnetic Materials 25: 83–89. doi:10.1016/0304-8853(81)90150-5. 
4. ^ "Glassy Steel". ORNL Review 38 (1). 2005. http://www.ornl.gov/info/ornlreview/v38_1_05/article17.shtml. 
5. ^ V. Ponnambalam, S. Joseph Poon and Gary J. Shiflet (2004). "Fe-based bulk metallic glasses with diameter thickness larger than one centimeter". Journal of Materials Research 19 (5): 1320. Bibcode 2004JMatR..19.1320P. doi:10.1557/JMR.2004.0176. http://lucy.mrs.org/publications/jmr/jmra/2004/may/0176.html. 
6. ^ Golden Kumar, Hong Tang, and Jan Schroers (Feb 2009). "Nanomoulding with amorphous metals". Nature 457 (7231): 868–72. doi:10.1038/nature07718. PMID 19212407. 
7. ^ Masaaki Maruyama (Jun 11, 2009). "Japanese Universities Develop Ti-based Metallic Glass for Artificial Finger Joint". Tech-on. http://techon.nikkeibp.co.jp/english/NEWS_EN/20090610/171551/?P=1. 
8. ^ "Fixing bones with dissolvable glass". Institute of Physics. October 1, 2009. http://physicsworld.com/cws/article/news/40573. 

External links

• "Metallic glass: a drop of the hard stuff" at New Scientist
• Glass-Like Metal Performs Better Under Stress Physical Review Focus, June 9, 2005
• "Overview of metallic glasses"
• New Computational Method Developed By Carnegie Mellon University Physicist Could Speed Design and Testing 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

See also

• Glass-ceramic-to-metal seals
• Materials science
• Bioabsorbable metallic glass