The following article is based on the MRS Medal talk presented by William L. Johnson at the 1998 MRS Fall Meeting on December 2, 1998. The MRS Medal is awarded for a specific outstanding recent discovery or advancement that has a major impact on the progress of a materials-related field. Johnson received the honor for his development of bulk metallic glass-forming alloys, the fundamental understanding of the thermodynamics and kinetics that control glass formation and crystallization of glass-forming liquids, and the application of these materials in engineering.

The development of bulk glass-forming metallic alloys has led to interesting advances in the science of liquid metals. This article begins with brief remarks about the history and background of the field, then follows with a discussion of multicomponent glass-forming alloys and deep eutectics, the chemical constitution of these new alloys, and how they differ from metallic glasses of a decade ago or earlier. Recent studies of deeply undercooled liquid alloys and the insights made possible by their exceptional stability with respect to crystallization will then be discussed. Advances in this area will be illustrated by several examples. The article then describes some of the physical and specific mechanical properties of bulk metallic glasses (BMGs), and concludes with some interesting potential applications.

The first liquid-metal alloy vitrified by cooling from the molten state to the glass transition was Au-Si, as reported by Duwez at Caltech in 1960. Duwez made this discovery as a result of developing rapid quenching techniques for chilling metallic liquids at very high rates of 105–106 K/s.

The study of processing stimulated by synchrotron radiation (SR) started about 13 years ago. Unfortunately, for semiconductor processing, the reaction rate of this technique was considered to be too slow for practical applications. However the situation is rapidly changing as device dimensions shrink to the nanometer range, which requires high controllability and low defect densities, but is not so reliant on quick processing since much less material is involved. SR etching—which has a typical etching rate of 1–10 nm/min, capability of high-resolution etching due to the short wavelength of SR photons, high controllability, low damage production, and a clean reaction system—is considered to be extremely suitable for nanometer processing.

The benefit of SR etching is that it has unique material selectivities. However the mechanisms for the selectivity are not yet clarified. Consideration of the future application of the SR process to nanometer structure fabrication is dependent upon the development of in situ observation techniques that can evaluate the reaction surface at an atomic or molecular level. Recently we have developed an in situ observation technique: infrared reflection absorption spectroscopy using buried metal layer substrates (BML-IRRAS), which is especially suitable for in situ monitoring of beam-induced reactions on the semiconductor surface in high vacuum.

The reduction of grain size to the nanometer range (˜2-100 nm) has led to many interesting materials properties, including those involving mechanical behavior. In the case of metals, the Hall-Petch equation, which relates the yield stress to the inverse square root of the grain size, predicts great increases in strength with grain refinement. On the other hand, theory indicates that the high volume fraction of interfacial regions leads to increased deformation by grain-boundary sliding in metals with grain size in the low end of the nanocrystalline range. Nanocrystalline ceramics also have desirable properties. Chief among these are lower sintering temperatures and enhanced strain to failure. These two properties acting in combination allow for some unique applications, such as low-temperature diffusion bonding (the direct joining of ceramics to each other using moderate temperatures and pressures). Mechanical properties sometimes are affected by the fact that ceramics in a fine-grained form are stable in a different (usually higher pressure) phase than that which is considered “normal” for the ceramic. To the extent that the mechanical properties of a ceramic are dependent on its crystal-lographic structure, these differences will become evident at the smaller size scales.

It is uncertain how deformation takes place in very fine-grained nanocrystalline materials. It has been recognized for some time that the Hall-Petch relationship, which usually is explained on the basis of dislocation pileups at grain boundaries, must break down at grain sizes such that a grain cannot support a pileup. Even some of the basic assumptions of dislocation theory may no longer be appropriate in this size regime. Recently considerable progress has been made in simulating the behavior of extremely fine-grained metals under stress using molecular-dynamics techniques. Molecular-dynamics (MD) simulations of deformation in nanophase Ni and Cu were carried out in the temperature range of 300–500 K, at constant applied uniaxial tensile stresses between 0.05 GPa and 1.5 GPa, on samples with average grain sizes ranging from 3.4 nm to 12 nm.

Soon after the identification of carbon nanotubes, produced by arc-discharge techniques, the possibility of introducing metals into the inner core of the tubes was considered (Figure 1). This idea followed logically from the successful observation of fullerenes containing endohedral metals. The introduction of metals or metal carbides and oxides into multiwalled nanotubes [usually 2–70 nm outside diameter (OD), <60 microns in length] may significantly alter their conducting, electronic, and mechanical properties, arising from the internal framework within these structures. Early theoretical work predicted that all carbon open nanotubes could behave as “molecular straws.” In this context, Ajayan and lijima were the first to introduce Pb by heating the metal with open-ended nanotubes (sometimes in the presence of oxygen). Capillarity, wetting, and surface tension play an important role in the process; other elements such as Bi, Cs, S, and Se were also introduced into nanotubes in this way. Generally, the filling of open nanotubes by capillary action is confined to low surface-tension substances. Alternative methods of encapsulating other materials within nanotubes have now been developed, including chemical treatment, arc discharge, catalyzed hydrocarbon pyrolysis, and electrochemical techniques. In addition, carbon nanotubes can be used as reactive templates to generate novel metal carbide and nitride nanorods. These developments represent only the tip of the iceberg, because numerous noncarbon materials (e.g., Si, SiOx, SiC, MoS2, WS2, etc.) are able to form novel nanowires and fullerene-like morphologies. This review discusses methods for generating these fascinating structures and evaluates their possible applications in materials science and engineering.

During the last three decades, various thermodynamic databases have been compiled to be applied mainly to the calculation of phase diagrams of alloys, salts, and oxides. The accumulation and assessment of thermodynamic data and phase-equilibrium information to establish those databases is sometimes called the CALPHAD (calculated phase diagram) approach. The CALPHAD approach has been recognized as useful in various aspects of materials science and engineering. In addition to the use of thermodynamic databases for the calculation of phase diagrams, it would be very desirable to apply them to the calculation of other physicochemical quantities, such as surface tension. By doing this, not only can the Utility of databases be enlarged, but also a deeper understanding of the physical properties in question can be reached.

On the basis of the concepts just mentioned, we have applied those thermodynamic databases to the calculation of the surface tension of liquid alloys and molten ionic mixtures. In these calculations, we have applied Butler's equation for the surface tension of liquid alloys. In addition, we have modified Butler's equation to be extended to molten ionic mixtures by considering the relaxation structure in the surface. These approaches will lead us to develop a multifunctional data-bank System that will be widely applicable in the evaluation of physicochemical properties of liquid alloys and molten ionic mixtures from thermodynamic data.

In this article, we explain some physical modeis for the surface tension and viscosity of liquid alloys and molten ionic mixtures, in which thermodynamic data can be directly applied to evaluate these physical properties. In addition, the concept for the just-mentioned multifunctional thermodynamic data-bank System will be described by demonstrating the simultaneous calculation of phase diagrams, surface tension, and viscosity of some alloys used for new, Pb-free soldering materials.

The vulnerabilities inherent in choosing an innovative material for a design can make for technological catastrophe. The points of weakness are not dependent on the technical nature of the innovation, but instead are intrinsic to human problem-solving and decision-making. We present a computational approach for managing and containing this fallibility using ideas from cognitive science and artificial intelligence, in particular, understanding how the boundedly rational behavior of humans and organizations leads to specific kinds of errors that affect the choice and use of materials.

Materials choice in an industrial setting is often the result of a long chain or network of circumstances whose origins lie in many domains—from traditional engineering practice to the very latest innovation, from the commercial to the technical. In turn, every materials-selection decision has a long chain of consequences that are difficult to compute. This lengthy chain of consequences of a single decision gives rise to numerous points of error. What is particularly troublesome about these errors is not that they arise because of incomplete scientific engineering knowledge, but rather that they occur in spite of the fact that all (or at least, almost all) of the technically relevant information is available and sometimes even known to the technical personnel on the project. We will illustrate this approach by using a historical example of a major materials failure. Advances in database-systems design present an opportunity for integrating the ontology of material attributes with properties data. This may enable the design of more appropriate validation procedures required in proving a material for an artifact.

The human eye places remarkably stringent requirements on the devices we use to illuminate objects or generate images. Exceedingly small deviations in color or contrast from what we consider natural are easily judged by the brain to be fake. Such cognition drives consumer practice, so great efforts have been made for over a century to synthesize emissive materials that match the response functions associated with the human perception of color. This is an extremely difficult task, given the diverse range of considerations, some of which include whether (1) the display is viewed under artificial light or natural sunlight, (2) the images are stationary or moving, and (3) the rendering of depth in a two-dimensional image is believable.

Established technologies including cathode-ray tubes (CRTs), vacuum fluorescent displays (VFDs), lamps, and x-ray phosphors have made possible a wide variety of display and imaging devices. However, continued advances are required to increase brightness, contrast, color purity, resolution, lifetime, and viewing angle while still lessening the cost, weight, volume, and power consumption. Mature or emerging technologies that address these issues include thin-film electroluminescent (TFEL) displays, liquid-crystal displays (LCDs),8 field-emission displays (FEDs),9 and plasma displays (PDs).10-12 Each of these technologies uses luminescent materials consisting typically of an activator from which light is emitted and a host for low concentrations of the activator (typically >1% activator). The requirements of the host and activator are discussed in a later section. The luminescent material can exhibit either a narrow emission spectrum, useful for color displays, or a broadband emission, which can extend into multiple colors. In addition, with multiple activator/host combinations, a luminescent material can emit several colors and even white light. While LCDs are light valves, which may be used in a reflective mode and therefore do not require a luminescent material, low-light situations require a backlight generated by a luminescent material. Many of the most versatile, efficient activators are rare-earth (RE) elements, for reasons that will be discussed. The ability of RE ions to emit red, green, and blue light make them well suited for application in visible-display technologies. This article reviews dopant and host material systems, excitation mechanisms, and the factors that limit the achievable luminescent intensity and efficiency. Device configurations for modern displays are discussed, as are materials and structures for next-generation technologies. Since each display technology has different performance and operational requirements, only the basic characteristics will be discussed here to enable an appreciation of emission from RE activators. References to the literature are supplied to further direct the reader to more in-depth discussions.