Mechanical properties of nanocrystalline materials

Understanding the correlation between magnetic properties and nanostructure involves collaborative efforts between chemists, physicists, and materials scientists to study both fundamental properties and potential applications. This article introduces a classification of nanostructure morphology according to the mechanism responsible for the magnetic properties. The fundamental magnetic properties of interest and the theoretical frameworks developed to model these properties are summarized. Common chemical and physical techniques for the fabrication of magnetic nanostructures are surveyed, followed by some examples of recent investigations of magnetic systems with structure on the nanometer scale. The article concludes with a brief discussion of some promising experimental techniques in synthesis and measurements.

Magnetic Properties of Nanostructured Materials

The creation of perfect nanometer-scale crystallites (nanocrystals), identically replicated in unlimited quantities, in a state that can be manipulated and understood as pure macromolecular substances, is an ultimate challenge of modern materials research with outstanding fundamental and potential technological consequences.[’l We report on the prediction, isolation, and characterization of a series of gold nanocrystals, passivated by self-assembled monolayers (SAMs) of straight-chain alkylthiolate molecules (RS, R

Nanocrystal gold molecules

A variety of spray pyrolysis (SP) techniques have been developed to directly produce ceramic powders from solutions. This paper reviews the current status of these processes in terms of the process parameters that enable the formation of particles with controlled morphology and composition. A model incorporating solute diffusion in the droplet and solvent evaporation from the droplet surface is presented to establish the critical parameters leading to solid particle formation. The model illustrates that solid particles can be obtained if solutes with high solubility and a large difference between the critical supersaturation and equilibrium concentration are used and if the process is designed to avoid solvent boiling. It is demonstrated that mixed metal oxide, non-oxide, and composite particles that are solid, hollow, porous, or fibrous can be produced by modifying the precursor characteristics, solution properties, and process parameters. The physical and chemical flexibility of SP processes offers numerous opportunities for the controlled synthesis of advanced ceramic powders and films. However, production rates are limited by the need to produce <5-[mu]m-diameter droplets and to avoid subsequent droplet coagulation. Developments in process controls, atomization, and system design are required for wider commercialization of SP-type processes.

Ceramic Powder Synthesis by Spray Pyrolysis

A method is presented to determine the absolute hydration enthalpy of the proton, ΔHaq°[H+], from a set of cluster-ion solvation data without the use of extra thermodynamic assumptions. The absolute proton hydration enthalpy has been found to be ∼50 kJ/mol different than traditional values and has been more precisely determined (by about an order of magnitude). Conventional ion solvation properties, based on the standard heat of formation of H+(aq) set to zero, have been devised that may be confusing to the uninitiated but are useful in thermochemical evaluations because they avoid the unnecessary introduction of the larger uncertainties in our knowledge of absolute values. In a similar strategy, we have motivated the need for a reassessment of ΔHaq°[H+] by the trends with increased clustering in conventional cluster-ion solvation enthalpy differences for pairs of oppositely charged cluster ions. The consequences of particular preferred values for ΔHaq°[H+] may be evaluated with regard to cluster-ion prop...

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The Proton's Absolute Aqueous Enthalpy and Gibbs Free Energy of Solvation from Cluster-Ion Solvation Data

The Panel was charged with assessing the present scientific understanding of the size-dependent physical and chemical properties of clusters, the methods of synthesis of macroscopic amounts of size-selected clusters with desired properties, and most importantly, the possibility of their controlled assembly into new materials with novel properties. The Panel was composed of both academic and industrial scientists from the physics, chemistry, and materials science communities, and met in January 1988.In materials (insulators, semiconductors, and metals) with strong chemical bonding, there is extensive spatial delocalization of valence electrons, and therefore the bulk physical properties which depend upon these electrons develop only gradually with cluster size. Recent research using supersonic-jet, gas-aggregation, colloidal, and chemical-synthetic methods indeed clearly establishes that intermediate size clusters have novel and hybrid properties, between the molecular and bulk solid-state limits. A scientific understanding of these transitions in properties has only been partially achieved, and the Panel believes that this interdisciplinary area of science is at the very heart of the basic nature of materials. In Sec. V (Future Challenges and Opportunities), a series of basic questions for future research are detailed. Each question has an obvious impact on our potential ability to create new materials.Present methods for the synthesis of useful amounts of size-selected clusters, with surface chemical properties purposefully controlled and/or modified, are almost nonexistent, and these fundamentally limit our ability to explore the assembly of clusters into potentially novel materials. While elegant spectroscopic and chemisorption studies of size-selected clusters have been carried out using molecular-beam technologies, there are no demonstrated methods for recovery and accumulation of such samples. Within the past year, the first reports of the chemical synthesis of clusters with surfaces chemically modified have been reported for limited classes of materials. Apparatus for the accumulation and consolidation of nanophase materials have been developed, and the first promising studies of their physical properties are appearing. In both the chemical and nanophase synthesis areas, clusters with a distribution of sizes and shapes are being studied. Progress on macroscopic synthetic methods for size-selected clusters of controlled surface properties is the most important immediate goal recognized by the Panel. Simultaneous improvement in physical characterization will be necessary to guide synthesis research.Assuming such progress will occur, the Panel suggests that self-assembly of clusters into new elemental polymorphs and new types of nanoscale heterogeneous materials offers an area of intriguing technological promise. The electrical and optical properties of such heterogeneous materials could be tailored in very specific ways. Such ideas are quite speculative at this time; their implementation critically depends upon controlled modification of cluster surfaces, and upon development of characterization and theoretical tools to guide experiments.The Panel concluded that a number of genuinely novel ideas had been enunciated, and that in its opinion some would surely lead to exciting new science and important new materials.

W. L. Brown

Papers

Research opportunities on clusters and cluster-assembled materials—A Department of Energy, Council on Materials Science Panel Report