Nanostructured materials are finding increasing applications. In characterizing the nanostructured materials, we have developed a technique using a conventional TEM to characterize the nanostructure. The technique is named selected reflection imaging and could be used for measuring the grain size, measuring the volume fraction of a second phase in a dual phase material, measuring the texture and identifying the crystal structure in multiphase materials.

The technique is evolved from dark field imaging which is known to generate strong contrast. In conventional materials with a grain size larger than 1 μm, selected area diffraction pattern is from a single crystal. Dark field image could be formed by allowing one of the diffracted beam to go through the objective aperture. In nanostructured materials, however, the diffraction pattern becomes a ring pattern. Ordinary dark field image could be formed by allowing one of the spot in the ring to go through the aperture. However, only a limited number of grains are differentiated from the rest.

Aluminum-copper-magnesium alloys also containing manganese and iron (commercial designation 2024) are susceptible to marine corrosion and stress corrosion cracking. Susceptibility depends on heat treatment, and is thought to involve redistribution of copper from within the microstructure onto the surface of the corroding alloy, but few direct observations of the mechanism have been made. Copper can be distributed in several ways throughout the microstructure, which complicates mechanism studies. The primary age-hardening phase is Al2CuMg (orthorhombic; a=4.01, b=9.25, c=7.15 Å) which appears as more or less large equiaxed S particles at equilibrium, and as metastable S’ plates after aging for shorter times at lower temperature (∼190°C). In addition, ubiquitous so-called “dispersoids” containing copper and manganese (prolate spheroid morphology) or iron (irregular “blocky” morphology) do not go into solution when the alloy is solid state homogenized (-495 °C) and are always present in the microstructure. All of these phases are copper-rich sources for surface redistribution relative to the matrix during corrosion.

Particulate materials with unique functional properties have been the focus of much attention in recent years. Of particular interest, due to their considerable scientific and technological importance, are particles coated with nanoparticles. These have greatly stimulated interest for their novel structure and properties. In these kinds of particulate materials, the interface structures between the support particle and the nanoparticle play a crucial role in controlling their properties. Consequently, imaging of the atomic structures at the interfaces can provide deep understanding of the relationship between the particulate and the corresponding properties. Z-contrast scanning transmission electron microscope (STEM) provides a new view of materials on the atomic scale, a direct image of atomic structure composition which can be interpreted without the need for any preconceived model structure. Therefore it is a powerful tool in the study of particulate materials. In this report, we will present the structures of 18 micron diameter alumina particles coated with Ag nanoparticles.

Nanoparticles and other nanostructured samples are developing into an increasingly important class of materials. Because of their small size (diameters less than 100 nm), reduced dimensionality, and large surface areas, nanoparticles often exhibit unusual physical, optical, mechanical, and electronic properties. In addition to providing valuable model systems in the pure sciences, nanoparticles are proving useful in technological applications, showing promise as biomedical imaging contrast agents, data storage media, magnetic inks and toners, ferrofluids, and as precursors for advanced compacted materials. Fulfilling this potential depends on characterizing the chemical inhomogeneities of the nanoparticles (and their surfaces) with very high spatial resolution. In this paper I examine the quantitative microanalysis of nanoparticles— electron energy-loss spectroscopy (EELS) and energy-dispersive x-ray spectrometry (EDS)— using transition metal alloy particles (Fig. 1) as a case study.

The microanalysis of nanoparticles presents unique challenges to the analyst because of the very small length scales in the system.

Modern high-performance computers are now capable of calculations that can be used to determine the preferred atomic arrangements in complex systems. Both first-principles and semiempirical approaches have been developed with complementary capabilities. At the same time, powerful transmission electron microscopes have been developed that yield direct atomic-scale images of crystals and extended defects such as dislocations, grain boundaries and buried interfaces. This paper presents several examples where a synergistic approach combining theoretical results, Z-contrast scanning transmission electron microscopy, and spatially resolved electron energy loss spectroscopy (EELS) have led to the elucidation of complex atomic structures. In some cases, theory predicts, experiment confirms and expands and theory revisits; in other cases, observations come first and theory helps put together a comprehensive picture or goes beyond the original observations with new predictions. In both cases, equilibrium structures, impurity or stressinduced structural transformations, and dynamical processes such as diffusion, segregation or precipitation are elucidated in great detail.

Since interfaces and grain boundaries affect critically many properties of materials, their atomic structure has been investigated very extensively using computer modeling. Most of these calculations have been made using semi-empirical central-force descriptions of atomic interactions, recently primarily the embedded-atom type many-body potentials. Owing to the approximate nature of such schemes, a connection with experimental observations that can validate the calculations is essential. The high resolution electron microscopy (HREM) is such experimental technique and it has, indeed, been frequently combined with calculations of interfacial structure and chemistry. In fact such a link is not only important for verification of the results of computer modeling but also crucial for meaningful interpretation of HREM observations. Hence, coupling the atomistic modeling with HREM is a synergistic procedure. It not only leads to better understanding of interfacial structures but may contribute significantly to the validation and assessment of limits of the schemes used for the description of atomic interactions.

Solute-atom segregation to grain boundaries has been of interest since the 1930's when it was realized that some steels were susceptible to failure by intergranular fracture when certain impurities were present. Segregation of impurities or intentionally added alloying elements at grain boundaries can greatly affect various grain boundary properties, which in turn affect numerous macroscopic properties. Materials phenomena that have been linked to grain boundary segregation include temper brittleness, fatigue strength, adhesion, precipitation, diffusional creep, intergranular corrosion, and grain boundary diffusivity. Although grain boundary segregation has been extensively studied for many years, the effects of different grain boundary structures on segregation was generally not considered. It has been established both experimentally and theoretically that the level of segregation varies from grain boundary to grain boundary in the same alloy, but there is little direct information on how grain boundary structure influences segregation.

The role of core level shifts at metallic interfaces has often been ignored in electron energy loss spectroscopy (EELS) even though very small changes in bond length can lead to large core level shifts. However, the popular interpretation of core level shifts as measures of charge transfer is highly problematic. For instance, in binary alloys systems, the core level shifts can be the same sign for both atomic constituents[l]. The simple interpretation would require that both atomic species had lost or gained charge. Further, the signs of the core level shifts can be opposite to those expected from electronegativity arguments[2]. A core level shift (CLS) is still possible, even when no charge transfer occurs. As illustrated in Fig. 1, if the valence band width is increased, the position of the center of the valence band with respect to the Fermi energy will change (as the number of electrons remains unchanged).

Metal/ceramic interfaces play a crucial role in materials science and for various industrial purposes. In technical applications these interfaces are often exposed to high temperatures and different atmospheres. This often results in a change of the mechanical stability via the morphology and electronic structure of the interfaces. We present a comprehensive analytical electron microcopy (AEM) and fracture mechanics study of this connection on a metal/ceramic-interface model system: Cu/ α-Al2O3.

The specimens were produced by UHV diffusion bonding of bulk Cu to (α-Al2O3 single crystals. Two different Cu materials were used, either pure Cu (noted: Cu) or Cu containing 83±12 ppm oxygen (noted: Cu(O)). After bonding the interfaces were annealed in an oxygen partial pressure at 1000°C between 20 and 120 h. Four point bending tests showed an increase of the fracture energy for the Cu(O)/α -Al2O3-interfaces compared to the Cu(O)/α-Al2O3-interfaces by a factor of 5±2.

Interfacial solute-atom segregation is known to have profound effects on macroscopic physical properties (e.g. electronic transport or fracture toughness) in interface-influenced or controlled materials. It has recently been shown that solute-atom segregation also can play an influential role in the dynamics of phase transformations, in particular the oxidation kinetics of alumina-forming alloys such as PtAl. By coupling analytical electron microscopy (AEM) with conventional macroscopic oxidation studies, we have demonstrated that oxidation kinetics are affected by atomic-scale segregation of dopant species to the grain boundaries and metal-oxide boundaries in the system. Furthermore, these studies illustrate the utility of AEM techniques in elucidating the atomic-scale aspects of macroscopic physical phenomena such as phase transformations.

Oxidation studies were carried out on PtAl alloys with and without small additions of Zr to the alloy. While the pure PtAl alloys exhibited oxide scale spallation and very fast oxidation rates, the Zrcontaining alloys maintained a well-adhered oxide scale and significantly lower oxidation rates.

Radiation-induced segregation (RIS) is the spatial redistribution of elements at defect sinks such as grain boundaries and free surfaces during irradiation. This phenomenon has been studied in a wide variety of alloys and has been linked to irradiation-assisted stress corrosion cracking (IASCC) of nuclear reactor core components. However, several recent studies have shown that Cr and Mo can be enriched to significant levels at grain boundaries prior to irradiation as a result of heat treatment. Segregation of this type may delay the onset of radiation-induced Cr depletion at the grain boundary, thus reducing IASCC susceptibility. Unfortunately, existing models of segregation phenomena do not correctly describe the physical processes and therefore are grossly inaccurate in predicting pre-existing segregation and subsequent redistribution during irradiation. Disagreement between existing models and measurement has been linked to potential interactions between the major alloying elements and lighter impurity elements such as S, P, and B.

Experiment and modeling show that there is a general mode of grain boundary dissociation, common in low stacking fault energy FCC metals, that can be well understood in terms of the emission of arrays of stacking faults from the grain boundary plane. Most extensively studied of such dissociated interfaces are the Σ=3 incoherent twin boundaries. Numerous observations now exist of grain boundary dissociation at such interfaces showing a layer that is well described as a narrow, several nanometer wide slab of 9R stacked material. The 9R stacking sequence is equivalent to a close-packed stacking of FCC ﹛111﹜ planes with an intrinsic stacking fault inserted every three planes (i.e., a stacking sequence of ABC/BCA/CBA …). The width of the 9R layer is sensitive to the local stress state. Figure 1 shows results of an atomistic calculation simulating the effect of an applied shear strain parallel to the boundary.

Although grain boundaries typically account for only a small fraction of a material, they can have far reaching effects on the overall bulk scale properties. These effects are usually simply linked to the boundary having a different atomic arrangement to the bulk. A necessary first step in understanding the structure-property relationships is therefore a detailed determination of the boundary structure.

One means of obtaining detailed information on the structure of grain boundaries is through correlated Z-contrast imaging and electron energy loss spectroscopy (EELS). The Z-contrast image generates a map of the grain boundary which can be used to position the probe in defined locations for spectroscopy. In the case of oxides, a structural model of the metal atom positions can be determined directly from the image. Furthermore, using a simple bond-valence sum minimization routine, the oxygen atoms can be placed so that the structure contains atoms that have valences consistent with their expected formal valence state.

Progress towards the large scale integration of active devices within electronics packages has imposed stringent heat dissipation requirements necessitating the development of innovative materials solutions. One possibility being considered is the use of chemically vapor deposited diamond (CVDD) thin films as heat sinks. However, there are technological challenges which must be overcome before these materials become commercially viable. For example, the CVDD substrate must be metallized to provide interconnections between the various devices in the package. Conventional metallizations, such as Au, Cu or Al, display poor adhesion to the diamond causing problems associated with the reliability and stability of metallized diamond packages. A novel solution has been proposed involving the consecutive deposition of a thin layer of Cr and an electrically insulating layer of alumina on the diamond substrate such that the thermal conductivity of the treated substrate is not degraded significantly.

Ceramic matrix composites (CMC's) rely on designed weaknesses in order to provide toughening mechanisms during failure. Specifically, the fiber/matrix interface is well established as the parameter having the most influence on CMC fracture behavior, as first noted by Sambell. With proper design, this interface can allow fracture energy to dissipate by two mechanisms: an increase in crack path tortuosity and frictional energy dissipation through fiber pullout.

One design approach in the area of oxide-based CMC's which has seen considerable success recendy has been in the use of “weakly bonding” oxide coating materials placed between the fiber and the matrix phases. Such CMC systems rely on the formation of a weak interface between the fiber and the coating itself to promote the desired fracture behavior. The most notable example of such a coating material is monazite, LaPO4, as observed by Morgan et al.

This paper focuses on the differences of physical properties, specifically local dielectric function, of biogenic and geological mineral CaCO3. The goal is to assess the role of organism in forming biogenic inorganic materials. Local dielectric functions of biogenic and geological minerals were determined by transmission electron energy loss spectroscopy using a previously developed strategy.

Previous work on microstructural characterization of biological hard tissues, e.g., abalone shells, has shown variations in terms of defects, morphology, crystallography, and organization of nano- and microstructures in two biological polymorphs of calcium carbonate, calcite and aragonite, in the prismatic and nacreous regions, respectively. In the abalone, the outer (1-5 mm thick) region of the shell is composed of calcite crystallites (1-5 μm diameter) with columnar organization perpendicular to shell plane. On the inner region, 1-10 mm thick nacre is composed of aragonite crystallites (0.5 μm thick and 5 -10 μm edge-length) forming flat platelets, parallel to the shell plane.

The analysis of the atomic structure of grain boundaries is often performed through the use of high-resolution transmission electron microscopy (HRTEM). A complication of the HRTEM technique is the inability to analyze directly the experimental images in order to determine projected atomic models of lattice defects. Since contrast features in HRTEM images, in general, do not correspond directly to atomic positions, experimental images are typically evaluated qualitatively through comparison with image simulation. Recently, the interest in quantitatively measuring the atomic structure of internal interfaces for comparison with theoretical calculations has motivated the development of computational methodologies to analyze HRTEM images.123 In this paper, the quantitative analysis of HRTEM images of twin boundaries in semiconductors and metals is described.

AΣ=3 coherent twin boundary in GaP was imaged along the <110> zone in a JEOL-4000EX HRTEM at Sandia National Laboratories, Livermore.

The physical properties of crystalline materials are dependent on the presence and nature of planar defects such as grain boundaries within the crystalline lattice. A comprehensive understanding of a material's properties requires a detailed knowledge of the atomic structure and chemistry of such defects. In general, the crystal orientation relationship at grain boundaries and related planar defects are described in geometric terms, such as the coincidence-site lattice (CSL) model. However, geometric models do not take account of the atomic bonding across grain boundaries whose characteristics differ from that in the bulk. In general, defect structures may relax from the exact CSL orientation in order to minimize the energy of the interface. Lattice relaxations can manifest as a local rearrangement of the atoms close to the boundary and/or rigid-body lattice translations which perturb the relative positions of the grains far from the interface.

A1N is an attractive material because of its mechanical, thermal and electronic properties. However, these properties are often adversely altered by extended defects such as inversion domain boundaries (IDBs), and through impurities associated with the defects, especially oxygen. Thus to improve the properties of the material it is important to understand the structures of the defects. A number of studies have been carried out to characterize these defects using fringe contrast, weak-beam, convergent-beam electron diffraction and conventional high-resolution phase contrast imaging. These techniques all require the use of model structures for data interpretation. In this paper, we report a direct determination of the structures of IDBs and dislocation cores in A1N by highresolution Z-contrast imaging using a 300 kV VG HB603U scanning transmission electron microscope, with a probe size of 1.3 Å.

Although grain boundaries are known to dominate the bulk properties of many technologically important materials, in most cases there is no fundamental atomic scale understanding of why they should have such an effect. One of the problems in developing this understanding is that conventional structure determination techniques, such as phase contrast imaging in TEM or Z-contrast imaging in STEM, produce only a 2-dimensional projection of the crystal structure. Atomic scale compositional changes must be simulated and a unique interpretation is clouded by boundary reconstructions and strain effects. Furthermore, neither technique provides any information on the local changes in the electronic structure that are critical for both the electrical and mechanical properties of the boundary.

EELS provides a means to quantify local changes in both composition and electronic structure. However, without a knowledge of the structure, interpretation of any observed changes at grain boundaries is extremely difficult.