Alkali-silica reaction, sulfate attack, and reinforcing steel corrosion can compromise the long-term durability of concrete structures. The anticipated economic impact of an extensive infrastructure repair scheme has produced a renewed interest in the development of advanced characterization methods to assess the degree of deterioration in the concrete experiencing these deleterious reactions. The products of the alkali silica reaction, sulfate attack, and corrosion as well as the cement hydration products are extremely sensitive to humidity. Consequently, characterization techniques that require high vacuum or drying, as many existing techniques do, are not particularly appropriate for the study of these reactions in concrete as artifacts are introduced. A high resolution instrument which allows the examination of these reactions and their products without drying and at normal pressures will promote understanding of the reactions and provide further insight into means of mitigating the damage they cause. Only soft x-ray transmission microscopy provides the required high spatial resolution to observe the reaction process in situ. The alkali-silica reaction can be observed over time, in a wet condition, and at normal pressures, features unavailable with most other high resolution techniques. Soft x-rays also reveal information on the internal structure of the sample. This paper reviews published and ongoing applications of soft x-ray transmission microscopy for the study of expansive reactions that occur in concrete.

A set of new infrared (IR) beamlines on the 1.4 bending magnet port at the Advanced Light Source, LBNL, are described. Using a synchrotron as an IR source provides considerable brightness advantages, which manifests itself most beneficially when performing spectroscopy on a microscopic length scale. Beamline (BL) 1.4.3 is a dedicated microspectroscopy beamline, where the much smaller focused spot size using the synchrotron source is utilized. This enables an entirely new set of experiments to be performed where spectroscopy on a truly microscopic scale is now possible. BL 1.4.2 consists of a vacuum FTIR bench with a wide spectral range and step-scan capabilities. The fast timing is demonstrated by observing the synchrotron electron storage pattern at the ALS.

Synchrotron microspectroscopy has been used to study the inorganic-organic interactions in the mid-infrared region (4000#x2013;400 cm#x2212;1) as Arthrobacter oxydans attach themselves to magnetite surfaces. Relative band intensities and band intensity ratios for functional groups of organically-derived biological molecules that are inherent to the experimental system are discussed. The molecular components as they are perturbed by interactions with water, dichromate and chromate metal ions on the mineral surfaces are investigated. Mapping of the spectral markers for the inorganic-organic interactions at the biological- mineral interfaces is presented and discussed. Comparative analyses of the synchrotron infrared microspectra suggest that the bacterial-chromium interactions depend on the solubility and toxicity of the chromium compounds.

X-ray Photoemission Electron Microscopy (X-PEEM) is a full-field imaging technique where the sample is illuminated by an x-ray beam and the photoemitted electrons are imaged on a screen by means of an electron optics. It therefore combines two well-established materials analysis techniques - photoemission electron microscopy (PEEM) and x-ray spectroscopy such as near edge x-ray absorption fine structure (NEXAFS) spectroscopy. This combination opens a wide field of new applications in materials research and has proven to be a powerful tool to investigate simultaneously topological, elemental, chemical state, and magnetic properties of surfaces, thin films, and multilayers at high spatial resolution. A new X-PEEM installed at the bend magnet beamline 7.3.1.1 at the Advanced Light Source (ALS) is designed for a spatial resolution of 20 nm and is currently under commissioning. An overview of the ongoing experimental program using X-PEEM in the field of materials research at the ALS is given by elemental and chemical bonding contrast imaging of hard disk coatings and sliders, field emission studies on diamond films as possible candidates for field-emission flat-panel displays, and the study of dewetting and decomposition phenomena of thin polymer blends and bilayers.

A hard X-ray microbeam with submicrometer spot size from synchrotron radiation (SR) sources is expected to add a new dimension to various X-ray analysis methods. A Fresnel zone plate (FZP) is one of the promising focusing elements for X-rays. In order to develop high performance multilayer FZP for use in the hard X-ray region, Cu/Al concentric multilayers were fabricated by use of a DC sputtering deposition process. Lower Ar gas pressure or higher rotating speed of a wire substrate has been effective in forming smoother multilayer interfaces. From a focusing test of the Cu/Al FZP (100-zones) by the SR (λ= 0.154nm), microbeams of 1.5 μm φ and 0.8 μm φ have been achieved for the first- and third-order focal beams, respectively.

The use of synchrotron polychromatic x-ray microbeams in the transmission geometry is described for mapping grain orientation as a function of position and for relating this microtexture to the formation of large asperities on fatigue crack surfaces in Al-Li 2090 T8E41. In common with the centers of rolled plates of many aluminum alloys, Al-Li 2090 T8E41 has a sharp average texture or macrotexture different from that in the outer portions of the plate. The geometry of large asperities in Al-Li 2090 has been related to this macrotexture, and the resulting roughness-induced crack closure is recognized to be responsible for the very low crack propagation rates in certain plate orientations. This report focuses on why asperities form at certain positions and why the crack remains relatively planar elsewhere. The microtexture (i.e., the grain-to-grain orientation variation) seems to be organized into a specific type of mesotexture: multiple adjacent grains have nearly identical orientations and form substantial volumes of near-single-crystal material. Transitions between differently oriented near-singlecrystal volumes or between a near-single- crystal region and more randomly oriented grains appear to bound asperities.

Polychromatic synchrotron x-ray microbeams offer a very efficient alternative to electron beam methods for quantifying the amount and character of grain subdivision accompanying large deformations. With a 0.01 mm diameter collimator, bending magnet radiation from a 3.0 GeV source and image storage plates, samples of copper with thicknesses greater than 0.1 mm have been studied. Results from an as-received sample and a sample deformed to 100% torsion are compared and illustrate how efficiently grain subdivision can be quantified with polychromatic microbeam diffraction.

Third generation hard x-ray synchrotron sources and new x-ray optics have revolutionized x-ray microbeams. Now intense sub-micron x-ray beams are routinely available for x-ray diffraction measurement. An important application of sub-micron xray beams is analyzing polycrystalline material by measuring the diffraction of individual grains. For these measurements, conventional analysis methods will not work. The most suitable method for microdiffraction on polycrystalline samples is taking broad-bandpass or white-beam Laue images. With this method, the crystal orientation and non-isostatic strain can be measured rapidly without rotation of sample or detector. The essential step is indexing the reflections from more than one grain. An algorithm has recently been developed to index broad bandpass Laue images from multi-grain samples. For a single grain, a unique set of indices is found by comparing measured angles between Laue reflections and angles between possible indices derived from the x-ray energy bandpass and the scattering angle 2 theta. This method has been extended to multigrain diffraction by successively indexing points not recognized in preceding indexing iterations. This automated indexing method can be used in a wide range of applications.

A micro x-ray diffraction facility is under development at the Advanced Light Source. Spot sizes are typically about 1-μm size generated by means of grazing incidence Kirkpatrick-Baez focusing mirrors. Photon energy is either white of energy range 6-14 keV or monochromatic generated from a pair of channel cut crystals. A Laue diffraction pattern from a single grain in a passivated 2-μm wide bamboo structured Aluminum interconnect line has been recorded. Acquisition times are of the order of a few seconds. The Laue pattern has allowed the determination of the crystallographic orientation of individual grains along the line length. The experimental and analysis procedures used are described, as is a grain orientation result. The future direction of this program is discussed in the context of strain measurements in the area of electromigration.

Synchrotron radiation diffraction imaging (‘topography’) was used at the ESRF to visualize ultrasonic standing waves in a magnetoacoustically excited FeBO3 crystal. Images were recorded at long sample-to-film distances (up to 1.5 m) without substantial loss of resolution. The resonant patterns reveal that the crystal acts as a pulsed X-ray focusing lens and strongly depend on both the amplitude of the magnetic field and the sample-to-detector distance. Different resonant frequencies can also lead to more complicated images due to interference effects of several vibrating modes present in the crystal. A model is proposed followed by a numerical integration which predicts the focusing of the X-ray beam and demonstrates the agreement between theory and experiment. This effect could be used to simultaneously monochromatize and focus the X-ray beam.

Synchrotron White Beam X-ray Topography (SWBXT) and synchrotron X-ray anomalous scattering have been employed to determine the polarity of {111} edge facets, anchored to the three phase boundary (TPB) on which twinning is observed to nucleate in Magnetic Liquid Encapsulated Czochralski (MLEC) grown sulfur doped, <001> InP single crystals. Analysis of the results indicates that both the formation of edge facets and the nucleation of twins occur preferentially on {111}P faces. Of the four possible sets of edge facets, belonging to the {111}P form, which are oriented so as to be thermodynamically favored to be anchored to the TPB, two can give rise to a {115} to {111}P external shoulder facet conversion upon twinning, while the other two can give rise to a {114} to {110} conversion. For these cases, twinning is only observed when the {111}P edge facets are anchored to the TPB in a region where the shoulder angle is close to 74.21° or 70.53°, facilitating the production of the {115} and {114} external shoulder facets, respectively, prior to twinning. These observations are discussed in light of calculated surface energies of the various internal and external facets.

The topographic contrast of superscrew dislocations in 6H-SiC crystals has been studied by synchrotron white-beam x-ray topography in the Bragg reflection geometry. The diffraction images of these dislocations are simulated using a ray-tracing method. Systematical simulations, which coincide with the dislocation images taken by back-and grazing-reflection topography, clearly reveal the kinematic diffraction mechanisms of the superscrew dislocation, and illustrate that synchrotron reflection topography is capable of providing accurate descriptions of the strain fields, the Burgers vector magnitudes, and the senses of these dislocations. In addition, our experiments and simulations demonstrate straightforwardly the relation between the topographic contrast and the lattice distortions, and therefore the general mechanisms underlying contrast formation of defect images in synchrotron reflection topographs are provided.

Experimentally observed X-ray reflectivity curves show bi-crystal(twin) characteristics. The study revealed that there was defect segregation at the twin boundary. Stress was relaxed at the edge of the boundary. Relaxation of the stress resulted in formation of twin and other defects. As a result of formation of such defects, a defect-free and stress-free zone or low defect density and small stress zone is created around the defects. So a twin model was proposed to explain the experimental results. Stress(mainly thermal stress), chemical stoichiometry deviation and impurities nonhomogeneous distributions are the key factors that cause twins in LEC InP crystal growth. Twins on (111) face in LEC InP crystal were studied. Experimental evidence of above mentioned twin model and suggestions on how to get twin-free LEC InP single crystals will be discussed.

An experimental apparatus, which is capable of performing real time in situ X-ray topographic observation of deformation process via synchrotron white beam topography, has been developed. This device enables both tensile data (load-displacement) and topographic images to be recorded simultaneously. It has been utilized to study the deformation behaviors of crystals of Mo and W.These specimens have been subject to mechanical cycling with increasing load, and their deformation processes have been observed in real time and in situ via x-ray topography. This leads to the observation of several phenomena, which would have been difficult to reveal by other experimental techniques. They include stress concentration, microyielding, reversible variation of contrasts and stress relaxation. In addition, the deformation behaviors of small angle grain boundaries have also been examined. Furthermore, the specimens can be heated through a heating device attached to the tensile stage, which allows high temperature topography to be performed in real time. The technique has been applied to the Ta films on Si (100) substrates. With increasing temperature, the topographic observations have revealed that the Ta films yield, fracture and then proceed to delaminate from their substrates.

We have developed a method to determine the relationship between strain and lateral size of coherent self-organized quantum dots. In our approach, X-ray grazing incidence diffraction is used to collect information on strain and shape effects in the vicinity of a prominent surface reflection. We demonstrate that for highly strained nano-scale islands it is possible to separate strain-induced and form factor-induced scattering without comparing different reflections. Experimental data from InAs on GaAs(100) quantum dots is discussed with respect to this model. Reciprocal space mapping around the (220) surface reflection shows a linear relationship between relaxation from the substrate lattice parameter and the outer perimeter of the dot. In addition, the functional form of the gradient of relaxation is found to be nonmonotonous and rapidly increasing towards the tip of the dot.

To characterize the point defects and point defect clusters introduced by ion implantation and annealing, we have used grazing incidence x-rays to measure the diffuse scattering in the tails of Bragg peaks (Huang Scattering). An analysis of the diffuse scattered intensity will allow us to characterize the nature of point defects or defect clusters introduced by ion implantation. We have also observed unexpected satellite peaks in the diffuse scattered tails. Possible causes for the occurrence of the peaks will be discussed.

Nanometric films of iron oxides (Fe3O4, α and γ Fe2O3) of high crystalline order and purity are epitaxially grown on α-A12O3(0001) by atomic oxygen assisted MBE. A complete characterization of the films structure has been performed by in situ LEED and RHEED, and ex situ GIXRD using synchrotron radiation. The films grown at room temperature and post annealed at 400°C and 700°C (po2=10−6 Torr) are respectively metastable γ-Fe2O3 (111) and α-Fe2O3 (0001). For a substrate temperature of 450°C during growth, Fe3O4 (111) is directly obtained. GIXRD shows an in-plane expansion of the films, which decreases with thickness (0.8 and 0.2% for film thickness of 20 and 80 Å, respectively).

Amorphous and crystalline content in sputtered B4C and SiC thin films has been analyzed by synchrotron grazing incidence x-ray scattering (GIXS). GIXS provided quantitative information on the average structure while TEM was used to find inhomogeneities such as small volume fraction phases. GIXS results were compared to simulations to determine average particle size or bond length for crystalline or amorphous phases respectively. In this work, we compared results from films deposited with, and without, an RF bias applied to the substrate during deposition. Results indicated that SiC can be described as strained polycrystalline material with particle size of approximately 13 Å for biased samples and 9Å for unbiased samples. Boron carbide deposited without bias was completely crystalline with a particle size of approximately 30 Å, while the data suggested that B4C deposited with bias is amorphous. The scattering from the biased materials was Fourier transformed to yield radial distribution functions (RDF). This provided nearest neighbor distances, and it was demonstrated that the technique can be used to determine full three-dimensional strain tensors in amorphous thin films.

Ta films 25Å to 200Å in thickness were sputter-deposited using different sputter gas (Ar) pressures and cathode power settings. The average in-plane stresses were determined using double crystal diffraction topography (DCDT). X-ray analysis (using the grazing incidence x-ray scattering (GIXS) geometry) was performed using a synchrotron light source. To study microstructure and phase content, transmission electron microscopy (TEM) and transmission electron diffraction (TED) were used. Well resolved x-ray patterns were collected for all of the films. The DCDT stress data was found to be consistent with stress effects evident in the GIXS data. In general, residual stress state was not strongly dependent upon Ar pressure. The strongest evidence of amorphous content was found in both x-ray and TED data taken from 25Å thick films deposited using 2mTorr Ar pressure and 460 W cathode power. These results show that it is possible to create and study ultra-thin Ta films which posses a range of residual stresses and phase compositions.

The Energy Dispersive X-ray Diffiractometry (EDXD) technique was tested for in-situ crystallographic characterization of nickel films processed by chemical vapor deposition (CVD). The diffracted beam at low Bragg angle was analyzed in energy by a solid state detector. A nickel reference sample was used to face the problems of EDXD background signal and uncertainty of sample location. The relative accuracy on lattice parameters measurements is 1.5.10−3, to be compared to 0.5.10−3 for classical (monochromatic) X-Ray diffraction. Texture measurements yields results in agreement with those obtained from recent texture goniometer. Finally, an estimation of the thickness was obtained from the intensity of nickel fluorescence peak. In view of the obtained results, EDXD appears to be a promising technique for in-situ studies. Although less powerful compared to the synchrotron facility, it is more flexible and can be applied at lower cost.