The direct carbonate procedure for accelerator mass spectrometry radiocarbon (AMS 14C) dating of submilligram samples of biogenic carbonate without graphitization is becoming widely used in a variety of studies. We compare the results of 153 paired direct carbonate and standard graphite 14C determinations on single specimens of an assortment of biogenic carbonates. A reduced major axis regression shows a strong relationship between direct carbonate and graphite percent Modern Carbon (pMC) values (m = 0.996; 95% CI [0.991–1.001]). An analysis of differences and a 95% confidence interval on pMC values reveals that there is no significant difference between direct carbonate and graphite pMC values for 76% of analyzed specimens, although variation in direct carbonate pMC is underestimated. The difference between the two methods is typically within 2 pMC, with 61% of direct carbonate pMC measurements being higher than their paired graphite counterpart. Of the 36 specimens that did yield significant differences, all but three missed the 95% significance threshold by 1.2 pMC or less. These results show that direct carbonate 14C dating of biogenic carbonates is a cost-effective and efficient complement to standard graphite 14C dating.

In North America, terrestrial records of biodiversity and climate change that span Marine Oxygen Isotope Stage (MIS) 5 are rare. Where found, they provide insight into how the coupling of the ocean–atmosphere system is manifested in biotic and environmental records and how the biosphere responds to climate change. In 2010–2011, construction at Ziegler Reservoir near Snowmass Village, Colorado (USA) revealed a nearly continuous, lacustrine/wetland sedimentary sequence that preserved evidence of past plant communities between ~140 and 55 ka, including all of MIS 5. At an elevation of 2705 m, the Ziegler Reservoir fossil site also contained thousands of well-preserved bones of late Pleistocene megafauna, including mastodons, mammoths, ground sloths, horses, camels, deer, bison, black bear, coyotes, and bighorn sheep. In addition, the site contained more than 26,000 bones from at least 30 species of small animals including salamanders, otters, muskrats, minks, rabbits, beavers, frogs, lizards, snakes, fish, and birds. The combination of macro- and micro-vertebrates, invertebrates, terrestrial and aquatic plant macrofossils, a detailed pollen record, and a robust, directly dated stratigraphic framework shows that high-elevation ecosystems in the Rocky Mountains of Colorado are climatically sensitive and varied dramatically throughout MIS 5.

Extended abstract of a paper presented at Microscopy and Microanalysis 2004 in Savannah, Georgia, USA, August 1–5, 2004.

Faceting in a polyhedral rutile particle was modeled from transmission electron microscopy images. A double-tilt, rotate transmission electron microscope (TEM) sample holder was used to manipulate the particle. Using this holder, it was possible to align the c axis of the particle along one of the axes of the sample holder. This alignment allowed images to be obtained of the particle in several orientations around its c axis. Comparison of dimensions and angles obtained to those obtained for hypothetical models of the particle gives information about its likely prismatic and pyramidal faceting. This approach to facet modeling is useful for more complete determination of the faceting in individual euhedral particles using transmission electron microscopy.

In the interim between the conception of this issue of MRS Bulletin on transparent conducting oxides (TCOs) and its publication, the remarkable applications dependent on these materials have continued to make sweeping strides. These include the advent of larger flat-screen high-definition televisions (HDTVs), larger and higher-resolution screens on portable computers, the increasing importance of low emissivity (“low-e”) and electrochromic windows, a significant increase in the manufacturing of thin-film photovoltaics (PV), and a plethora of new hand-held and smart devices, all with smart displays.1-7 Coupled with the increased importance of TCO materials to these application technologies has been a renaissance over the last two years in the science of these materials. This has included new n-type materials, the synthesis of true p-type materials, and the theoretical prediction and subsequent confirmation of the applicability of codoping to produce p-type ZnO. Considering that over the last 20 years much of the work on TCOs was empirical and focused on ZnO and variants of InxSn1-xO2, it is quite remarkable how this field has exploded. This may be a function of not only the need to achieve higher performance levels for these devices, but also of the increasing importance of transition-metal-based oxides in electro-optical devices. This issue of MRS Bulletin is thus well timed to provide an overview of this rapidly expanding area. Included are articles that cover the industrial perspective, new n-type materials, new p-type materials, novel deposition methods, and approaches to developing both an improved basic understanding of the materials themselves as well as models capable of predicting performance limits.

The use of digital electron microprobe x-ray compositional mapping with wavelength dispersive spectrometers to understand the microstructure of yttria stabilized zirconia thermal barrier coatings is described. Data from quantification of element x-ray maps can be utilized to infer what phase or phases are present. Analysis of a plasma-sprayed coating prepared from a fused and crushed feedstock is compared to an annealed specimen of the same material.

Phase evolution in a yttria-partially-stabilized zirconia (Y-PSZ) thermal barrier coating (TBC) was studied by using quantitative electron probe x-ray mapping combined with microbeam x-ray diffraction. The as-sprayed coating contains a single t' phase with the composition of the feedstock material. After annealing at 1400 °C for 1 hour, the yttria content of the t' phase increases slightly to compensate for the formation of 0.06 mass fraction of a t phase containing 0.01 mole fraction YO1.5. These results are in contrast to those determined by bulk x-ray and neutron diffraction, and therefore highlight the need for multiple techniques of phase analysis in Y-PSZ.

Electron-excited X-ray maps recorded with the scanning electron microscope (SEM)/electron probe X-ray microanalyzer (EPMA) are a major method of presenting compositional information. Digitally recorded maps are processed in a variety of ways to improve the visibility of features. Scaling of the recorded signal to match the 8-bit gray-scale intensity range of a typical computer display system is almost always necessary. Inherent limitations of gray-scale displays have led to other intensity-encoding methods for X-ray maps, including clipping, histogram normalization, and pseudocolor scales. While feature visibility is improved by applying these scales, comparisons among image sets are difficult. Quantitative comparisons must be based on standardized intensities corrected for background to produce intensity ratio (k-value) maps. We have developed a new logarithmic, multiband color-encoding method to view these k-value maps more effectively. Three color bands are defined, starting with a dark primary color and grading to a bright pastel: blue = trace (0.001 to 0.01); green = minor (0.01 to 0.1); and red = major (0.1 to 1.0). Within each band, the color is assigned according to a logarithmic scale that depends on intensity ratio or compositional measurements. Logarithmic multiband color encoding permits direct comparisons of maps, such as maps of different elements in the same field of view or maps of the same element in different areas, because the color scale is identical for all maps.

X-ray mapping is one of the most popular modes for displaying information obtained with x-ray spectrometry performed in the scanning electron microscope. This popularity arises from the ready accessibility and apparent simplicity of information presented in a pictorial fashion, especially when used in conjunction with other SEM imaging modes, such as backscattered, secondary, and specimen current electron images. Further, the rise of powerful, inexpensive computer systems capable of image processing and display has given the analyst a dedicated, on-line tool with the capacity and flexibility needed for problem solving. Figure 1 shows a typical example of mapping. Although the interpretation of x-ray images obtained with a modern digital control and recording system would seem to be straightforward and relatively trivial, there are significant pitfalls and limitations that can easily fool the unwary. In Figure 1, within an individual x-ray map, the observer can reasonably judge where the concentration is lower or higher, at least for a group of contiguous pixels. Can such judgments be made among a set of maps of the same region for different elements, or even for the same element from different regions of the same specimen? With current x-ray processing and display systems, the answers are generally no. In fact, problems that can influence interpretation can arise at each stage of x-ray generation/emission, x-ray spectral collection, processing, and display.

Compositional mapping with energy dispersive x-ray spectrometry (EDS) in the scanning electron microscope (SEM) is one of the most widely used techniques for elemental imaging of microstructures. SEM/EDS maps are usually qualitative presentations of elemental distributions in x-y space. In older implementations of mapping, the x-ray intensity from a single spectral region of interest (ROI) above a threshold was recorded on film as a white “dot” during analog scanning. With modem digital control and data recording, x-ray intensities from many ROIs can be recorded in parallel and true counts stored in memory. For display purposes a gray level or color value is used to represent the stored x-ray intensity at each pixel. For major constituents (arbitrarily, major >10%), it is generally possible to make valid, robust comparisons between regions within an individual compositional map, but comparisons may be problematic among several maps of different constituents within the same field of view, depending on the sophistication of the mapping software.

Accurate characterization of electron diffraction patterns can be tedious, which encourages development of computer assisted tools and methods. We developed a spot measurement tool to characterize rapidly arrays of diffraction spots that are characteristic of a single crystal, and to measure precisely the d-spacing values for individual spots. The spot tool determines these vectors for averaged measurements from many spots in a digital image of the diffraction pattern. Previously we developed automated methods for spot pattern analysis. Why make an operator-assisted tool? This tool is faster than either our automated or entirely manual methods, and it allows assessment of the quality of the data at the beginning of the analysis.

It is easy to see regular patterns of spots in a zone axis diffraction pattern (Fig. 1.1). An operator guides the initial calculations by adjusting an array of circles to approximately cover the spots in the pattern to be analyzed.

Yttria-doped zirconia plasma-sprayed thermal barrier coatings (TBC’s) have been used successfully to improve the performance and extend the life of industrial equipment such as jet engines. For this reason, there is considerable interest in understanding and improving the plasma spray process and resulting TBC’s. A collaborative research program exists between Sandia National Laboratories and the National Institute of Science and Technology (NIST) to study the materials and processes used in preparing the coatings as well as the relationship between the physical properties of the coating and its microstructure.

The purpose of this work was to determine the elemental compositions on a micrometer scale of an yttria-doped zirconia coating. The cubic and tetragonal crystal forms of the yttria-doped zirconia have the most favorable thermal expansion coefficient, therefore providing the most effective thermal barrier. The Y concentration in these crystal phases is known to be 6-7 wt%, while the less desirable monoclinic phase, having a less favorable thermal expansion coefficient, contains less that 3 wt% Y.

Platinum and platinum-gold metallurgy was fully developed by smiths in the Esmeraldas-Tumaco Pacific coast area of present day Ecuador and Colombia long before the arrival of Europeans in South America and centuries before platinum metallurgy became practicable in the Western world. Using gold to sinter together nuggets of native placer platinum, then alternately working and annealing the resultant solid, these South American smiths produced hard, fairly homogeneous platinum-gold alloys of a range of colors for fabrication into items of adornment, and small tools, such as needles, tweezers, awls, and fishhooks.

The microstructures and compositions of sintered Pt-Au objects from La Tolita, Ecuador, and of experimentally simulated Pt-Au alloy samples were analyzed using new electron microprobe microanalysis (EPMA) techniques and data from the Pt-Au phase diagram in an effort to determine the fabrication temperatures used by Pre-Hispanic South American smiths. A comparison of EPMA results from the simulated materials with the corresponding results from the La Tolita Pt-Au objects suggests that the Pt-Au objects were never heated as high as 1100°C and probably never contained a liquid phase. As illustrated by this comparison, the qualitative and quantitative information provided by these new digital acquisition and display techniques far exceeds what conventional line scan and x-ray dot maps could provide.