Direct observation of individual hydrogen atoms at trapping sites in a ferritic steel.

The design of atomic-scale microstructural traps to limit the diffusion of hydrogen is one key strategy in the development of hydrogen-embrittlement-resistant materials. In the case of bearing steels, an effective trapping mechanism may be the incorporation of finely dispersed V-Mo-Nb carbides in a ferrite matrix. First, we charged a ferritic steel with deuterium by means of electrolytic loading to achieve a high hydrogen concentration. We then immobilized it in the microstructure with a cryogenic transfer protocol before atom probe tomography (APT) analysis. Using APT, we show trapping of hydrogen within the core of these carbides with quantitative composition profiles. Furthermore, with this method the experiment can be feasibly replicated in any APT-equipped laboratory by using a simple cold chain.

Clustered field evaporation of metallic glasses in atom probe tomography.

Field evaporation of metallic glasses is a stochastic process combined with spatially and temporally correlated events, which are referred to as clustered evaporation (CE). This phenomenon is investigated by studying the distance between consecutive detector hits. CE is found to be a strongly localized phenomenon (up to 3nm in range) which also depends on the type of evaporating ions. While a similar effect in crystals is attributed to the evaporation of crystalline layers, CE of metallic glasses presumably has a different - as yet unknown - physical origin. The present work provides new perspectives on quantification methods for atom probe tomography of metallic glasses.

Diffusion on demand to control precipitation aging: application to Al-Mg-Si alloys.

We demonstrate experimentally that a part-per-million addition of Sn solutes in Al-Mg-Si alloys can inhibit natural aging and enhance artificial aging. The mechanism controlling the aging is argued to be vacancy diffusion, with solutes trapping vacancies at low temperature and releasing them at elevated temperature, which is supported by a thermodynamic model and first-principles computations of Sn-vacancy binding. This "diffusion on demand" solves the long-standing problem of detrimental natural aging in Al-Mg-Si alloys, which is of great scientific and industrial importance. Moreover, the mechanism of controlled buffering and release of excess vacancies is generally applicable to modulate diffusion in other metallic systems.

Element-resolved corrosion analysis of stainless-type glass-forming steels.

Ultrathin passive films effectively prevent the chemical attack of stainless steel grades in corrosive environments; their stability depends on the interplay between structure and chemistry of the constituents iron, chromium, and molybdenum (Fe-Cr-Mo). Carbon (C), and eventually boron (B), are also important constituents of steels, although in small quantities. In particular, nanoscale inhomogeneities along the surface can have an impact on material failure but are still poorly understood. Addressing a stainless-type glass-forming Fe50Cr15Mo14C15B6 alloy and using a combination of complementary high-resolution analytical techniques, we relate near-atomistic insights into increasingly inhomogeneous nanostructures with time- and element-resolved dissolution behavior. The progressive elemental partitioning on the nanoscale determines the degree of passivation. A detrimental transition from Cr-controlled passivity to Mo-controlled breakdown is dissected atom by atom, demonstrating the importance of nanoscale knowledge for understanding corrosion.

Quantitative APT analysis of Ti(C,N).

A specially produced Ti(C,N) standard material, with a known nominal composition, was investigated with laser assisted atom probe tomography. The occurrence of molecular ions and single/multiple events was found to be influenced by the laser pulse energy, and especially C related events were affected. Primarily two issues were considered when the composition of Ti(C,N) was determined. The first one is connected to detector efficiency, due to the detector dead-time. The second one is connected to peak overlap in the mass spectrum. A method is proposed for quantification of the C content in order to establish the C/N ratio. A correction was made to the major C peaks, C at 6 and 12 Da, with the (13)C isotopes, at 6.5 and 13 Da, according to the known natural abundance. In addition, a correction of the peak at 24 Da, where C and Ti overlap, is proposed based on the occurrence of single/multiple events for respective element. The results were compared to the results from other techniques such as electron energy loss spectroscopy, chemical analysis and X-ray diffraction. After applying the corrections, atom probe tomography results were satisfactory. Furthermore, the content of dissolved O in Ti(C,N) was successfully quantified.

Pulsed-laser atom probe studies of a precipitation hardened maraging TRIP steel.

A precipitation hardened maraging TRIP steel was analyzed using a pulsed laser atom probe. The laser pulse energy was varied from 0.3 to 1.9 nJ to study its effect on the measured chemical compositions and spatial resolution. Compositional analyses using proximity histograms did not show any significant variations in the average matrix and precipitate compositions. The only remarkable change in the atom probe data was a decrease in the ++/+ charge state ratios of the elements. The values of the evaporation field used for the reconstructions exhibit a linear dependence on the laser pulse energy. The adjustment of the evaporation fields used in the reconstructions for different laser pulse energies was based on the correlation of the obtained cluster shapes to the TEM observations. No influence of laser pulse energy on chemical composition of the precipitates and on the chemical sharpness of their interfaces was detected.

Investigation of the analysis parameters and background subtraction for high-k materials with atom probe tomography.

In this paper we present depth profiles of a high-k layer consisting of HfO(2) with an embedded sub-nm thick ZrO(2) layer obtained with atom probe tomography (APT). In order to determine suitable measurement parameters for reliable, reproducible, and quantitative analysis, we have investigated the influence of the laser energy and the specimen temperature on the resulting elemental composition. In addition we devise a procedure for local background subtraction both for the composition and the depth scale that is crucial for gaining reproducible results. We find that the composition of the high-k material remains unaffected even for extreme laser energies and base temperatures, while higher laser energies lead to an accumulation of silicon at the upper interface of the high-k layer. Furthermore we show that APT is capable of providing sub-nm depth resolution for high-k materials with high reproducibility, good compositional accuracy, and high measurement yield.

Improvements in planar feature reconstructions in atom probe tomography.

Standard atom probe tomography spatial reconstruction techniques have been reasonably successful in reproducing single crystal datasets. However, artefacts persist in the reconstructions that can be attributed to the incorrect assumption of a spherical evaporation surface. Using simulated and experimental field evaporation, we examine the expected shape of the evaporating surface and propose the use of a variable point projection position to mitigate to some degree these reconstruction artefacts. We show initial results from an implementation of a variable projection position, illustrating the effect on simulated and experimental data, while still maintaining a spherical projection surface. Specimen shapes during evaporation of model structures with interfaces between regions of low- and high-evaporation-field material are presented. Use of two-and three-dimensional projection-point maps in the reconstruction of more complicated datasets is discussed.

Investigations of field-evaporated end forms in voltage- and laser-pulsed atom probe tomography.

Atom Probe Tomography (APT) consists of analyzing a needle-shaped specimen on an atom-by-atom basis. In recent years, instruments have become commercially available, enabling the sequential analysis of the same specimen in both laser- and voltage-pulsed modes. In this contribution, a comparison of field evaporated end-forms as a function of the voltage and laser power is presented for silicon. Electron microscopy is utilized for visual inspection of the final tip end-forms. The field of evaporation for silicon is calculated based on these radius measurements for voltage and laser pulsing. Electron microscopy and analysis of the atom probe data show that the specimen end-forms for both pulsing modes can be different. We have observed two effects on the shape of a field-ion emitter when irradiated by a focused laser beam. One is a change in the 3-dimensional topology of the emitter due to different crystallographic orientations. Secondly, exposure to focused laser beam from one side may lead to a non-hemispherical tip shape especially when reasonably high laser energy is utilized. For comparison purposes to the laser mode, the voltage pulse evaporated tip end form is also analyzed for different specimen temperatures. Consequently, evaporation fields are calculated for different temperatures and laser conditions for silicon.

Drug policy for visceral leishmaniasis: a cost-effectiveness analysis.

OBJECTIVE: To facilitate the choice of the best visceral leishmaniasis (VL) treatment strategy for first-line health services in (VL)-endemic areas, we compared in a formal decision analysis the cost and the cost-effectiveness of the different available options. METHODS: We selected four drug regimens for VL on the basis of frequency of use, feasibility and reported efficacy studies. The point estimates and the range of plausible values of effectiveness and cost were retrieved from a literature review. A decision tree was constructed and the strategy minimizing the cost per death averted was selected. RESULTS: Treatment with amphotericin B deoxycholate was the most effective approach in the baseline analysis and averted 87.2% of all deaths attributable to VL. The least expensive and the most cost-effective treatment was the miltefosine regimen, and the most expensive and the least cost-effective was AmBisome treatment. The cost of drug and medical care are the main determinants of the cost-effectiveness ranking of the alternative schemes. Sensitivity analysis showed that antimonial was competitive with miltefosine in the low-resistance regions. CONCLUSION: In areas with >94% response rates to antimonials, generic sodium stibogluconate remains the most cost-effective option for VL treatment, mainly due to low drug cost. In other regions, miltefosine is the most cost-effective option of treatment, but its use as a first-line drug is limited by its teratogenicity and rapid resistance development. AmBisome in mono- or combination therapy is too expensive to compete in cost-effectiveness with the other regimens.

Unacceptably high mortality related to measles epidemics in Niger, Nigeria, and Chad.

BACKGROUND: Despite the comprehensive World Health Organization (WHO)/United Nations Children's Fund (UNICEF) measles mortality-reduction strategy and the Measles Initiative, a partnership of international organizations supporting measles mortality reduction in Africa, certain high-burden countries continue to face recurrent epidemics. To our knowledge, few recent studies have documented measles mortality in sub-Saharan Africa. The objective of our study was to investigate measles mortality in three recent epidemics in Niamey (Niger), N'Djamena (Chad), and Adamawa State (Nigeria). METHODS AND FINDINGS: We conducted three exhaustive household retrospective mortality surveys in one neighbourhood of each of the three affected areas: Boukoki, Niamey, Niger (April 2004, n = 26,795); Moursal, N'Djamena, Chad (June 2005, n = 21,812); and Dong District, Adamawa State, Nigeria (April 2005, n = 16,249), where n is the total surveyed population in each of the respective areas. Study populations included all persons resident for at least 2 wk prior to the study, a duration encompassing the measles incubation period. Heads of households provided information on measles cases, clinical outcomes up to 30 d after rash onset, and health-seeking behaviour during the epidemic. Measles cases and deaths were ascertained using standard WHO surveillance-case definitions. Our main outcome measures were measles attack rates (ARs) and case fatality ratios (CFRs) by age group, and descriptions of measles complications and health-seeking behaviour. Measles ARs were the highest in children under 5 y old (under 5 y): 17.1% in Boukoki, 17.2% in Moursal, and 24.3% in Dong District. CFRs in under 5-y-olds were 4.6%, 4.0%, and 10.8% in Boukoki, Moursal, and Dong District, respectively. In all sites, more than half of measles cases in children aged under 5 y experienced acute respiratory infection and/or diarrhoea in the 30 d following rash onset. Of measles cases, it was reported that 85.7% (979/1,142) of patients visited a health-care facility within 30 d after rash onset in Boukoki, 73.5% (519/706) in Moursal, and 52.8% (603/1,142) in Dong District. CONCLUSIONS: Children in these countries still face unacceptably high mortality from a completely preventable disease. While the successes of measles mortality-reduction strategies and progress observed in measles control in other countries of the region are laudable and evident, they should not overshadow the need for intensive efforts in countries that have just begun implementation of the WHO/UNICEF comprehensive strategy.

High sensitivity and specificity of the Pastorex latex agglutination test for Neisseria meningitidis serogroup A during a clinical trial in Niger.

There is a great need for a rapid diagnostic test to guide vaccine choice during outbreaks of meningococcal meningitis in resource-poor countries. During a randomised clinical trial conducted during an epidemic of Neisseria meningitidis serogroup A in Niger in 2003, the sensitivity and specificity of the Pastorex latex agglutination test for this serogroup under optimal field conditions were assessed, using culture and/or PCR as the gold standard. Results from 484 samples showed a sensitivity of 88% (95% CI 85-91%) and a specificity of 93% (95% CI 90-95%). Pastorex could be a good alternative to current methods, as it can be performed in a local laboratory with rapid results and is highly specific. Sensitivity can be improved with prior microscopy where feasible. A study specifically to evaluate the Pastorex test under epidemic conditions, using laboratories with limited resources, is recommended.

Accessibility of diagnostic and treatment centres for visceral leishmaniasis in Gedaref State, northern Sudan.

OBJECTIVE: To evaluate the accessibility of visceral leishmaniasis (VL) treatment. METHOD: Community-based study using in-depth qualitative interviews and focus group discussions with key informants, as well as quantitative questionnaires with 448 randomly selected heads of households in nine representative villages in three geographical sub-regions. RESULTS: Despite the high incidence of the disease, most people in Gedaref State know little about VL, and help at a treatment centre is usually sought only after traditional remedies and basic allopathic drugs have failed. Factors barring access to treatment are: lack of money for treatment and transport, impassability of roads, work priorities, severe cultural restrictions of women's decision-making power and distance to the next health center. CONCLUSIONS: To provide more VL patients with access to treatment in this highly endemic area, diagnostic and treatment services should be decentralized. Health education would be a useful tool to rationalise people's health-seeking behaviour.

Multi-Gaussian phase function model for off-axis laser beam scattering.

Within the small-angle approximation, a multi-Gaussian phase function model provides a new description of the multiple-scattering process and leads to improved agreement with experimental data. A general formula for the off-axis laser beam irradiance is given explicitly for a two-component Gaussian phase function. The predictions of the theory are compared with both the calculations based on the Mie scattering phase function and the results of measurements. It appears that the best fit of the model to experimental results requires an adjustment of the weight factors of the component phase functions. The solution, written in the form of a multiple-scattering series, allows one to interpret individual terms of the scattering series as scattering events of different orders.

Discrete-ordinated finite-element method for atmospheric radiative transfer and remote sensing.

Advantages and disadvantages of modern discrete-ordinates finite-element methods for the solution of radiative transfer problems in meteorology, climatology, and remote sensing applications are evaluated. After the common basis of the formulation of radiative transfer problems in the fields of neutron transport and atmospheric optics is established, the essential features of the discrete-ordinates finite-element method are described including the limitations of the method and their remedies. Numerical results are presented for 1-D and 2-D atmospheric radiative transfer problems where integral as well as angular dependent quantities are compared with published results from other calculations and with measured data. These comparisons provide a verification of the discrete-ordinates results for a wide spectrum of cases with varying degrees of absorption, scattering, and anisotropic phase functions. Accuracy and computational speed are also discussed. Since practically all discrete-ordinates codes offer a builtin adjoint capability, the general concept of the adjoint method is described and illustrated by sample problems. Our general conclusion is that the strengths of the discrete-ordinates finite-element method outweight its weaknesses. We demonstrate that existing general-purpose discrete-ordinates codes can provide a powerful tool to analyze radiative transfer problems through the atmosphere, especially when 2-D geometries must be considered.

Coupled atmosphere/canopy model for remote sensing of plant reflectance features.

Solar radiative transfer through a coupled system of atmosphere and plant canopy is modeled as a multiple-scattering problem through a layered medium of random scatterers. The radiative transfer equation is solved by the discrete-ordinates finite-element method. Analytic expressions are derived that allow the calculation of scattering and absorption cross sections for any plant canopy layer from measurable biophysical parameters such as the leaf area index, leaf angle distribution, and individual leaf reflectance and transmittance data. An expression for a canopy scattering phase function is also given. Computational results are in good agreement with spectral reflectance measurements directly above a soybean canopy, and the concept of greenness- and brightness-transforms of Landsat MSS data is reconfirmed with our computed results. A sensitivity analysis with the coupled atmosphere/canopy model quantifies how satellite-sensed spectral radiances are affected by increased atmospheric aerosols, by varying leaf area index, by anisotropic leaf scattering, and by non-Lambertian soil boundary conditions. Possible extensions to a 2-D model are also discussed.