Segmentability evaluation of back-scattered SEM images of multiphase materials.

Segmentation methods are very useful tools in the Electron Microscopy inspection of materials, enabling the extraction of quantitative results from microscopy images. Back-Scattered Electron (BSE) images carry information of the mean atomic number in the interaction volume and hence can be used to quantify the phase composition in multiphase materials. Since phase composition and proportion affects the material properties and hence its applications, the segmentation accuracy of such images rendered of critical importance for material science. In this work, the notion of segmentability for BSE images is proposed to define the ability of an image to be segmented accurately. This notion can be used to guide the image acquisition process so that segmentability is maximized and segmentation accuracy is ensured. An index is devised to quantify segmentability based on a combination of the modified Fisher Discrimination Ratio and of the second Minkowski functional capturing intensity and spatial aspects of BSE images respectively. The suggested Segmentability Index (SI) is validated in synthetic BSE images which are generated with a novel algorithm allowing the independent control of spatial distribution of phases and their grayscale intensity histograms. Additionally, SI is applied in real-synthetic BSE images, where the real greyscale distributions of Ordinary Portland Cement (OPC) clinker crystallographic phases are used, to demonstrate the ability of SI to indicate the optimum choice of critical image acquisition settings leading to the more accurate segmentation output.

CO2-Derived Nanocarbons with Controlled Morphology and High Specific Capacitance.

The conversion of CO2 to nanocarbons addresses a dual goal of harmful CO2 elimination from the atmosphere along with the production of valuable nanocarbon materials. In the present study, a simple one-step metallothermic CO2 reduction to nanocarbons was performed at 675 °C with the usage of a Mg reductant. The latter was employed alone and in its mixture with ferrocene, which was found to control the morphology of the produced nanocarbons. Scanning electron microscopy (SEM) analysis reveals a gradual increase in the amount of nanoparticles with different shapes and a decrease in tubular nanostructures with the increase of ferrocene content in the mixture. A possible mechanism for such morphological alterations is discussed. Transmission electron microscopy (TEM) analysis elucidates that the nanotubes and nanoparticles gain mainly amorphous structures, while sheet- and cloud-like morphologies also present in the materials possess significantly improved crystallinity. As a result, the overall crystallinity was preserved constant for all of the samples, which was confirmed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques. Finally, electrochemical tests demonstrated that the prepared nanocarbons retained high specific capacitance values in the range of 200-310 F/g (at 0.1 V/s), which can be explained by the measured high specific surface area (650-810 m2/g), total pore volume (1.20-1.55 cm3/g), and the degree of crystallinity. The obtained results demonstrate the suitability of ferrocene for managing the nanocarbons' morphology and open perspectives for the preparation of efficient "green" nanocarbon materials for energy storage applications and beyond.

Segmentation of SEM images of multiphase materials: When Gaussian mixture models are accurate?

Scanning electron microscopy has been a powerful technique to investigate the structural and chemical properties of multiphase materials on micro and nanoscale due to its high-resolution capabilities. One of the main outcomes of the SEM-based analysis is the calculation of the fractions of material components constituting the multiphase material by means of the segmentation of their back scattered electron SEM images. In order to segment multiphase images, Gaussian mixture models (GMMs) are commonly used based on the deconvolution of the image pixel histogram. Despite its extensive use, the accuracy of GMM predictions has not been validated yet. In this paper, we proceed to a systematic study of the evaluation of the accuracy and the limitations of the GMM method when applied to the segmentation of a four-phase material. To this end, first, we build a modelling framework and propose an index to quantify the accuracy of GMM predictions for all phases. Then we apply this framework to calculate the impact of collective parameters of image histogram on the accuracy of GMM predictions. Finally, some rules of thumb are concluded to guide SEM users about the suitability of using GMM for the segmentation of their SEM images based only on the inspection of the image histogram. A suitable histogram for GMM is a histogram with number of peaks equal to the number of Gaussian components, and if that is not the case, kurtosis and skewness should be smaller than 2.35 and 0.1, respectively.

Crystal and electronic facet analysis of ultrafine Ni2P particles by solid-state NMR nanocrystallography.

Structural and morphological control of crystalline nanoparticles is crucial in the field of heterogeneous catalysis and the development of "reaction specific" catalysts. To achieve this, colloidal chemistry methods are combined with ab initio calculations in order to define the reaction parameters, which drive chemical reactions to the desired crystal nucleation and growth path. Key in this procedure is the experimental verification of the predicted crystal facets and their corresponding electronic structure, which in case of nanostructured materials becomes extremely difficult. Here, by employing 31P solid-state nuclear magnetic resonance aided by advanced density functional theory calculations to obtain and assign the Knight shifts, we succeed in determining the crystal and electronic structure of the terminating surfaces of ultrafine Ni2P nanoparticles at atomic scale resolution. Our work highlights the potential of ssNMR nanocrystallography as a unique tool in the emerging field of facet-engineered nanocatalysts.

The Role of Titanium Dioxide on the Hydration of Portland Cement: A Combined NMR and Ultrasonic Study.

Titanium dioxide (TiO2) is an excellent photocatalytic material that imparts biocidal, self-cleaning and smog-abating functionalities when added to cement-based materials. The presence of TiO2 influences the hydration process of cement and the development of its internal structure. In this article, the hydration process and development of a pore network of cement pastes containing different ratios of TiO2 were studied using two noninvasive techniques (ultrasonic and NMR). Ultrasonic results show that the addition of TiO2 enhances the mechanical properties of cement paste during early-age hydration, while an opposite behavior is observed at later hydration stages. Calorimetry and NMR spin-lattice relaxation time T1 results indicated an enhancement of the early hydration reaction. Two pore size distributions were identified to evolve separately from each other during hydration: small gel pores exhibiting short T1 values and large capillary pores with long T1 values. During early hydration times, TiO2 is shown to accelerate the formation of cement gel and reduce capillary porosity. At late hydration times, TiO2 appears to hamper hydration, presumably by hindering the transfer of water molecules to access unhydrated cement grains. The percolation thresholds were calculated from both NMR and ultrasonic data with a good agreement between both results.

Iron-substituted cubic silsesquioxane pillared clays: Synthesis, characterization and acid catalytic activity.

Novel pillared structures were developed from the intercalation of iron-substituted cubic silsesquioxanes in a sodium and an acid-activated montmorillonite nanoclay and evaluated as acid catalysts. Octameric cubic oligosiloxanes were formed upon controlled hydrolytic polycondensation of the corresponding monomer (a diamino-alkoxysilane) and reacted with iron cations to form complexes that were intercalated within the layered nanoclay matrices. Upon calcination iron oxide nanoparticles are formed which are located on the silica cubes (pillars) and on the surfaces of the clay platelets. Acid activation of the nanoclay was performed in order to increase the number of acid active sites in the pristine clay and thus increase its catalytic activity. A plethora of analytical techniques including X-ray diffraction, thermal analyses, Fourier transform infrared, electron paramagnetic resonance, Raman, Mössbauer and X-ray photoelectron spectroscopies and porosimetry measurements were used in order to follow the synthesis steps and to fully characterize the final catalysts. The resulting pillared clays exhibit a high specific area and show significant acid catalytic activity that was verified using the catalytic dehydration of isopropanol asa probe reaction.

Cytotoxicity of prion protein-derived cell-penetrating peptides is modulated by pH but independent of amyloid formation.

Prion diseases are associated with conversion of cellular prion protein (PrPC) into an abnormally folded and infectious scrapie isoform (PrPSc). We previously showed that peptides derived from the unprocessed N-termini of mouse and bovine prion proteins, mPrP1-28 and bPrP1-30, function as cell-penetrating peptides (CPPs), and destabilize model membrane systems, which could explain the infectivity and toxicity of prion diseases. However, subsequent studies revealed that treatment with mPrP1-28 or bPrP1-30 significantly reduce PrPSc levels in prion-infected cells. To explain these seemingly contradictory results, we correlated the aggregation, membrane perturbation and cytotoxicity of the peptides with their cellular uptake and intracellular localization. Although the peptides have a similar primary sequence, mPrP1-28 is amyloidogenic, whereas bPrP1-30 forms smaller oligomeric or non-fibrillar aggregates. Surprisingly, bPrP1-30 induces much higher cytotoxicity than mPrP1-28, indicating that amyloid formation and toxicity are independent. The toxicity is correlated with prolonged residence at the plasma membrane and membrane perturbation. Both ordered aggregation and toxicity of the peptides are inhibited by low pH. Under non-toxic conditions, the peptides are internalized by lipid-raft dependent macropinocytosis and localize to acidic lysosomal compartments. Our results shed light on the antiprion mechanism of the prion protein-derived CPPs and identify a potential site for PrPSc formation.