Protocrystallinity of Monodispersed Ultra-Small Templated Mesoporous Silica Nanoparticles.

Monodisperse and semi-faceted ultra-small templated mesoporous silica nanoparticles (US-MSNs) of 20-25 nm were synthesized using short-time hydrolysis of tetraethoxysilane (TEOS) at room temperature, followed by a dilution for nucleation quenching. According to dynamic light scattering (DLS), a two-step pH adjustment was necessary for growth termination and colloidal stabilization. The pore size was controlled by cetyltrimethylammonium bromide (CTAB), and a tiny amount of neutral surfactant F127 was added to minimize the coalescence between US-MSNs and to favor the transition towards internal ordering. Flocculation eventually occurred, allowing us to harvest a powder by centrifugation (~60% silica yield after one month). Scanning transmission electron microscopy (STEM) and 3D high-resolution transmission electron microscopy (3D HR-TEM) images revealed that the US-MSNs are partially ordered. The 2D FT transform images provide evidence for the coexistence of four-, five-, and sixfold patterns characterizing an "on-the-edge" crystallization step between amorphous raspberry and hexagonal pore array morphologies, typical of a protocrystalline state. Calcination preserved this state and yielded a powder characterized by packing, developing a hierarchical porosity centered at 3.9 ± 0.2 (internal pores) and 68 ± 7 nm (packing voids) of high potential for support for separation and catalysis.

Deep learning detection of nanoparticles and multiple object tracking of their dynamic evolution during in situ ETEM studies.

In situ transmission electron microscopy (TEM) studies of dynamic events produce large quantities of data especially under the form of images. In the important case of heterogeneous catalysis, environmental TEM (ETEM) under gas and temperature allows to follow a large population of supported nanoparticles (NPs) evolving under reactive conditions. Interpreting properly large image sequences gives precious information on the catalytic properties of the active phase by identifying causes for its deactivation. To perform a quantitative, objective and robust treatment, we propose an automatic procedure to track nanoparticles observed in Scanning ETEM (STEM in ETEM). Our approach involves deep learning and computer vision developments in multiple object tracking. At first, a registration step corrects the image displacements and misalignment inherent to the in situ acquisition. Then, a deep learning approach detects the nanoparticles on all frames of video sequences. Finally, an iterative tracking algorithm reconstructs their trajectories. This treatment allows to deduce quantitative and statistical features about their evolution or motion, such as a Brownian behavior and merging or crossing events. We treat the case of in situ calcination of palladium (oxide) / delta-alumina, where the present approach allows a discussion of operating processes such as Ostwald ripening or NP aggregative coalescence.

Highly ductile amorphous oxide at room temperature and high strain rate.

Oxide glasses are an integral part of the modern world, but their usefulness can be limited by their characteristic brittleness at room temperature. We show that amorphous aluminum oxide can permanently deform without fracture at room temperature and high strain rate by a viscous creep mechanism. These thin-films can reach flow stress at room temperature and can flow plastically up to a total elongation of 100%, provided that the material is dense and free of geometrical flaws. Our study demonstrates a much higher ductility for an amorphous oxide at low temperature than previous observations. This discovery may facilitate the realization of damage-tolerant glass materials that contribute in new ways, with the potential to improve the mechanical resistance and reliability of applications such as electronic devices and batteries.

Electron Tomography of Plasmonic Au Nanoparticles Dispersed in a TiO2 Dielectric Matrix.

Plasmonic Au nanoparticles (AuNPs) embedded into a TiO2 dielectric matrix were analyzed by combining two-dimensional and three-dimensional electron microscopy techniques. The preparation method was reactive magnetron sputtering, followed by thermal annealing treatments at 400 and 600 °C. The goal was to assess the nanostructural characteristics and correlate them with the optical properties of the AuNPs, particularly the localized surface plasmon resonance (LSPR) behavior. High-angle annular dark field-scanning transmission electron microscopy results showed the presence of small-sized AuNPs (quantum size regime) in the as-deposited Au-TiO2 film, resulting in a negligible LSPR response. The in-vacuum thermal annealing at 400 °C induced the formation of intermediate-sized nanoparticles (NPs), in the range of 10-40 nm, which led to the appearance of a well-defined LSPR band, positioned at 636 nm. Electron tomography revealed that most of the NPs are small-sized and are embedded into the TiO2 matrix, whereas the larger NPs are located at the surface. Annealing at 600 °C promotes a bimodal size distribution with intermediate-sized NPs embedded in the matrix and big-sized NPs, up to 100 nm, appearing at the surface. The latter are responsible for a broadening and a redshift, to 645 nm, in the LSPR band because of increase of scattering-to-absorption ratio. Beyond differentiating and quantifying the surface and embedded NPs, electron tomography also provided the identification of "hot-spots". The presence of NPs at the surface, individual or in dimers, permits adsorption sites for LSPR sensing and for surface-enhanced spectroscopies, such as surface-enhanced Raman scattering.

Contribution of Local Analysis Techniques for the Characterization of Iron and Alloying Elements in Nitrides: Consequences on the Precipitation Process in Fe⁻Si and Fe⁻Cr Nitrided Alloys.

Atom Probe Tomography (APT), Transmission Electron Microscopy (TEM), and 3D mechanical calculations in complex geometry and anisotropic strain fields were employed to study the role of minor elements in the precipitation process of silicon and chromium nitrides in nitrided Fe⁻Si and Fe⁻Cr alloys, respectively. In nitrided Fe⁻Si alloys, an original sequence of Si3N4 precipitation was highlighted. Al⁻N clusters form first and act as nucleation sites for amorphous Si3N4 nitrides. This novel example of particle-simulated nucleation opens a new way to control Si3N4 precipitation in Fe⁻Si alloys. In nitrided Fe⁻Cr alloys, both the presence of iron in chromium nitrides and excess nitrogen in the ferritic matrix are unquestionably proved. Only a certain part of the so-called excess nitrogen is shown to be explained by the elastic accommodation of the misfit between nitride and the ferritic matrix. The presence of immobile excess nitrogen trapped at interfaces can be highly suspected.

Evaluation of noise and blur effects with SIRT-FISTA-TV reconstruction algorithm: Application to fast environmental transmission electron tomography.

Fast tomography in Environmental Transmission Electron Microscopy (ETEM) is of a great interest for in situ experiments where it allows to observe 3D real-time evolution of nanomaterials under operating conditions. In this context, we are working on speeding up the acquisition step to a few seconds mainly with applications on nanocatalysts. In order to accomplish such rapid acquisitions of the required tilt series of projections, a modern 4K high-speed camera is used, that can capture up to 100 images per second in a 2K binning mode. However, due to the fast rotation of the sample during the tilt procedure, noise and blur effects may occur in many projections which in turn would lead to poor quality reconstructions. Blurred projections make classical reconstruction algorithms inappropriate and require the use of prior information. In this work, a regularized algebraic reconstruction algorithm named SIRT-FISTA-TV is proposed. The performance of this algorithm using blurred data is studied by means of a numerical blur introduced into simulated images series to mimic possible mechanical instabilities/drifts during fast acquisitions. We also present reconstruction results from noisy data to show the robustness of the algorithm to noise. Finally, we show reconstructions with experimental datasets and we demonstrate the interest of fast tomography with an ultra-fast acquisition performed under environmental conditions, i.e. gas and temperature, in the ETEM. Compared to classically used SIRT and SART approaches, our proposed SIRT-FISTA-TV reconstruction algorithm provides higher quality tomograms allowing easier segmentation of the reconstructed volume for a better final processing and analysis.

Mechanical characterization of diesel soot nanoparticles: in situ compression in a transmission electron microscope and simulations.

Incomplete fuel burning inside an internal combustion engine results in the creation of soot in the form of nanoparticles. Some of these soot nanoparticles (SNP) become adsorbed into the lubricating oil film present on the cylinder walls, which adversely affects the tribological performance of the lubricant. In order to better understand the mechanisms underlying the wear caused by SNPs, it is important to understand the behavior of SNPs and to characterize potential changes in their mechanical properties (e.g. hardness) caused by (or during) mechanical stress. In this study, the behavior of individual SNPs originating from diesel engines was studied under compression. The experiments were performed in a transmission electron microscope using a nanoindentation device. The nanoparticles exhibited elasto-plastic behavior in response to consecutive compression cycles. From the experimental data, the Young's modulus and hardness of the SNPs were calculated. The Young's modulus and hardness of the nanoparticles increased with the number of compression cycles. Using an electron energy loss spectroscopy technique, it was shown that the sp2/sp3 ratio within the compressed nanoparticle decreases, which is suggested to be the cause of the increase in elasticity and hardness. In order to corroborate the experimental findings, molecular dynamics simulations of a model SNP were performed. The SNP model was constructed using carbon and hydrogen atoms with morphology and composition comparable to those observed in the experiment. The model SNP was subjected to repeated compressions between two virtual rigid walls. During the simulation, the nanoparticle exhibited elasto-plastic behavior like that in the experiments. The results of the simulations confirm that the increase in the elastic modulus and hardness is associated with a decrease in the sp2/sp3 ratio.

Tracking the restructuring of oxidized silver-indium nanoparticles under a reducing atmosphere by environmental HRTEM.

Multimetallic nano-alloys display a structure and consequently physicochemical properties evolving in a reactive environment. Following and understanding this evolution is therefore crucial for future applications in gas sensing and heterogeneous catalysis. In view hereof, the structural evolution of oxidized Ag25In75 bimetallic nanoparticles under varying H2 partial pressures (PH2) and substrate temperatures (Ts) has been investigated in real-time through environmental transmission microscopy (E-TEM) while maintaining the atomic resolution. Small Ag25In75 bimetallic nanoparticles, produced by laser vaporization, are found (after air transfer) to contain an indium-oxide shell surrounding a silver-rich alloyed phase. For high PH2 and Ts, the direct reduction of the indium oxide shell, immediately followed by the melting or the diffusion onto the carbon substrate of the reduced indium atoms, is found to be the dominant mechanism. This reduction is concomitant with the growth of the core, indicating a partial diffusion of indium atoms from the shell towards the particle volume. The "surviving" particles therefore consist of a silver-indium alloy, very stable and remarkably resistant against oxidation contrary to native clusters. Interestingly, in the (PH2, Ts) space, the transition from "soft" (core-shell particles for low (PH2, Ts) values) to "strong" reduction conditions (silver-rich alloys for high (PH2, Ts) products) defines an intermediate domain where the preferred formation of Janus structures is detected. These results are discussed in terms of thermodynamic driving forces in relation to alloying and interface energies. This work shows the potential of high-resolution ETEM for unravelling the mechanisms of nanoparticle reorganization in a chemically reactive environment.

Tuning the Structure of Platinum Particles on Ceria In†Situ for Enhancing the Catalytic Performance of Exhaust Gas Catalysts.

A dynamic structural behavior of Pt nanoparticles on the ceria surface under reducing/oxidizing conditions was found at moderate temperatures (<500 °C) and exploited to enhance the catalytic activity of Pt/CeO2 -based exhaust gas catalysts. Redispersion of platinum in an oxidizing atmosphere already occurred at 400 °C. A protocol with reducing pulses at 250-400 °C was applied in a subsequent step for controlled Pt-particle formation. Operando X-ray absorption spectroscopy unraveled the different extent of reduction and sintering of Pt particles: The choice of the reductant allowed the tuning of the reduction degree/particle size and thus the catalytic activity (CO>H2 >C3 H6 ). This dynamic nature of Pt on ceria at such low temperatures (250-500 °C) was additionally confirmed by in situ environmental transmission electron microscopy. A general concept is proposed to adjust the noble metal dispersion (size, structure), for example, during operation of an exhaust gas catalyst.

Three-Dimensional Self-Organization in Nanocomposite Layered Systems by Ultrafast Laser Pulses.

Controlling plasmonic systems with nanometer resolution in transparent films and their colors over large nonplanar areas is a key issue for spreading their use in various industrial fields. Using light to direct self-organization mechanisms provides high-speed and flexible processes to meet this challenge. Here, we describe a route for the laser-induced self-organization of metallic nanostructures in 3D. Going beyond the production of planar nanopatterns, we demonstrate that ultrafast laser-induced excitation combined with nonlinear feedback mechanisms in a nanocomposite thin film can lead to 3D self-organized nanostructured films. The process, which can be extended to complex layered composite systems, produces highly uniform large-area nanopatterns. We show that 3D self-organization originates from the simultaneous excitation of independent optical modes at different depths in the film and is activated by the plasmon-induced charge separation and thermally induced NP growth mechanisms. This laser color marking technique enables multiplexed optical image encoding and the generated nanostructured Ag NPs:TiO2 films offer great promise for applications in solar energy harvesting, photocatalysis, or photochromic devices.

Internalization pathways into cancer cells of gadolinium-based radiosensitizing nanoparticles.

Over the last few decades, nanoparticles have been studied in theranostic field with the objective of exhibiting a long circulation time through the body coupled to major accumulation in tumor tissues, rapid elimination, therapeutic potential and contrast properties. In this context, we developed sub-5 nm gadolinium-based nanoparticles that possess in vitro efficient radiosensitizing effects at moderate concentration when incubated with head and neck squamous cell carcinoma cells (SQ20B). Two main cellular internalization mechanisms were evidenced and quantified: passive diffusion and macropinocytosis. Whereas the amount of particles internalized by passive diffusion is not sufficient to induce in vitro a significant radiosensitizing effect, the cellular uptake by macropinocytosis leads to a successful radiotherapy in a limited range of particles incubation concentration. Macropinocytosis processes in two steps: formation of agglomerates at vicinity of the cell followed by their collect via the lamellipodia (i.e. the "arms") of the cell. The first step is strongly dependent on the physicochemical characteristics of the particles, especially their zeta potential that determines the size of the agglomerates and their distance from the cell. These results should permit to control the quantity of particles internalized in the cell cytoplasm, promising ambitious opportunities towards a particle-assisted radiotherapy using lower radiation doses.

Toward an image-guided microbeam radiation therapy using gadolinium-based nanoparticles.

Ultrasmall gadolinium-based nanoparticles (GBNs) induce both a positive contrast for magnetic resonance imaging and a radiosentizing effect. The exploitation of these characteristics leads to a greater increase in lifespan of rats bearing brain tumors since the radiosensitizing effect of GBNs can be activated by X-ray microbeams when the gadolinium content is, at the same time, sufficiently high in the tumor and low in the surrounding healthy tissue. GBNs exhibit therefore an interesting potential for image-guided radiotherapy.

Complex precipitation pathways in multicomponent alloys.

One usual way to strengthen a metal is to add alloying elements and to control the size and the density of the precipitates obtained. However, precipitation in multicomponent alloys can take complex pathways depending on the relative diffusivity of solute atoms and on the relative driving forces involved. In Al-Zr-Sc alloys, atomic simulations based on first-principle calculations combined with various complementary experimental approaches working at different scales reveal a strongly inhomogeneous structure of the precipitates: owing to the much faster diffusivity of Sc compared with Zr in the solid solution, and to the absence of Zr and Sc diffusion inside the precipitates, the precipitate core is mostly Sc-rich, whereas the external shell is Zr-rich. This explains previous observations of an enhanced nucleation rate in Al-Zr-Sc alloys compared with binary Al-Sc alloys, along with much higher resistance to Ostwald ripening, two features of the utmost importance in the field of light high-strength materials.