Karine Masenelli-Varlot

Facile and rapid synthesis of highly luminescent nanoparticles via pulsed laser ablation in liquid.

This paper demonstrates the usefulness of pulsed laser ablation in liquids as a fast screening synthesis method able to prepare even complex compositions at the nanoscale. Nanoparticles of Y2O3:Eu3+, Lu2O2S:Eu3+, Gd2SiO5:Ce3+, Lu3TaO7:Gd3+ and Tb3+ are successfully synthesized by pulsed laser ablation in liquids. The phase and stoichiometries of the original materials are preserved while the sizes are reduced down to 5-10 nm. The optical properties of the materials are also preserved but show some small variations and some additional structures which are attributed to the specificities of the nanoscale (internal pressure, inhomogeneous broadening, surface states, etc).

Image analysis characterization of multi-walled carbon nanotubes

An original image analysis method is presented to characterize multi-walled carbon nanotubes from transmission electron microscopy images. The analysis is performed in three steps: (i) image preprocessing in order to isolate the nanotubes from the background, (ii) image segmentation, aiming at keeping only the measurable sections of nanotubes, and finally (iii) tube characteristics measurement. The measurement is based on a Lambert-like electron absorption law and is performed on the original gray level image itself. Two geometrical and one physical characteristics are determined for each tube, namely, its outer and inner radius and a linear electron absorption coefficient. The method is illustrated by comparing a pristine and an annealed carbon nanotube samples. The compaction of the tube walls during annealing is shown to result from a lowering of the external radius while the inner radius is left unchanged.

Electron tomography combining ESEM and STEM: A new 3D imaging technique

This paper presents the development and the application of a new electron tomography technique based on STEM (Scanning Transmission Electron Microscopy) configuration in ESEM (Environmental Scanning Electron Microscopy). This combination provides a new approach for the characterization of the 3D structure of materials, as it optimizes a compromise between the resolution level of a few tens of nm and the large tomogram size due to the high thickness of transparency. The method is well adapted for non-conductive samples, and exhibits good contrast even for materials with low atomic number. The paper describes the development of a dedicated stage for this new tomography technique. Taking advantage of the size of the ESEM chamber, the range of tilt angles is not limited by the space around the sample. The performance of this device is illustrated through the three-dimensional characterization of samples issued from materials science and chosen to illustrate the results in resolution, contrast and thickness.

Wet-STEM tomography: principles, potentialities and limitations.

The characterization of biological and inorganic materials by determining their three-dimensional structure in conditions closer to their native state is a major challenge of technological research. Environmental scanning electron microscopy (ESEM) provides access to the observation of hydrated samples in water environments. Here, we present a specific device for ESEM in the scanning transmission electron microscopy mode, allowing the acquisition of tilt-series suitable for tomographic reconstructions. The resolution which can be obtained with this device is first determined. Then, we demonstrate the feasibility of tomography on wet materials. The example studied here is hydrophilic mesoporous silica (MCM-41). Finally, the minimum thickness of water which can be detected is calculated from Monte Carlo simulations and compared with the resolution expected in the tomograms.

Intense visible emission from ZnO/PAAX (X = H or Na) nanocomposite synthesized via a simple and scalable sol-gel method.

Intense visible nano-emitters are key objects for many technologies such as single photon source, bio-labels or energy convertors. Chalcogenide nanocrystals have ruled this domain for several decades. However, there is a demand for cheaper and less toxic materials. In this scheme, ZnO nanoparticles have appeared as potential candidates. At the nanoscale, they exhibit crystalline defects which can generate intense visible emission. However, even though photoluminescence quantum yields as high as 60% have been reported, it still remains to get quantum yield of that order of magnitude which remains stable over a long period. In this purpose, we present hybrid ZnO/polyacrylic acid (PAAH) nanocomposites, obtained from the hydrolysis of diethylzinc in presence of PAAH, exhibiting quantum yield systematically larger than 20%. By optimizing the nature and properties of the polymeric acid, the quantum yield is increased up to 70% and remains stable over months. This enhancement is explained by a model based on the hybrid type II heterostructure formed by ZnO/PAAH. The addition of PAAX (X = H or Na) during the hydrolysis of ZnEt2 represents a cost effective method to synthesize scalable amounts of highly luminescent ZnO/PAAX nanocomposites.

Analysis of liquid suspensions using scanning electron microscopy in transmission: estimation of the water film thickness using Monte–Carlo simulations

Environmental scanning electron microscopy (ESEM) allows the observation of liquids under specific conditions of pressure and temperature. Moreover, when working in the transmission mode, that is in scanning transmission electron microscopy (STEM), nano‐objects can be analysed inside a liquid. The contrast in the images is mass‐thickness dependent as in STEM‐in‐TEM (transmission electron microscopy) using closed cells. However, in STEM‐in‐ESEM, as the liquid–vapour equilibrium is kept dynamically, the thickness of the water droplet remains unknown. In this paper, the contrasts measured in the experimental images are compared with calculations using Monte‐Carlo simulations in order to estimate the thickness of water. Two examples are given. On gold nanoparticles, the thickness of a thick film can be estimated thanks to a contrast inversion. On core‐shell latex particles, the grey level of the shell compared with those of the core and of the water film gives a relatively precise measurement of the water film thickness.

Thickness evaluation of thermally sprayed coatings after exposure to boiler tube environments by eddy current testing

This paper discusses the feasibility of determining the thickness of Ni-based alloy sprayed coatings that have been heated in plant environments using swept frequency eddy current testing based on the measurement of the impedance spectrum of the measurement coil. Through a comparison of the experimental and computed signals, an electromagnetic model simulating the test geometry including the coating and the substrate is presented, with particular focus on the effects of heat treatment. Using these models, the coating thickness is estimated using the measured impedance spectra, and the estimation error was found to be around 30 μm.

A global investigation into in situ nanoindentation experiments on zirconia: from the sample geometry optimization to the stress nanolocalization using convergent beam electron diffraction

Nanoindentation experiments inside a transmission electron microscope are of much interest to characterize specific phenomena occuring in materials, like for instance dislocation movements or phase transformations. The key points of these experiments are (i) the sample preparation and the optimization of its geometry to obtain reliable results and (ii) the choice of the transmission electron microscope observation mode, which will condition the type of information which can be deduced from the experiment. In this paper, we will focus on these two key points in the case of nanoindentation of zirconia, which is a ceramic material well known to be sensitive to stress because it can undergo a phase transformation. In this case, the information sought is the stress localization at the nanometre scale and in real time. As far as the sample preparation is concerned, one major drawback of nanoindentation inside a transmission electron microscope is indeed a possible bending of the sample occurring during compression, which is detrimental to the experiment interpretation (the stress is not uniaxial anymore). In this paper, several sample preparation techniques have been used and compared to optimize the geometry of the sample to avoid bending. The results obtained on sample preparation can be useful for the preparation of ceramics samples but can also give interesting clues and experimental approaches to optimize the preparation of other kinds of materials.

Study of the surfactant role in latex–aerogel systems by scanning transmission electron microscopy on aqueous suspensions

For insulation applications, boards thinner than 2 cm are under design with specific thermal conductivities lower than 15 mW m−1 K−1. This requires binding slightly hydrophobic aerogels which are highly nanoporous granular materials. To reach this step and ensure insulation board durability at the building scale, it is compulsory to design, characterise and analyse the microstructure at the nanoscale. It is indeed necessary to understand how the solid material is formed from a liquid suspension. This issue is addressed in this paper through wet‐STEM experiments carried out in an Environmental Scanning Electron Microscope (ESEM). Latex–surfactant binary blends and latex–surfactant–aerogel ternary systems are studied, with two different surfactants of very different chemical structures. Image analysis is used to distinguish the different components and get quantitative morphological parameters which describe the sample architecture. The evolution of such morphological parameters during water evaporation permits a good understanding of the role of the surfactant.

3D Multiscale Characterization of Silica Aerogels Composites

New composites based on a matrix of silica aerogel grains are currently being developed to answer the expectations of thermal renovation. One of the key parameters for their commercial use is the control of their porous network. In this study, we aim to propose a three-dimensional characterization from the nanometer to the millimeter scale of the silica aerogel particles themselves. Transmission electron microscopy (TEM) is used to characterize the mesoporous network within the aerogel grain. The arrangement in three dimensions of the grains and the voids within the aerogel grain pileup is investigated at the micron scale by X-ray tomography.