Archive 4 November 2019

Coupling Bragg Coherent Diffraction Imaging (BCDI) and Molecular Dynamics to investigate nanostructure

Fig. 1 (top) Experimental reconstruction of the u111 displacement field on a 250 nm Pt NP (bottom)  u111 displacement field obtained by energy minimization of a simulated Pt NP (right) εxx, εyy and  εzz components of the strain tensor derived from the simulation

Physical properties at small length scale deviate strongly from the bulk counterpart, typically below the micrometer. For instance, mechanical strength increases with reducing size, large residual strain due to processing are present in nanostructures. Thus a better understanding of the physical properties in relationship with the microstructure is needed for nanoscale materials. Because of its good spatial resolution (~ 10 nm) and excellent sensitivity to atomic displacements and local strain [1,2], Bragg coherent diffraction imaging (BCDI) has emerged in the past two decades as a powerful tool to probe the structure and local displacement field inside nanoscale objects [3]. When combined with in situ mechanical loading, BCDI is particularly relevant for the study of defect nucleations in isolated nanoparticles [4] or to investigate intragranular deformation mechanisms in polycrystalline thin films [5].

Nowadays, the length scales that are accessible by BCDI and that can be simulated by Molecular Dynamics (MD) simulation are almost converging. The coupling between the two methods is therefore particularly relevant and allows to get a detailed picture of the deformation mechanisms in nanostructures at the atomic scale. This coupled approach has been used to study the surface relaxation of metallic nanoparticles (Au, Pt). An excellent quantitative agreement is obtained between the component of the displacement field measured experimentally and calculated by energy minimization (Molecular Statics) (Fig. 1). With this approach, the measurement of only one Bragg reflection is required to derive the 3D displacement field and the six independent components of the strain tensor from the simulation [6]. The two techniques can also be combined to  identify defect structures nucleated during in situ  mechanical loading [4,5] and to interpret the evolution of the strain field in nanoparticle catalysts during gas reaction [7,8]..

[1] Watari, M. et al. Nature Materials 10, 862–866 (2011).

[2] Labat, S. et al. ACS Nano 9, 9210–9216 (2015).

[3] Robinson, I. & Harder, R. Nat Mater 8, 291–298 (2009).

[4] Dupraz, M. et al. Nano Lett. 17(11) (2017).

[5] Cherukara, M. et al. Nat. Comm. (2018).

[6] Dupraz et al.  to be submitted (2019)

[7] Kim, D. et al. Nat. Comm. 9, 3422 (2018).

[8] Dupraz, M. et al. in preparation

Speaker: Dr. Maxime Dupraz

Date and Location: Monday 25/11/19, 14h00 LEM meeting room (E2.01.20), Châtillon.

Modelling the mechanical behaviour of polycrystalline materials

Understanding the deformation processes that lead to the failure of polycrystalline structural materials is one of the main challenges in materials science. Significant progress has been made in recent decades, thanks to the development of new experimental characterisation techniques and advanced simulation methods.

However, the localisation of plasticity in slip bands and the propagation of plasticity through a polycrystalline aggregate are not fully understood.

One of the difficulties in modelling the mechanical behaviour of polycrystalline materials is its intrinsically  multi-scale nature. Inelastic deformation mechanisms occur at the dislocation scale (dislocation is a crystalline defect ,vector of plastic deformation) that result in the formation of intra-granular microstructures which, in turn, interact with grain boundaries.

This internship project aims to study the first stages of plastic deformation in policrystalline materials (Cu, Ni) using dislocation dynamics (DD). In particular, the microMegas DD code coupled with a mechanical solver will be used, to correctly handle boundary conditions,  to capture the onset of    plastic deformation localisation and thus model the interaction between a slip band and  grain boundaries. 
This mechanism will be studied in a “model” polycrystalline aggregate, and then, if possible,  extended to a digital twin of a real polycrystal.

 

Job: Internship (4-6 months)

Academic level : Master degree

Location: LEM, Châtillon

Expertise: : Solid state physics, Materials Science. Interest in theoretical physics and numerical simulations

Contacts: Benoit Devincre

Elaboration and characterization of metallic nanoparticles; analysis of synthesis effects in the growth of carbon nanotubes by CVD

The proposed internship topic is part of a cooperative project on the development of new catalysts (metal or bimetallic nanoparticles) for the growth of carbon nanotubes, aiming at controlling their electronic properties during their synthesis.

The nanoparticles as catalysts will be synthesized, in collaboration with the partnering group of Pr V. Huc at the Institute of Molecular Chemistry and Orsay Materials (ICCMO) by combining surface chemistry and coordination chemistry. We propose to compare the same set of metallic or bimetallic nanoparticles synthesized using very different synthetic pathways and then we will compare the catalytic action of these nanoparticles in the growth of nanotubes.

We will focus on the Ni-Ru catalytic system, identified as a good candidate for achieving the desired electronic character selectivity.

– A first part of the experimental work will be to synthesize the nanoparticles using soft chemistry via the colloidal route (optimization of the synthesis by first reducing the Ru3 + in Ru2 + and then combining it with Ni) and Prussian Blue Analogues at ICMMO. The latter will be calcined under argon in order to obtain carbureted species. We will do the structural study (size distribution, composition, crystalline structure) at LEM. For the latter, we will use a powerful set of investigation techniques (high-resolution transmission electron microscopy, diffraction, energy loss spectroscopy and X-ray spectroscopy) present in the laboratory (LEM).

– A second part of the experimental work will be to grow carbon nanotubes by CVD using the nanoparticles developed as a catalyst (colloidal, by “Prussian blue” and Prussian blue “carbides”) and to characterize their structures (chirality, length, type of adhesion to the nanoparticle) by TEM (imaging and diffraction) and Raman spectroscopy. These three sets of catalysts should be compared to observe the influence of the synthesis route and the influence of the carburized phase on the growth of carbon nanotubes.

Job: Internship (4-6 months)

Academic level : Master degree

Location: LEM, Châtillon

Expertise: Good training in condensed matter physics and chemistry with a major focus on nanoscience and courses on synthesis and characterization.
Strong interest for experiments

Contacts: Armelle Girard, Annick.Loiseau

Chemistry and morphology of nanoalloys for growth catalysis of carbon nanotubes by CVD

The proposed internship topic is part of a cooperative project on the development of new bimetallic catalysts in the solid solution state for the growth of carbon nanotubes, aiming at controlling their electronic properties during their synthesis.

Although several techniques are available for the synthesis of transition metal-based bimetallic catalysts, they generally lead to nanoparticles with a core/shell or janus morphology. Nevertheless, our previous studies have shown that it is possible to synthesize bimetallic particles in solid solution state, that is with no elemental segregation within the nanoparticle by combining surface chemistry and coordination chemistry under particular temperature conditions.

However, studying the thermodynamic behavior of these bimetallic catalysts often requires the implementation of complicated experimental techniques that often need to be coupled with theoretical approaches, even if the latter are still far from being able to reach such a level of complexity while remaining predictive. In collaboration with the partnering group of numerical simulations at the Institute of Molecular Chemistry and Orsay Materials (ICCMO) (Jérôme Creuze and Fabienne Berthier), we will undertake theoretical study to better characterize the behavior of these nanoparticles, in equilibrium and under ultra-vacuum first. Indeed, it is necessary to know the thermodynamics of nanoalloys as isolated systems before studying the influence of external perturbations. We will also study the kinetics of return to equilibrium in order to determine the stability and the lifetime of metastable configurations that will have been identified during the first step of the study.

The internship will thus identify and quantify the key thermodynamic parameters involved in the distribution of constituents within the bimetallic nanoparticles and understand how the thermodynamic variables influence the equilibrium configuration using these parameters. The candidate will be able to compare his results with experiences when possible.

Job: Internship (4-6 months)

Academic level : Master degree

Location: LEM, Châtillon

Expertise: Good training in condensed matter physics and chemistry with a major focus on nanoscience, thermodynamics. Strong interest for numerical calculations

Contacts: Armelle Girard, Annick.Loiseau