Denis Machon

Materials Physics, Experimental Physics, Condensed Matter Physics

PhD
35.01

Publications

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    Denis Machon

    Full-text · Book · Nov 2015
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    ABSTRACT: The mechanical stability of single-wall carbon nanotubes (SWCNTs) at high pressure was studied by high-resolution resonant Raman and wavelength-dependent fluorescence-excitation (PLE) spectroscopy resolving the vibrational and electronic resonances of 18 individual chiralities and furthermore even resolving the different behaviour of empty (closed, pristine) and water-filled (opened) SWCNTs (diameter range = 0.6-1.42 nm). We find that water-filling exerts a stabilizing counter-pressure on the SWCNT walls, leading to an increasing difference between the radial breathing mode frequencies of water-filled and empty SWCNTs at elevated pressures. For small diameter SWCNTs (d < 1 nm) with a chiral angle of ∼12°, in particular for the (7,2) chirality, an anomalous behaviour is observed, revealing an increased mechanical instability for these SWCNTs. We furthermore ascribe the longstanding contradiction between experiments and theory on the collapse pressure of SWCNTs to the presence of filling in most experiments to date, while empty SWCNTs follow the theoretically predicted collapse behaviour.
    No preview · Article · Aug 2015 · Carbon
  • P. Mélinon · D. Machon · S. Daniele · B. Masenelli

    No preview · Article · Jan 2015
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    Denis Machon · Patrice Mélinon
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    ABSTRACT: Below a critical particle size, some pressurized compounds (e.g. TiO2, Y2O3, PbTe) undergo a crystal-to-amorphous transformation instead of a polymorphic transition. This effect reflects the greater propensity of nanomaterials for amorphization. In this work, a panorama of thermodynamic interpretations is given: first, a descriptive analysis based on the energy landscapes concept gives a general comprehension of the balance between thermodynamics and kinetics to obtain an amorphous state. Then, a formal approach based on Gibbs energy to describe the thermodynamics and phase transitions in nanoparticles gives a basic explanation of size-dependent pressure-induced amorphization. The features of this transformation (amorphization occurs at pressures lower than the polymorphic transition pressure!) and the nanostructuration can be explained in an elaborated model based on the Ginzburg-Landau theory of phase transition and on percolation theory. It is shown that the crossover between polymorphic transition and amorphization is highly dependent on the defect density and interfacial energy, i.e., on the synthesis process. Their behavior at high pressure is a quality control test for the nanoparticles.
    Full-text · Article · Nov 2014 · Physical Chemistry Chemical Physics
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    Full-text · Dataset · Aug 2014
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    ABSTRACT: Perfectly crystalline solids are excellent heat conductors. Prominent counterexamples are intermetallic clathrates, guest-host systems with a high potential for thermoelectric applications due to their ultralow thermal conductivities. Our combined experimental and theoretical investigation of the lattice dynamics of a particularly simple binary representative, Ba_{8}Si_{46}, identifies the mechanism responsible for the reduction of lattice thermal conductivity intrinsic to the perfect crystal structure. Above a critical wave vector, the purely harmonic guest-host interaction leads to a drastic transfer of spectral weight to the guest atoms, corresponding to a localization of the propagative phonons.
    Full-text · Article · Jul 2014 · Physical Review Letters
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    ABSTRACT: The effect of an applied high pressure on the optical and acoustic vibrations of small anatase TiO2 nanoparticles is studied using Raman scattering. All the Raman peaks show a significant variation of their frequency with pressure, except for the low-frequency peak which is due to acoustic vibrations confined in the nanoparticles. These variations (or lack thereof) are compared to first-principles calculations of the stiffness tensor and phonons of bulk anatase TiO2 as a function of pressure. In particular, the variation of the shape of the low-frequency peak is explained by the increase of the elastic anisotropy of anatase TiO2 as pressure is increased.
    Full-text · Article · Apr 2014 · The Journal of Physical Chemistry C
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    ABSTRACT: In situ studies have provided valuable new information on the synthesis mechanisms, low temperature properties and high pressure behavior of semiconductor clathrates. Here we review work using synchrotron and laboratory X-ray diffraction and Raman scattering used to study mainly Si-based clathrates under a variety of conditions. During synthesis of the Type I clathrate Na8Si46 by metastable thermal decomposition from NaSi in vacuum, we observe an unusual quasiepitaxial process where the clathrate structure appears to nucleate and grow directly from the Na-deficient Zintl phase surface. Low temperature X-ray studies of the guest-free Type II clathrate framework Si136 reveal a region of negative thermal expansion behavior as predicted theoretically and analogous to that observed for diamond-structured Si. High pressure studies of Si136 lead to metastable production of the b-Sn structured Si-II phase as well as perhaps other metastable crystalline materials. High pressure investigations of Type I clathratesshow evidence for a new class of apparently isostructural densification transformations followed by amorphization in certain cases.
    Full-text · Article · Jan 2014 · Springer Series in Materials Science
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    ABSTRACT: The effects of surface and interface on the thermodynamics of small particles require a deeper understanding. This step is crucial for the development of models that can be used for decision-making support to design nanomaterials with original properties. Based on experimental results for phase transitions in compressed ZnO nanoparticles, we show the limitations of classical thermodynamics approaches (Gibbs and Landau). We develop a new model based on the Landau-Ginzburg theory that requires the consideration of several terms, such as the interaction between nanoparticles, pressure gradients, defect density, and so on. This phenomenological approach sheds light on the discrepancies in the literature as it identifies several possible parameters that should be taken into account to properly describe the transformations. For the sake of clarity and standardization, we propose an experimental protocol that must be followed during high-pressure investigations of nanoparticles in order to obtain coherent, reliable data that can be used by the scientific community.
    Full-text · Article · Dec 2013 · Nano Letters
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    ABSTRACT: Nanoparticles have more propensities for amorphization than their bulk counterparts, opening the opportunity to achieve the amorphous states in well-known poor glass-former compounds. Classical size effects are often invoked to explain such phenomenon. However, this argument is not sufficient to cover all experimental results such as functionalization effect. In this work, Y2O3 nanoparticles of 7 nm diameter are investigated under pressure. Special care is taken on the surface state of the particles by comparing the pressure-induced transformation of nanoparticles stored under different conditions (atmospheric vs argon environment). A clear difference is reported as one batch shows a transformation to an amorphous state, whereas the second undergoes a crystal-to-crystal transition. These results are discussed in terms of interface energy taking into account not only the usual surface energy but also the surface state contribution. The link between different types of amorphization (pressure-, mechanical-, and radiation-induced amorphization) in nanoparticles is underlined as a critical defect density is required to achieve the crystal-to-amorphous transformation. Defect creation may arise from multiple sources: irradiation, functionalization, and reconstructive transition.
    Full-text · Article · May 2013 · The Journal of Physical Chemistry C
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    Denis Machon

    Full-text · Article · Apr 2013 · The Journal of Physical Chemistry C
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    Full-text · Dataset · Feb 2013
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    ABSTRACT: Pressure-induced amorphization (PIA) is a phenomenon that involves an abrupt transition between a crystalline material and an amorphous solid through application of pressure at temperatures well below the melting point or glass transition range. Amorphous states can be produced by PIA for substances that do not normally form glasses by thermal quenching. It was first reported for ice Ih in 1984 following prediction of a metastable melting event associated with the negative initial melting slope observed for that material. The unusual phenomenon attracted intense interest and by the early 1990’s PIA had been reported to occur among a wide range of elements and compounds. However, with the advent of powerful experimental techniques including high resolution synchrotron X-ray and neutron scattering combined with more precise control over the pressurization environment, closer examination showed that some of the effects previously reported as PIA were likely due to formation of nanocrystals, or even that PIA was completely bypassed during examination of single crystals or materials treated under more hydrostatic compression conditions. Now it is important to understand these results together with related discussions of polyamorphic behavior to gain better understanding and control over these metastable transformations occurring in the low temperature range where structural relaxation and equilibration processes are severely constrained. The results will lead to useful new high-density amorphous materials or nanocrystalline composites containing metastable crystalline varieties and the experiments have driven new theoretical approaches to modeling the phenomena. Here we review the incidence and current understanding of PIA along with related phenomena of density- and entropy-driven liquid-liquid phase transitions (LLPT) and polyamorphism. We extend the discussion to include polymeric macromolecules and biologically-related materials, where the phenomena can be correlated with reversible vs irreversible unfolding and other metastable structural transformations.
    Full-text · Article · Jan 2013 · Progress in Materials Science
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    ABSTRACT: The vibrational and structural properties of modified double-wall carbon nanotubes (DWNTs) were investigated by high-pressure resonance Raman scattering. We studied bromine-intercalated DWNTs grown by chemical vapor deposition (CVD) and 13 C 60 peapod-derived DWNTs in comparison with pristine CVD-grown DWNTs. The effects of chemical modification, carbon interwall geometry, and inhomogeneous filling on the high-pressure evolution of the DWNTs have been investigated. We find that the mechanical resistance of the DWNT system is affected both in the case of bromine-intercalated CVD-DWNTs and also for the 13 C 60 peapod-derived DWNTs, thus lowering the onset of collapse pressure P (onset) c compared with pristine CVD-DWNTs. For bromine CVD-DWNTs, P (onset) c was observed to be 13 GPa, well below the 21 GPa found for pristine CVD-DWNTs. Uniaxial constrains in the interstitial regions of the DWNT bundle due to the presence of bromine arrangements explains this mechanical instability rather than a charge transfer process. Isotopic 13 C enrichment of the inner tube reduces the frequency of its tangential contribution to the G-band Raman spectrum, which appears to be an effective method to separate the contribution of inner-and outer-tube G + components during pressure evolution. P (onset) c was found to be 12 GPa for the 13 C 60 -derived DWNT system. In this case, the instability of the DWNT is mainly due to the high inhomogeneous filling of the outer tube, as a consequence of the conversion method used to produce the inner-wall nanotube from the peapods, which produces inner tubes which are usually shorter than the outer tubes, leading to the outer tube not being completely filled.
    Full-text · Article · Nov 2012 · Physical review. B, Condensed matter
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    ABSTRACT: Several-nanometer-size mechanical oscillators, or nanoresonators, may complement electronic and optical technologies in future terahertz devices, but they can be useful only if they can be made to have relatively light damping, that is, a quality factor as high as possible. Completely mechanically isolated nanoparticles a few nanometers in size would of course be very high-quality factor terahertz nanoresonators but would be totally unsuitable for integration into practical devices. We report the fabrication of solid-embedded nanoparticles whose natural mechanical vibrations have a usefully high quality factor. In this proof-of-concept study, a powder of approximately spherical, monodisperse 5 nm diameter ZrO2 nanoparticles is compressed to 20 GPa, whereas their mechanical vibrations are directly observed using Raman spectroscopy. Even though they are compressed very tightly in a solid, the individual nanoparticles vibrate essentially independently, being minimally coupled to their neighbors. This mechanical isolation is attributed to a subnanometer-thickness adsorbed water molecule layer, which we theoretically show to be more than sufficient to create a significant impedance mismatch. We also investigated the propagation of sound waves through the nanopowder using Brillouin scattering. The speed of long-wavelength acoustic waves is strongly dependent on the internanoparticle coupling, as revealed by the extreme variation with pressure of the speed of sound. In addition, the low-frequency Raman spectra provide an indication of the solid-state character of nanoscale ZrO2. There is a transition of the Zr-O bonds from being primarily ionic at low pressures to being primarily covalent at high pressures. Finally, a strong background in these Raman spectra is due to quasielastic scattering, which disappears at high pressure or low temperature.
    Full-text · Article · Sep 2012 · The Journal of Physical Chemistry C
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    I M Pelin · A Piednoir · D Machon · P Farge · C Pirat · S M M Ramos
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    ABSTRACT: In this work, we study the adhesion forces between atomic force microscopy (AFM) tips and superficial dentin etched with phosphoric acid. Initially, we quantitatively analyze the effect of acid etching on the surface heterogeneity and the surface roughness, two parameters that play a key role in the adhesion phenomenon. From a statistical study of the force-distance curves, we determine the average adhesion forces on the processed substrates. Our results show that the average adhesion forces, measured in water, increase linearly with the acid exposure time. The highest values of such forces are ascribed to the high density of collagen fibers on the etched surfaces. The individual contribution of exposed collagen fibrils to the adhesion force is highlighted. We also discuss in this paper the influence of the environmental medium (water/air) in the adhesion measurements. We show that the weak forces involved require working in the aqueous medium.
    Full-text · Article · Mar 2012 · Journal of Colloid and Interface Science
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    ABSTRACT: Through a systematic structural search we found an allotrope of carbon with Cmmm symmetry which we predict to be more stable than graphite for pressures above 10 GPa. This material, which we refer to as Z-carbon, is formed by pure sp(3) bonds and it provides an explanation to several features in experimental x-ray diffraction and Raman spectra of graphite under pressure. The transition from graphite to Z-carbon can occur through simple sliding and buckling of graphene sheets. Our calculations predict that Z-carbon is a transparent wide band-gap semiconductor with a hardness comparable to diamond.
    Full-text · Article · Feb 2012 · Physical Review Letters
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    ABSTRACT: We investigate the interface energy impact on phase stability using the shining example of TiO2 nanoparticles under pressure. We revisit the previously reported phase diagram of this system and propose a new mechanism allowing the control of pressure-induced amorphization of TiO2 ultrafine particles. We demonstrate that the size effect is necessary for stabilizing the amorphous state but is not sufficient in the sense that surface chemical functionalization of nanoparticles is determinant. This discovery opens the possibility to select the high-pressure phase in nanomaterials and, consequently, the recovered structure under ambient conditions.
    Full-text · Article · Nov 2011 · The Journal of Physical Chemistry C
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    ABSTRACT: Exfoliated graphene and few layer graphene samples supported on SiO(2) have been studied by Raman spectroscopy at high pressure. For samples immersed on a alcohol mixture, an electron transfer of ∂n/∂P ∼ 8 × 10(12) cm(-2) GPa(-1) is observed for monolayer and bilayer graphene, leading to giant doping values of n ∼ 6 × 10(13) cm(-2) at the maximum pressure of 7 GPa. Three independent and consistent proofs of the doping process are obtained from (i) the evolution of the Raman G-band to 2D-band intensity ratio, (ii) the pressure coefficient of the G-band frequency, and (iii) the 2D band components splitting in the case of the bilayer sample. The charge transfer phenomena is absent for trilayer samples and for samples immersed in argon or nitrogen. We also show that a phase transition from a 2D biaxial strain response, resulting from the substrate drag upon volume reduction, to a 3D hydrostatic compression takes place when going from the bilayer to the trilayer sample. By model calculations we relate this transition to the unbinding of the graphene-SiO(2) system when increasing the number of graphene layers and as function of the surface roughness parameters. We propose that the formation of silanol groups on the SiO(2) substrate allows for a capacitance-induced substrate-mediated charge transfer.
    Full-text · Article · Aug 2011 · Nano Letters
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    ABSTRACT: We identify a mechanism responsible for amorphization of rare-earth molybdate isostructural compounds by means of x-ray absorption spectroscopy (XAS) and Raman spectroscopy as well as first-principles calculations. Our present Raman spectra show that both β′ and α-Eu2(MoO4)3 undergo a pressure-induced amorphization. Both first-principles calculations and XAS measurements explain the process of amorphization by a spatial self-reorganization of the oxygen clouds around the Mo and Eu subnetworks as the pressure is increased inducing a change in the coordination number of the Mo atoms. This latter transforms the eg crystal field of the tetrahedra into a series of stabilization-degenerated peaks, which energetically favors a disordered overlapping of the former MoO4 tetrahedra instead of a mere ordered compression and rotation of these fragments.
    Full-text · Article · Jun 2011 · Physical review. B, Condensed matter

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