arXiv subjects

M. Micoulaut

Publications and source records attributed to M. Micoulaut.

At least 19 recordsLinked to original sources

arXiv2018

Reading the structure of amorphous materials from diffraction patterns and neighbor distribution functions

An exact analytical expression for the static structure factor $S(k)$ in disordered materials is derived from Fourier transformed neighbor distribution decompositions in real space, and permits to reconstruct the function $S(k)$ in an iterative fashion. The result is successfully compared to experimental data of archetypal glasses or amorphous materials (GeS$_2$, As$_2$Se$_3$, GeTe), and links quantitatively knowledge of structural information on short and intermediate -range order with the motifs found on the diffraction patterns in reciprocal space. The approach furthermore reveals that only a limited number of neighbor shells is sufficient to reasonably describe the structure factor for $k>$2~Å$^{-1}$. In the limit of the high momentum transfer, the oscillation characteristics of the interference function are related with new informations on the short-range order of disordered materials.

cond-mat.mtrl-sci↗

arXiv2016

Revealing the role of molecular rigidity on the fragility evolution of glass-forming liquids

If quenched fast enough, a liquid is able to avoid crystallization and will remain in a metastable supercooled state down to the glass transition, with an important increase in viscosity upon further cooling. There are important differences in the way liquids relax as they approach the glass transition, rapid or slow variation in dynamic quantities under moderate temperature changes, and a simple means to quantify such variations is provided by the concept of "fragility". Here, we report molecular dynamics simulations of a typical network-forming glass, Ge-Se, and find that the relaxation behaviour of the supercooled liquid is strongly correlated to the variation of rigidity with temperature and the spatial distribution of the corresponding topological constraints which, ultimately connect to fragility minima. This permits extending the fragility concept to aspects of topology/rigidity, and to the degree of homogeneity of the atomic-sale interactions for a variety of structural glasses.

cond-mat.dis-nn↗

arXiv2016

Relaxation and physical aging in network glasses: a review

Recent progresses in the description of glassy relaxation and ageing are reviewed for the wide class of network-forming materials such as $GeO_2$, Ge$_x$Se$_{1-x}$, silicates (SiO$_2$-Na$_2$O) or borates (B$_2$O$_3$-Li$_2$O), all of them having an important usefulness in domestic, geological or optoelectronic applications. A brief introduction of the glass transition phenomenology is given, together with the salient features that are revealed both from theory and experiments. Standard experimental methods used for the characterization of the slowing down of the dynamics are reviewed. We then discuss the important role played by aspect of network topology and rigidity for the understanding of the relaxation of the glass transition, while also permitting analytical predictions of glass properties from simple and insightful models based on the network structure. We also emphasize the great utility of computer simulations which probe the dynamics at the molecular level, and permit to calculate various structure-related functions in connection with glassy relaxation and the physics of ageing which reveals the off-equilibrium nature of glasses. We discuss the notion of spatial variations of structure which leads to the picture of "{\em dynamic heterogeneities}", and recent results of this important topic for network glasses are also reviewed.

cond-mat.dis-nn↗

arXiv2013

Crucial effect of glass processing and melt homogenization on the fragility of non-stoichiometric chalcogenides

The kinetics of homogenization of binary As$_x$Se$_{100-x}$ melts in the As concentration range $0\%$ $<$ $x$ $<$ $50\%$ are followed in FT-Raman profiling experiments, and show that 2 gram sized melts in the middle concentration range $20\%$ $<$ $x$ $<$ $30\%$ take nearly two weeks to homogenize when starting materials are reacted at 700$^o$C. In glasses of proven homogeneity, we find molar volumes to vary non-monotonically with composition, and the fragility index ${\cal M}$ displays a broad global minimum in the $20\%$ $<$ $x$ $<$ $30\%$ range of $x$ wherein ${\cal M}<$ 20. We show that properly homogenized samples have a lower measured fragility when compared to larger under-reacted melts. The enthalpy of relaxation at T$_g$, $Δ$H$_{nr}$($x$) shows a minimum in the $27\%$ $<$ $x$ $<$ $37\%$ range. The super-strong nature of melt compositions in the $20\%$ $<$ $x$ $<$ $30\%$ range suppresses melt diffusion at high temperatures leading to the slow kinetics of melt homogenization.

cond-mat.mtrl-sci↗

arXiv2013

Designing heavy metal oxide glasses with threshold properties from network rigidity

Here we show that a new class of glasses composed of heavy metal oxides involving transition metals (V$_\text {2}$O$_\text{}$5-TeO$_\text{2}$), can surprisingly be designed from very basic tools using topology and rigidity of their underlying molecular networks. When investigated as a function of composition, such glasses display abrupt changes in network packing and enthalpy of relaxation at Tg, underscoring presence of flexible to rigid elastic phase transitions. We find that these elastic phases are fully consistent with polaronic nature of electronic conductivity at high V$_\text{2}$O$_\text{5}$ content. Such observations have new implications for designing electronic glasses which differ from the traditional amorphous electrolytes having only mobile ions as charge carriers.

cond-mat.mtrl-sci↗

arXiv2013

Fragility and molar volumes of non-stoichiometric chalcogenides -- the crucial role of melt/glass homogenization

Melt-fragility index (m) and glass molar volumes (Vm) of binary Ge-Se melts/glasses are found to change reproducibly as they are homogenized. Variance of Vm decreases as glasses homogenize, and the mean value of Vm increases to saturate at values characteristic of homogeneous glasses. Variance in fragility index of melts also decreases as they are homogenized, and the mean value of m decreases to acquire values characteristic of homogeneous melts. Broad consequences of these observations on physical behavior of chalcogenides melts/glasses are commented upon. The intrinsically slow kinetics of melt homogenization derives from high viscosity of select super-strong melt compositions in the Intermediate Phase that serve to bottleneck atomic diffusion at high temperatures.

cond-mat.dis-nn↗

arXiv2013

Superstrong nature of covalently bonded glass-forming liquids at select compositions

Variation of fragility (m) of specially homogenized GexSe100-x melts are established from complex specific heat measurements, and show m(x) has a global minimum at an extremely low value (m=14.8(0.5)) in the 21.5% Tg, we observe a slowdown of melt-homogenization by the super-strong melt compositions, 21.5%<x<23%. This range furthermore appears to be correlated to the one observed between the flexible and stressed rigid phase in network glasses. These spectacular features underscore the crucial role played by topology and rigidity in the properties of network-forming liquids and glasses which are highlighted when fragility is represented as a function of variables tracking the effect of rigidity. Finally, we investigate the fragility-glass transition temperature relationship, and find that reported scaling laws do not apply in the flexible phase, while being valid for intermediate and stressed rigid compositions.

cond-mat.dis-nn↗

arXiv2012

Viscosity and viscosity anomalies of model silicates and magmas: a numerical investigation

We present results for transport properties (diffusion and viscosity) using computer simulations. Focus is made on a densified binary sodium disilicate 2SiO$_2$-Na$_2$O (NS2) liquid and on multicomponent magmatic liquids (MORB, basalt). In the NS2 liquid, results show that a certain number of anomalies appear when the system is densified: the usual diffusivity maxima/minima is found for the network-forming ions (Si,O) whereas the sodium atom displays three distinct régimes for diffusion. Some of these features can be correlated with the obtained viscosity anomaly under pressure, the latter being be fairly well reproduced from the simulated diffusion constant. In model magmas (MORB liquid), we find a plateau followed by a continuous increase of the viscosity with pressure. Finally, having computed both diffusion and viscosity independently, we can discuss the validity of the Eyring equation for viscosity which relates diffusion and viscosity. It is shown that it can be considered as valid in melts with a high viscosity. On the overall, these results highlight the difficulty of establishing a firm relationship between dynamics, structure and thermodynamics in complex liquids.

cond-mat.mtrl-sci↗

arXiv2011

Melt homogenization and self-organization of chalcogenides glasses: evidence of sharp rigidity, stress and nanoscale phase separation transitions in the GexSe100-x binary

A Raman profiling method is used to monitor growth of GexSe100-x melts and reveals a two step process of homogenization. Resulting homogeneous glasses show the non-reversing enthalpy at Tg, ΔHnr(x), to show a square-well like variation with x, with a rigidity transition near xc(1) = 19.5(5)% and stress transition near xc(2) = 26.0(5)%) representing the boundaries of the rigid but stress-free Intermediate Phase (IP). The square-well like variation of ΔHnr(x) develops sloping walls, a triangular shape and eventually disappears in glasses having an increasing heterogeneity. The ΔHnr term ages over weeks outside the IP but not inside the IP. An optical analogue of the reversibility window is observed with Raman spectra of as-quenched melts and Tg cycled glasses being the same for glass compositions in the IP but different for compositions outside the IP. Variations of Molar volumes, display three regimes of behavior with a global minimum in the IP and a pronounced increase outside that phase. The intrinsic physical behavior of dry and homogeneous chalcogenides glasses can vary sharply with composition near elastic and chemical phase transitions, showing that the physics of network glasses requires homogeneous samples, and may be far more interesting than hitherto recognized.

cond-mat.dis-nn↗

arXiv2011

Meeting experimental challenges to physics of network glasses: assessing role of sample homogeneity

We introduce a Raman profiling method to track homogenization of Ge$_x$Se$_{100-x}$ melts in real time, and show that 2 gram melts reacted at 950°C in high vacuum homogenize in 168 hours on a scale of 10μm. Homogenization of melts is precursive to self-organization of glasses. In the present glasses, compositional variation of Raman active corner-sharing mode frequency of GeSe$_4$ units, molar volumes, and the enthalpy of relaxation at Tg, reveal the rigidity (xc(1)= 19.5(3)%) and the stress (xc(2) = 26.0(3)%) transitions to be rather sharp (Δx < 0.6%). These abrupt elastic phase transitions are intrinsic to these materials and have a direct bearing on physics of glasses.

cond-mat.dis-nn↗

arXiv2010

Direct evidence for a characteristic dynamic lengthscale in the intermediate phase of glasses

AC conductivity spectra of xAgI-(1-x)AgPO$_3$ fast ion conducting glasses spanning the flexible, intermediate (isostatically rigid) and stressed rigid phases are analyzed. The rescaled frequency dependent spectra are mapped into time-dependent mean square displacements out of which a typical lengthscale characterizing the spatial extent $\sqrt{\langle R^2(\infty)\rangle}$ of non-random diffusion paths is computed. The latter quantity is studied as a function of AgI composition, it is found to display a maximum in the intermediate phase, providing the first clear evidence of a typical lengthscale of a dynamical nature when a system becomes isostatically rigid and enters the intermediate phase.

cond-mat.dis-nn↗

arXiv2010

Angular rigidity in tetrahedral network glasses

A set of oxide and chalcogenide tetrahedral glasses are investigated using molecular dynamics simulations. It is shown that unlike stoichiometric selenides such as GeSe$_2$ and SiSe$_2$, germania and silica display large standard deviations in the associated bond angle distributions. Within bond-bending constraints theory, this pattern can be interpreted as a manifestation of {\it {broken}} (i.e. ineffective) oxygen bond-bending constraints. The same analysis reveals that the changes in the Ge composition affects mostly bending around germanium in binary Ge-Se systems, leaving Se-centred bending almost unchanged. In contrast, the corresponding Se twisting (quantified by the dihedral angle) depends on the Ge composition and is reduced when the system becomes rigid. Our results establishes the atomic-scale foundations of the phenomelogical rigidity theory, thereby profoundly extending its significance and impact on the structural description of network glasses.

cond-mat.dis-nn↗

arXiv2009

Fast-ion conduction and flexibility and rigidity of solid electrolyte glasses

Electrical conductivity of dry, slow cooled (AgPO$_3$)$_{1-x}$(AgI)$_x$ glasses is examined as a function of temperature, frequency and glass composition. From these data compositional trends in activation energy for conductivity E$_A$(x), Coulomb energy E$_c$(x) for Ag$^+$ ion creation, Kohlrausch stretched exponent $β$(x), low frequency ($\varepsilon_s$(x)) and high-frequency ($\varepsilon_\infty$(x)) permittivity are deduced. All parameters except E$_c$(x) display two compositional thresholds, one near the stress transition, x = x$_c$(1)= 9%, and the other near the rigidity transition, x = x$_c$(2)= 38% of the alloyed glass network. These elastic phase transitions were identified in modulated- DSC, IR reflectance and Raman scattering experiments earlier. A self-organized ion hopping model (SIHM) of a parent electrolyte system is developed that self-consistently incorporates mechanical constraints due to chemical bonding with carrier concentrations and mobility. The model predicts the observed compositional variation of $σ$(x), including the observation of a step-like jump when glasses enter the Intermediate Phase at x$>$x$_c$(1), and an exponential increase when glasses become flexible at x$>$x$_c$(2). Since E$_c$ is found to be small compared to network strain energy (E$_s$), we conclude that free carrier concentrations are close to nominal AgI concentrations, and that fast-ion conduction is driven largely by changes in carrier mobility induced by an elastic softening of network structure.

cond-mat.mtrl-sci↗

arXiv2009

Understanding amorphous phase-change materials from the viewpoint of Maxwell rigidity

Phase-change materials (PCMs) are the subject of considerable interest because they have been recognized as potential active layers for next-generation non-volatile memory devices, known as Phase Change Random Access Memories (PRAMs). By analyzing First Principles Molecular Dynamics simulations we develop a new method for the enumeration of mechanical constraints in the amorphous phase and show that the phase diagram of the most popular system (Ge-Sb-Te) can be split into two compositional regions having a well-defined mechanical character: a Tellurium rich flexible phase, and a stressed rigid phase that encompasses the known PCMs. This sound atomic scale insight should open new avenues for the understanding of PCMs and other complex amorphous materials from the viewpoint of rigidity.

cond-mat.mtrl-sci↗

arXiv2009

Improved modelling of liquid GeSe$_2$: the impact of the exchange-correlation functional

The structural properties of liquid GeSe$_2$ are studied by using first-principles molecular dynamics in conjuncton with the Becke, Lee, Yang and Parr (BLYP) generalized gradient approximation for the exchange and correlation energy. The results on partial pair correlation functions, coordination numbers, bond angle distributions and partial structure factors are compared with available experimental data and with previous first-principle molecular dynamics results obtained within the Perdew and Wang (PW) generalized gradient approximation for the exchange and correlation energy. We found that the BLYP approach substantially improves upon the PW one in the case of the short-range properties. In particular, the Ge$-$Ge pair correlation function takes a more structured profile that includes a marked first peak due to homopolar bonds, a first maximum exhibiting a clear shoulder and a deep minimum, all these features being absent in the previous PW results. Overall, the amount of tetrahedral order is significantly increased, in spite of a larger number of Ge$-$Ge homopolar connections. Due to the smaller number of miscoordinations, diffusion coefficients obtained by the present BLYP calculation are smaller by at least one order of magnitude than in the PW case.

cond-mat.mtrl-sci↗

arXiv2008

Intermediate phase, network demixing, boson and floppy modes, and compositional trends in glass transition temperatures of binary AsxS1-x system

The structure of binary As_xS_{1-x} glasses is elucidated using modulated-DSC, Raman scattering, IR reflectance and molar volume experiments over a wide range (8% 29.5%. Raman scattering supported by first principles cluster calculations reveal existence of both pyramidal (PYR, As(S1/2)3) and quasi-tetrahedral(QT, S=As(S1/2)3) local structures. The QT unit concentrations show a global maximum in the IP, while the concentration of PYR units becomes comparable to those of QT units in the phase, suggesting that both these local structures contribute to the width of the IP. The IP centroid in the sulfides is significantly shifted to lower As content x than in corresponding selenides, a feature identified with excess chalcogen partially segregating from the backbone in the sulfides, but forming part of the backbone in selenides. These ideas are corroborated by the proportionately larger free volumes of sulfides than selenides, and the absence of chemical bond strength scaling of Tgs between As-sulfides and As-selenides. Low-frequency Raman modes increase in scattering strength linearly as As content x of glasses decreases from x = 20% to 8%, with a slope that is close to the floppy mode fraction in flexible glasses predicted by rigidity theory. These results show that floppy modes contribute to the excess vibrations observed at low frequency. In the intermediate and stressed rigid elastic phases low-frequency Raman modes persist and are identified as boson modes. Some consequences of the present findings on the optoelectronic properties of these glasses is commented upon.

cond-mat.dis-nn↗

arXiv2008

Abrupt boundaries of intermediate phases and space filling in oxide glasses

Modulated DSC measurements on bulk (Na2O)x(GeO2)1-x glasses show a sharp reversibility window in the 14% < x < 19% soda range, which correlates well with a broad global minimum in molar volumes. Raman and IR reflectance TO and LO mode frequencies exhibit anomalies between xc(1) = 14% (stress transition) and xc(2) = 19% (rigidity transition), with optical elasticity power-laws confirming the nature of the transitions . Birefringence measurements dramatize the macroscopically stress-free nature of the Intermediate Phase in the reversibility window.

cond-mat.dis-nn↗

arXiv2007

Aging, Fragility and Reversibility Window in Bulk Alloy Glasses

Non-reversing relaxation enthalpies (DHnr) at glass transitions Tg(x) in the PxGexSe1-2x ternary display wide, sharp and deep global minima (~ 0) in the 0.09 < x < 0.145 range, within which Tgs become thermally reversing. In this reversibility window, glasses are found not to age, in contrast to aging observed for fragile glass compositions outside the window. Thermal reversibility and lack of aging seem to be paradigms of self-organization which molecular glasses share with protein structures which repetitively and reversibly change conformation near Tg and the folding temperature respectively.

cond-mat.soft↗