Biomedical subjects

D Fioretto

Publications and source records attributed to D Fioretto.

At least 19 recordsLinked to original sources

PubMed2006

Is there any fast sound in water?

We measured the dynamic structure factor S(Q,omega) of liquid and undercooled water down to 253 K in the Q approximately 0.02-0.1 nm;{-1} momentum transfer region. We observe the neat departure of the apparent speed of sound from the adiabatic regime as a function of decreasing temperature. Our evaluation of the infinite-frequency limit of sound velocity, c_{infinity}, matches with the results obtained in the high momentum transfer limit by inelastic neutron and x-ray scattering. These results strongly support the viscoelastic interpretation of the dynamics of water. Hence, we propose to call c_{infinity} the high-frequency speed of sound and to abandon the term fast sound, which recalls a propagation mechanism through lighter atoms, like in gas mixtures.

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PubMed2006

Effect of densification on the density of vibrational states of glasses.

We studied the effect of densification on the vibrational dynamics of a Na(2)FeSi(3)O(8) glass. The density of vibrational states (DOS) has been measured using nuclear inelastic scattering. The corresponding changes in the microscopic, intermediate-range, and macroscopic properties have also been investigated. The results reveal that, in the absence of local structure transformations, the Debye level and the glass-specific excess of vibrational states above it have the same dependence on density, and the evolution of the DOS is fully described by the transformation of the elastic medium.

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PubMed2006

Evidence for a crossover in the frequency dependence of the acoustic attenuation in vitreous silica.

We report measurements of the sound attenuation coefficient in vitreous silica, for sound waves of wavelength between 50 and 80 nm, performed with the new inelastic UV light scattering technique. These data indicate that in silica glass a crossover between a temperature-dependent (at low frequency) and a temperature-independent (at high frequency) acoustic attenuation mechanism occurs at Q approximately equal to 0.15 nm(-1). The absence of any signature in the static structure factor at this Q value suggests that the observed crossover should be associated with local elastic constant fluctuations.

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PubMed2006

Bond-induced ergodicity breakdown in reactive mixtures.

We have studied by inelastic x-ray scattering, at wave vectors 1 nm < or =q< or =15 nm(-1), the high-frequency dynamics of epoxy-amine mixtures as the monomers irreversibly polymerize. We find that chemical bonding, while inducing molecular ordering on a mesoscopic length scale, also efficiently realizes the mechanism of dynamical arrest described by the mode-coupling theory, as manifested by a cusp singularity in the behavior of the nonergodicity factor as a function of the number of chemical bonds. These results confront positively the mode-coupling theory with a new control parameter.

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PubMed2006

Density of vibrational states of a hyperquenched glass.

The vibrational density of states of a hyperquenched and an annealed glass has been measured using nuclear inelastic scattering. The hyperquenched sample shows a higher number of vibrational states in the low-energy region with respect to the annealed glass. It reveals, however, lower density and sound velocity and, therefore, smaller Debye energy. After rescaling the energy axes in Debye energy units and area renormalization, the density of states of both samples becomes identical. Thus, the effect of quenching is described by the transformation of the continuous medium.

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PubMed2005

Rubberlike dynamics in sulphur above the lambda-transition temperature.

The high-frequency acoustic dynamics of sulfur across the liquid-liquid, lambda transition has been studied using inelastic x-ray scattering. The combination of these high-frequency data with lower frequency, literature data indicates that liquid sulfur develops, in the high-temperature, polymeric solution phase, some characteristic features of a rubber. In particular, entanglement coupling among polymeric chains plays a relevant role in the dynamics of this liquid phase.

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PubMed2005

Ergodic to nonergodic transition in liquids with a local order: the case of m-toluidine.

The dynamic structure factor of m-toluidine has been measured by inelastic x-ray scattering in the mesoscopic Q range between 1 and 10 nm(-1), where a prepeak is revealed in the static structure factor resulting from the existence of hydrogen bonded, nanometer size clusters. Evidence is given of (i) a square-root cusp in the nonergodicity factor and of (ii) critical nonergodicity parameters which oscillate in phase with the static structure factor. These results demonstrate that local order in a liquid can coexist with the signatures of the ergodic to nonergodic transition predicted by the mode coupling theory for simple, dense liquids.

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PubMed2005

Hard-sphere-like dynamics in a non-hard-sphere liquid.

The collective dynamics of liquid gallium close to the melting point has been studied using inelastic x-ray scattering to probe length scales smaller than the size of the first coordination shell. Although the structural properties of this partially covalent liquid strongly deviate from a simple hard-sphere model, the dynamics, as reflected in the quasielastic scattering, are beautifully described within the framework of the extended heat mode approximation of Enskog's kinetic theory, analytically derived for a hard-sphere system. The present work demonstrates, therefore, the applicability of Enskog's theory beyond simple liquids.

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PubMed2005

Clustering and cooperative dynamics in a reactive system.

We study the dependence of the dynamics on the size of particle clusters that grow by stepwise aggregation in a reactive epoxy-amine mixture. The data reveal the cluster property involved in the glasslike arrest and its quantitative link with the structural relaxation time. We find that the number-average cluster size xn governs the formation of a glassy phase as distinct from a gel phase, and that xn correlates to the size of the "cooperatively rearranging regions" postulated by the Adam-Gibbs model for glass forming liquids. These results suggest that the step polymerization process generates clusters that behave much like dynamical heterogeneities observed in supercooled liquids.

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PubMed2004

Slow dynamics of salol: a pressure- and temperature-dependent light scattering study.

We study the slow dynamics of salol by varying both temperature and pressure using photon correlation spectroscopy and pressure-volume-temperature measurements, and compare the behavior of the structural relaxation time with equations derived within the Adam-Gibbs entropy theory and the Cohen-Grest free volume theory. We find that pressure-dependent data are crucial to assess the validity of these model equations. Our analysis supports the entropy-based equation, and estimates the configurational entropy of salol at ambient pressure approximately 70% of the excess entropy. Finally, we investigate the evolution of the shape of the structural relaxation process, and find that a time-temperature-pressure superposition principle holds over the range investigated.

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PubMed2004

Inelastic ultraviolet scattering from high frequency acoustic modes in glasses.

The dynamic structure factor of vitreous silica and glycerol has been measured as a function of temperature and of the momentum transfer up to Q=0.105 nm(-1) using a novel experimental technique, the inelastic ultraviolet scattering. As in the case of Brillouin light scattering and ultrasonic measurements, the temperature dependence of the acoustic attenuation shows a plateau below the glass transition whose amplitude scales as Q2. Moreover, a slight temperature dependence of attenuation has been found in vitreous silica at about 130 K, which seems to be reminiscent of the peak measured at lower Qs. These two findings strongly support the idea that anharmonicity is responsible for sound attenuation at ultrasonic and hypersonic frequencies. Finally, we demonstrate that the attenuation mechanism should show a change of regime between 0.105 and 1 nm(-1).

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PubMed2004

Can experiments select the configurational component of excess entropy?

Configurational entropy is frequently used to rationalize the structural dynamics of glass-forming liquids. The main problem with this concept is that it is not directly accessible to experiments. We introduce a procedure to estimate the configurational component of the excess entropy of a liquid --specifically, the configurational-entropy contribution from the structural relaxation process-- through a combined investigation of dynamic and thermodynamic properties as functions of temperature and pressure. We test our method on orthoterphenyl, salol, and glycerol, and find that the fraction of excess entropy that arises from structural configurations is about 70% for all three materials.

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PubMed2001

Effect of pressure on the dynamics of glass formers.

A description of the pressure dependence of the structural relaxation time has been derived from the Adam-Gibbs theory by writing the configurational entropy in terms of the excess heat capacity and the molar thermal expansion. This new equation was tested successfully on dielectric relaxation data for an epoxy compound over a wide range of temperature and pressure.

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PubMed2001

Glass transition and density fluctuations in the fragile glass former orthoterphenyl.

High-resolution Brillouin light scattering is used to measure the dynamic structure factor of the fragile glass former orthoterphenyl (OTP) in a wide temperature range around the glass transition region and up to the boiling point. The whole set of spectra is described in terms of a phenomenological generalized hydrodynamic model. In the supercooled phase, we show the contemporary existence of the structural process, whose main features come out to be consistent with the results obtained with other spectroscopies, and of a secondary, activated process, which occurs on the 10(-11) s time scale and has a low activation energy (E(f)(a)=0.28 kcal/mol). This latter process, which is also present in the glassy phase and seems to be insensitive to the glass transition, is attributed to the coupling between the density modes and intramolecular degrees of freedom. In the normal liquid phase, the two processes merge together, and the resulting characteristic time is no longer consistent with those derived with other spectroscopies. The analysis points to the conclusion that, for what concerns the long-wavelength density fluctuations in fragile glass formers such as OTP, the universal dynamical features related to the glass transition come out clearly only in the supercooled phase and at frequencies lower than approximately 10(6) Hz.

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PubMed2000

Intramolecular origin of the fast relaxations observed in the brillouin light scattering spectra of molecular glass formers

The Brillouin light scattering spectra of the o-terphenyl single crystal are compared with those of the liquid and the glass phases. This shows (i) the direct evidence of a fast relaxation at frequencies nu approximately 5 GHz in both the single crystal and the glass; (ii) a similar temperature dependence for the attenuation of the longitudinal sound waves in the single crystal and the glass; and (iii) the absence of coupling between the fast relaxation and the transverse acoustic waves. These results allow us to assign such a relaxation to the coupling between the longitudinal acoustic waves and intramolecular vibrations, and therefore to exclude any relationship between it and the glass transition.

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PubMed1999

Light-scattering study of a supercooled epoxy resin.

The dynamics of the fragile glass-forming liquid diglycidyl ether of bisphenol-A was studied by depolarized Rayleigh-Brillouin light-scattering and photon correlation spectroscopy above the glass transition, in the temperature range from 261 to 473 K and in the frequency range from 1 Hz to 300 GHz. The structural (alpha-) relaxation process was revealed and no signature of the secondary relaxation previously evidenced by dielectric spectroscopy at about 0.1 GHz was observed. The characteristic time of the alpha process differs from that determined by dielectric spectroscopy of an amount, which increases with increasing temperature. The relaxation times were compared with viscosity data to test the predictions of the classic Stokes-Einstein-Debye model. The tau proportional, variant eta behavior was verified for dielectric data, while a fractional power law of viscosity tau proportional, variant eta(0.89) was obtained for light-scattering relaxation times, extending over more than seven decades in viscosity and time. This deviation of light scattering from viscosity data could be interpreted in terms of cooperative motion in the supercooled liquid with a characteristic length xi(a) proportional, variant(T-T0)(-v) where T(0)=229 K is the Vogel temperature and v is close to 2 / 3 which is consistent with the prediction of the fluctuation theory of glass transition.

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PubMed1999

Influence of temperature and pressure on dielectric relaxation in a supercooled epoxy resin.

Isothermal and isobaric dielectric measurements of a supercooled epoxy resin have been compared. A simple scaling relates isobaric and isothermal spectra corresponding to the same frequency of the main loss peak. Thus, the main and secondary processes retain a relative weight that is the same under isothermal and isobaric conditions. It is inferred that both pressure and temperature, equivalently, are able to take effect on the relaxation processes, without changing the relaxation mechanism itself. Careful analysis of the structural relaxation time behavior revealed that the traditional free volume equation, where only the macroscopic volume controls the pressure evolution of free volume, is not a suitable description of the data, as well as a Vogel-Fulcher (VF) type pressure dependent function. Based on a derivative method, a different function for describing the bidimensional surface tau(T,P) has been proposed, which accounts for the observed behavior through a nonlinear correction of the critical temperature T0 in the VF law. The function we propose predicts pressure dependencies of the glass transition temperature and fragility which are appealing in view of a comparison with experimental results in this and many other systems. Interesting hints for interpreting the phenomenological results can be obtained within the Adam-Gibbs theory.

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PubMed1999

Brillouin and Umklapp scattering in polybutadiene: comparison of neutron and x-ray scattering.

We report a comparison of high resolution inelastic x-ray Brillouin scattering to coherent inelastic neutron scattering for amorphous deuterated polybutadiene, done for one temperature in the glass phase and another one in the melt. The x-ray scattering proves to be by far the better technique for such a polymer within its present resolution bounds. The neutron scattering allows one to extend these measurements to a much better resolution, showing an additional quasielastic signal in the melt. The results suggest x-ray measurements at higher momentum transfer, to see whether they are complementary to neutrons.

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