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A Bragg glass phase in the vortex lattice of a type II superconductor.

Although crystals are usually quite stable, they are sensitive to a disordered environment: even an infinitesimal amount of impurities can lead to the destruction of crystalline order. The resulting state of matter has been a long-standing puzzle. Until recently it was believed to be an amorphous state in which the crystal would break into 'crystallites'. But a different theory predicts the existence of a novel phase of matter: the so-called Bragg glass, which is a glass and yet nearly as ordered as a perfect crystal. The 'lattice' of vortices that contain magnetic flux in type II superconductors provide a good system to investigate these ideas. Here we show that neutron-diffraction data of the vortex lattice provides unambiguous evidence for a weak, power-law decay of the crystalline order characteristic of a Bragg glass. The theory also predicts accurately the electrical transport properties of superconductors; it naturally explains the observed phase transitions and the dramatic jumps in the critical current associated with the melting of the Bragg glass. Moreover, the model explains experiments as diverse as X-ray scattering in disordered liquid crystals and the conductivity of electronic crystals.

Journal Article↗

Formation of zirconium metallic glass.

Bulk metallic glasses are commonly produced by the rapid cooling of liquid alloys. They have emerged over the past decade as a novel class of materials, with attractive properties and technological promise. The bulk metallic glasses so far produced contain three or more component elements. These complex compositions are necessary to frustrate the crystallization of the liquid melt on cooling, but can also lead to phase separation, which is detrimental to the thermal and mechanical properties of metallic glasses. Here we report, using X-ray diffraction measurements, the formation of a bulk metallic glass from elemental zirconium at high static pressures and low temperatures (relative to its melting temperature at atmospheric pressure). Amorphous zirconium can be recovered at ambient conditions and demonstrates a superior thermal stability compared to amorphous alloys, which could lead to new high-temperature applications of amorphous metals.

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Water Behaviour: glass transition in hyperquenched water?

It has been unclear whether amorphous glassy water heated to around 140-150 K remains glassy until it crystallizes or whether instead it turns into a supercooled and very viscous liquid. Yue and Angell compare the behaviour of glassy water under these conditions to that of hyperquenched inorganic glasses, and claim that water stays glassy as it heats up to its crystallization point; they also find a 'hidden' glass-to-liquid transition at about 169 K. Here we use differential scanning calorimetry (DSC) heating to show that hyperquenched water deposited at 140 K behaves as an ultraviscous liquid, the limiting structure of which depends on the cooling rate--as predicted by theoretical analysis of the liquid-to-glass transition. Our findings are consistent with a glass-to-liquid transition-onset temperature (T(g)) in the region of 136 K (refs 3,4), and they indicate that measurements of the liquid's properties may clarify the anomalous properties of supercooled water.

Comment↗

Making metallic glasses plastic by control of residual stress.

Metallic glasses, now that many compositions can be made in bulk, are of interest for structural applications exploiting their yield stress and yield strain, which are exceptionally high for metallic materials. Their applicability is limited by their near-zero tensile ductility resulting from work-softening and shear localization. Even though metallic glasses can show extensive local plasticity, macroscopically they can effectively be brittle, and much current research is directed at improving their general plasticity. In conventional engineering materials as diverse as silicate glasses and metallic alloys, we can improve mechanical properties by the controlled introduction of compressive surface stresses. Here we demonstrate that we can controllably induce such residual stresses in a bulk metallic glass, and that they improve the mechanical performance, in particular the plasticity, but that the mechanisms underlying the improvements are distinct from those operating in conventional materials.

Journal Article↗

Nanophase separation and hindered glass transition in side-chain polymers.

Nanophase separation on length scales of 1-5 nanometres has been reported previously for small-molecule liquids, metallic glasses and also for several semicrystalline, liquid-crystalline and amorphous polymers. Here we show that nanophase separation of incompatible main and side-chain parts is a general phenomenon in amorphous side-chain polymers with long alkyl groups. We conclude from X-ray scattering and relaxation spectroscopy data for higher poly(n-alkyl acrylates) (PnAA) and poly(n-alkyl methacrylates) (PnAMA) that alkyl groups of different monomeric units aggregate in the melt and form self-assembled alkyl nanodomains with a typical size of 0.5-2 nm. A comparison with data for other polymer series having alkyl groups reveals that important structural and dynamic aspects are main-chain independent. A polyethylene-like glass transition within the alkyl nanodomains is observed and discussed in the context of a hindered glass transition in self-assembled confinements. This is an interesting link between central questions in glass-transition research and structural aspects in nanophase-separated materials.

Acrylates↗

What variable-pressure variable-temperature measurements are telling us about ion transport in glass.

Variable-pressure, variable-temperature (VPVT) measurements of ionic conductivity in typical inorganic (sodium aluminoborate and lithium-sodium phosphate) glasses provide information concerning two independent activation parameters: the activation energy (E(A) = - R d ln sigma T/d(1/T)) and the activation volume (V(A) = - RT d ln sigma/dP). In single-cation glasses there is no simple link between E(A) and V(A). The strong increase in E(A) seen with decreasing alkali content is not paralleled by an increase in V(A). However, in mixed cation glasses, maxima are observed in both E(A) and V(A). To account for these observations, a new model is being developed where ion transport is limited by a shortage of available volume. In this model, the measured V(A) values represent the volumes of opened up 'target sites', the larger values observed in mixed-cation glasses providing evidence for the coupled motion of unlike ions. The extent of this pairwise coupling increases with increasing temperature.

Journal Article↗

Determination of optimal parameters for laser for nonablative remodeling with a 1.54 microm Er:glass laser: a dose-response study.

BACKGROUND: Nonablative subsurface heating is a challenge for medical laser companies. Among the different lasers proposed today, the erbium-glass (Er:glass) laser combined with contact cooling could be an alternative for nonablative remodeling. OBJECTIVE: To investigate the risk of side effects according to the quality of cooling and number of pulses. METHODS: A clinical evaluation was performed on 10 patients using an Er:glass laser (1.54 microm) with contact sapphire cooling handpiece (+5 degrees C). Periorbital and perioral areas were treated with a number of pulses increasing gradually from three to eight for a total energy of 24-64 J/cm2. The presence or absence of swelling, crust, blister, and erythema were graded at 7 days. At 3 months postoperatively, hypopigmentation, hyperpigmentation, textural changes, and scars were evaluated clinically. RESULTS: Periorbital and perioral areas respond differently to the number of pulses defining a "safe" clinical threshold. The periorbital site is very sensitive to dermal heating and efficacy of contact cooling; the anatomic features of this body location may explain these differences. CONCLUSION: Selective dermal heating can be achieved with an Er:glass laser coupled with a contact cooling handpiece. The quality of the contact cooling and the number of pulses appear to be important parameters for safety and reproducible clinical results.

Adult↗

[Efficiency of conventional glass wool and SpermFertil columns with respect to ROS-reduction, leukocyte reduction, and CASA-generated sperm counts in semen].

OBJECTIVE: Glass wool filtration has proved to be useful to separate motile from defective spermatozoa and leukocytes in semen from patients with oligozoospermia and azoospermia. With regard to that, we set out to investigate the efficiency of two widely used filter systems. MATERIAL AND METHODS: Semen from 10 patients attending the Dept. of Andrology, FSU Jena, were investigated with home-made coarse glass wool filters and SpermFertil columns regarding elimination of reactive oxygen species (ROS) and enrichment of semen with motile and progressive spermatozoa. RESULTS: Filtration with home-made glass wool columns did not affect the percentage of motile spermatozoa but increased that of progressive spermatozoa. The whole cell count was decreased by a third. Leukocytes were reduced by half and ROS by more than half. SpermFertil columns increased the percentage of both motile and progressive spermatozoa and the whole cell count was decreased severely. Leukocytes were eliminated almost completely, as were ROS. CONCLUSIONS: Our results show the higher potential of SpermFertil columns to enrich semen specimens with motile and progressive spermatozoa and to almost completely eliminate leukocytes and ROS in comparison to home-made glass wool columns. However, SpermFertil columns reduce the whole cell count to about 10% of the original cell count.

Adult↗

[Contact glass for the study of the corneal endothelium and epithelium in the slit-lamp radius].

Specular endothelioscopy can be improved by an appropriate contact glass in three ways: The blurring front reflex of the cornea disappears, a two-fold magnification permits the use of routine slit-lamps for observation at higher magnification, and the field of specular illumination is increased considerably. The posterior surface of the contact glass is made plane, which offers the following advantages: a fluid chamber in front of the cornea is created which avoids any deformation of the cornea through the contact glass; the reflex of the posterior surface can be deflected by tilting the contact glass slightly so that the weak specular reflex of the epithelium becomes visible.

Corneal Diseases↗

Influence of confinement on the vibrational density of states and the Boson peak in a polymer glass.

We have performed a normal-mode analysis on a glass forming polymer system for bulk and free-standing film geometries prepared under identical conditions. It is found that for free-standing film glasses, the normal-mode spectrum exhibits significant differences from the bulk glass with the appearance of an additional low-frequency peak and a higher intensity at the Boson peak frequency. A detailed eigenvector analysis shows that the low-frequency peak corresponds to a shear-horizontal mode which is predicted by continuum theory. The peak at higher frequency (Boson peak) corresponds to motions that are correlated over a length scale of approximately twice the interaction site diameter. These observations shed some light on the microscopic dynamics of glass formers, and help explain decreasing fragility that arises with decreasing thickness in thin films.

Journal Article↗

The Adam-Gibbs equation and the out-of-equilibrium alpha relaxation of glass forming systems.

The temperature dependence of the alpha-relaxation time out of equilibrium has been investigated by means of dielectric relaxation in a series of fragile glass formers including several polymers. The influence of physical aging on this behavior has also been studied. The experimental results have been quantitatively compared with the predictions of the Adam-Gibbs equation. It has been found that, whereas for small molecule glass formers the experimental values of the apparent activation energy agree quite well with the prediction of the Adam-Gibbs equation, for polymers the experimental activation energy values are systematically higher. Moreover, whereas for small molecule glass formers the experimental values of the apparent activation energy remains essentially unaffected by physical aging, for polymers a pronounced reduction of the experimental apparent activation energy is observed. These results are found to be consistent with the Adam-Gibbs equation if a significant temperature variation of the configurational entropy in the investigated temperature range would occur for nonannealed polymers, being the possible variation hardly noticeable for the small molecules. With this assumption, all the obtained results would support the validity of the Adam-Gibbs equation for describing the temperature dependence of the time scale of the alpha-relaxation also out of equilibrium, at least for fragile glass formers.

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Molecular dynamics investigation of a density-driven glass transition in a liquid crystal system.

Molecular dynamics simulations are carried out to address the density-driven glass transition in a system of rodlike particles that interact with the Gay-Berne potential. Since crystallization occurs in this system on the time scale of the simulations, direct simulation of the glass transition is not possible. Instead, glasses with isotropic orientational order are heated to a temperature T, and the relaxation times by which nematic orientational order develops are determined. These relaxation times appear to diverge at a critical density rho(c); i.e., the system can equilibrate at rho rho(c) (at the temperature T). The relaxation times follow a power-law scaling as the critical density is approached, suggesting that this density-driven glass transition concurs with mode coupling theory.

Computer Simulation↗

A molecular dynamics simulation of the melting points and glass transition temperatures of myo- and neo-inositol.

The heat of sublimation, density, melting point, and glass transition temperature are calculated for myo- and neo-inositol, using the condensed-phase optimized molecular potentials for atomistic simulation studies (COMPASS) force field and molecular dynamics techniques. Our results show that the calculated heats of sublimation and density are very close to the experimental values for both compounds. Furthermore, our simulated melting temperatures for myo- and neo-inositol also compare very well to the experimentally obtained data. The glass transition temperatures for myo- and neo-inositol have been calculated to be ca. 494 K and ca. 518 K, respectively, and the shape of the volume versus temperature plots produced are typical for a glass transition. As a result, it is our view that the COMPASS force field suitably describes these two compounds in molecular simulations and that molecular dynamics techniques, combined with this force field, can be used to simulate the melt and glass transitions for such molecules.

Journal Article↗

Restricted orientational motion of nitroxides in molecular glasses: direct estimation of the motional time scale basing on the comparative study of primary and stimulated electron spin echo decays.

A comparative study of anisotropic relaxation in two-pulse primary and three-pulse stimulated electron spin echo decays provides a direct way to distinguish fast (correlation time tau(c)<10(-6) s) and slow (tau(c)>10(-6) s) motions. Anisotropic relaxation is detected as a difference of the decay rates for different resonance field positions in anisotropic electron paramagnetic resonance spectra. For fast motion anisotropic relaxation influences the primary echo decay and does not influence the stimulated echo decay. For slow motion it is seen in both two-pulse echo and three-pulse stimulated echo decays. For nitroxide spin probes dissolved in glassy glycerol only fast motion was found below 200 K. Increase of temperature above 200 K results in the appearance of slow motion. Its amplitude increases rapidly with temperature increase. While in glycerol glass slow motion appears above glass transition temperature T(g), in ethanol glass it is observable below T(g). The scenario of motional dynamics in glasses is proposed which involves the broadening of the correlation time distribution with increasing temperature.

Journal Article↗

Shear softening and structure in a simulated three-dimensional binary glass.

Three-dimensional model binary glasses produced by quenching from a range of liquid temperatures were tested in shear over a range of strain rates using molecular-dynamics techniques. Tests were performed under constant volume and constant pressure constraints. The simulations revealed a systematic change in short-range order as a function of the thermal and strain history of the glass. While subtle signs of differences in short-range order were evident in the pair distribution function, three-body correlations were observed to be markedly more sensitive to the changes in structure. One particular structural parameter, the number of aligned three-atom clusters, was analyzed as a function of the degree of supercooling, the strain and the strain rate. The glasses quenched from the supercooled liquid regime were observed to contain an initially higher number of such clusters, and this number decreased under shear. Those quenched from high-temperature equilibrium liquids contained lower numbers of such clusters and these increased or remained constant under shear. The glasses quenched from the supercooled liquid regime showed higher strength, more marked shear softening, and an increased propensity toward shear localization. The evolution of this structural parameter depended both on its initial value and on the imposed shear rate. These results were observed to hold for simulations performed under both constant density and constant pressure boundary conditions.

Journal Article↗

Direct computation of characteristic temperatures and relaxation times for glass-forming polymer liquids.

Characteristic temperatures and structural relaxation times for different classes of glass-forming polymer liquids are computed using a revised entropy theory of glass formation that permits the chain backbone and the side groups to have different rigidities. The theory is applied to glass formation at constant pressure or constant temperature. Our calculations provide new insights into physical factors influencing the breadth of the glass transition and the associated growth of relaxation times.

Journal Article↗

Local environment and dynamics of PO4 tetrahedra in Na-Al-PO3 glasses and melts.

Glasses and melts in the system (NaPO3)(1-x)(Al(PO3)3)x were studied with the aim of obtaining information about the structure on the next larger scale beyond the PO4 group. Magic angle spinning NMR was applied to the pure NaPO3 glass and Raman scattering to systems with x = 0.00, 0.03, 0.06, 0.15, and 0.60 in the temperature range T = 300-1100 K. Comparison of the 31P chemical shift between glass and crystalline forms revealed that polymerization of the metaphosphate into tricyclophosphatelike (PO3)3(3-) rings is the dominant structure, ca. 80%, formed by the twofold vertex-joined PO4 groups in the glass. In the Raman study we focused on the prominent polarized band at ca. 1170 cm(-1) which is due to the symmetric breathing mode of the tetrahedral PO4 group. This band was decomposed into a few Gaussian lines. These component lines could be identified using the NMR results: two narrow components are due to PO4 groups in the tricyclophosphatelike rings, which have either a Na or an Al counterion and a third broad component is due to chain-polymerized (PO3(-))n. The variations of the component lines (peak positions, widths, and intensities) with respect to x and T are presented. We derive the shifts of the symmetric breathing mode frequency which are caused by Na or Al counterions, by ring closure, by x > 0, etc. The relative intensities of the narrow and broad components in the 1170-cm(-1) band of the Raman spectra are discussed. The amount of ring-to-chain transformation on addition of Al3+, and as functions of T and x, is derived. Indications for ordering on a next larger scale, derivable from Raman, NMR, and thermodynamics, are compared.

Journal Article↗

Relaxation dynamics in AgI-doped silver vanadate superionic glasses.

Relaxation dynamics of Ag+ ions in several series of AgI-Ag2O-V2O5 superionic glasses has been studied in the frequency range from 10 Hz to 2 MHz and in the temperature range from 93 to 323 K. The composition dependence of the dc conductivity and the activation energy of these glasses has been compared with those of AgI-doped silver phosphate and borate glasses. The frequency-dependent electrical data have been analyzed in the framework of conductivity formalism. We have obtained the mobile ion concentration and the power-law exponent from the analysis of the conductivity spectra. We have observed that the concentration of Ag+ ions is independent of temperature and the conductivity is primarily determined by the mobility. A fraction of the Ag+ ions in the glass compositions are involved in the dynamic process. We have also shown that the power-law exponent is independent of temperature. The results are also supported by the temperature and composition independence of the scaling of the conductivity spectra.

Journal Article↗