Fragile Glass Research Articles

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Nonlinear acoustics at GHz frequencies in a viscoelastic fragile glass former.

Using a picosecond pump-probe ultrasonic technique, we study the propagation of high-amplitude, laser-generated longitudinal coherent acoustic pulses in the viscoelastic fragile glass former DC704. We observe an increase of almost 10% in acoustic pulse propagation speed at the highest optical pump fluence which is a result of the supersonic nature of nonlinear propagation in the viscous medium. From our measurement, we deduce the nonlinear acoustic parameter of the glass former in the gigahertz frequency range across the glass transition temperature.

Glass formers display universal non-equilibrium dynamics on the level of single-particle jumps

Glasses are inherently out-of-equilibrium systems evolving slowly toward their equilibrium state in a process called physical aging. During aging, dynamic observables depend on the history of the system, hampering comparative studies of dynamics in different glass formers. Here, we demonstrate how glass formers can be directly compared on the level of single-particle jumps, i.e. the structural relaxation events underlying the α-process. Describing the dynamics in terms of a continuous-time random walk, an analytic prediction for the jump rate is derived. The result is subsequently compared to molecular-dynamics simulations of amorphous silica and a polymer melt as two generic representatives of strong and fragile glass formers, and good agreement is found.

Sorbitol Crystallization-Induced Aggregation in Frozen mAb Formulations

Sorbitol crystallization-induced aggregation of mAbs in the frozen state was evaluated. The effect of protein aggregation resulting from sorbitol crystallization was measured as a function of formulation variables such as protein concentration and pH. Long-term studies were performed on both IgG1 and IgG2 mAbs over the protein concentration range of 0.1-120 mg/mL. Protein aggregation was measured by size-exclusion HPLC (SE-HPLC) and further characterized by capillary-electrophoresis SDS. Sorbitol crystallization was monitored and characterized by subambient differential scanning calorimetry and X-ray diffraction. Aggregation due to sorbitol crystallization is inversely proportional to both protein concentration and formulation pH. At high protein concentrations, sorbitol crystallization was suppressed, and minimal aggregation by SE-HPLC resulted, presumably because of self-stabilization of the mAbs. The glass transition temperature (Tg ') and fragility index measurements were made to assess the influence of molecular mobility on the crystallization of sorbitol. Tg ' increased with increasing protein concentration for both mAbs. The fragility index decreased with increasing protein concentration, suggesting that it is increasingly difficult for sorbitol to crystallize at high protein concentrations.

Generation of hydrate forms of paroxetine HCl from the amorphous state: An evaluation of thermodynamic and experimental predictive approaches

In this study, we evaluate the use of theoretical thermodynamic analysis of amorphous paroxetine hydrochloride (HCl) as well as experimental assessment in order to identify the most promising approach to stability and dissolution behaviour prediction, particularly in relation to stoichiometric and nonstoichiometric hydrate formation. Differential scanning calorimetry, thermogravimetric analysis, Fourier transform infrared and X-ray diffraction techniques were used. Parameters including heat capacity, configurational thermodynamic quantities, fragility and relaxation time classified amorphous paroxetine HCl as a moderate fragile glass with a considerable degree of molecular mobility. Solubility studies indicated little advantage of the amorphous form over the crystalline due to conversion to the hydrate Form I during equilibration, while the dissolution rate was higher for the amorphous form under sink conditions. A marked difference in the physical stability of amorphous paroxetine HCl was observed between dry and low humidity storage, with the system recrystallizing to the hydrate form. We conclude that, in this particular case (amorphous conversion to the hydrate), water may be playing a dual role in both plasticizing the amorphous form and driving the equilibrium towards the hydrate form, hence prediction of recrystallization behaviour from amorphous characteristics may be confounded by the additional process of hydrate generation.

Relationship between particle elasticity, glass fragility, and structural relaxation in dense microgel suspensions.

"Fragile" glassy materials, which include most polymeric materials and organic liquids, exhibit a steep and super-Arrhenius dependence of relaxation time with temperature upon the glass transition and have been extensively studied. Yet, a full understanding of strong glass formers that exhibit an Arrhenius dependence on temperature is still lacking. In this work, we have investigated the glassy dynamics of poly(N-isopropylacrylamide) (PNIPAM) microgel particles of varied elasticity in dense aqueous suspensions, giving rise to a full spectrum of strong to fragile glass-forming behaviors. We have observed the dependence of particle motions and structural relaxation on particle volume fraction can be weakened by decreasing particle elasticity, due to particle deformation and the resulting interparticle elastic interaction upon intimate particle contacts at high particle concentration. Both measured α-relaxation time scales and dynamic length scales for cooperative rearranging motions of microgels in suspensions show similarly dependence on particle volume fraction and elasticity, thereby quantifying the glass fragility of dense microgel suspension of varied particle elasticity.

Glass-like dynamics in confined and congested ant traffic.

The collective movement of animal groups often occurs in confined spaces. As animal groups are challenged to move at high density, their mobility dynamics may resemble the flow of densely packed non-living soft materials such as colloids, grains, or polymers. However, unlike inert soft-materials, self-propelled collective living systems often display social interactions whose influence on collective mobility are only now being explored. In this paper, we study the mobility of bi-directional traffic flow in a social insect (the fire ant Solenopsis invicta) as we vary the diameter of confining foraging tunnels. In all tunnel diameters, we observe the emergence of spatially heterogeneous regions of fast and slow traffic that are induced through two phenomena: physical obstruction, arising from the inability of individual ants to interpenetrate, and time-delay resulting from social interaction in which ants stop to briefly antennate. Density correlation functions reveal that the relaxation dynamics of high density traffic fluctuations scale linearly with fluctuation size and are sensitive to tunnel diameter. We separate the roles of physical obstruction and social interactions in traffic flow using cellular automata based simulation. Social interaction between ants is modeled as a dwell time (Tint) over which interacting ants remain stationary in the tunnel. Investigation over a range of densities and Tint reveals that the slowing dynamics of collective motion in social living systems are consistent with dynamics near a fragile glass transition in inert soft-matter systems. In particular, flow is relatively insensitive to density until a critical density is reached. As social interaction affinity is increased (increasing Tint) traffic dynamics change and resemble a strong glass transition. Thus, social interactions play an important role in the mobility of collective living systems at high density. Our experiments and model demonstrate that the concepts of soft-matter physics aid understanding of the mobility of collective living systems, and motivate further inquiry into the dynamics of densely confined social living systems.

PH sensitivity of emeraldine salt polyaniline and poly(vinyl butyral) blend

pH sensitivity of emeraldine salt polyaniline (ES-PANI) and poly(vinyl butyral) (PVB) blend film was investigated. This blend film can be used as a pH sensing element in new-type pH sensors to replace traditional instruments based on fragile glass electrodes for pH measurement of water in aquaculture farming. Structural and optical characteristic of PANI were studied by Fourier transform infrared spectroscopy (FTIR) and ultraviolet visible spectroscopy (UV–vis). Electrical characterization of ES-PANI:PVB blend films versus pH was performed with chemiresistors fabricated by micro-lithography. A ES-PANI:PVB layer was drop-coated on comb-shaped platinum electrodes patterned on SiO2/Si substrates. Scanning electron microscope (SEM) and optical microscope were used to investigate morphology of the fabricated platinum electrodes and the coated polymer blend films. I–V measurements of the polymer-coated chemiresistors were performed at very low relative humidity after the polymer films were exposed to pH 1–8. The results showed that logarithm of electrical resistance of the ES-PANI:PVB films increased almost linearly as pH increased from 1 to 8. The initial results showed that the PANI blend-coated chemiresistors can be used as pH sensors for water quality monitoring.

Molecular dynamics of amorphous pharmaceutical fenofibrate studied by broadband dielectric spectroscopy

Fenofibrate is mainly used to reduce cholesterol level in patients at risk of cardiovascular disease. Thermal transition study with the help of differential scanning calorimetry (DSC) shows that the aforesaid active pharmaceutical ingredient (API) is a good glass former. Based on our DSC study, the molecular dynamics of this API has been carried out by broadband dielectric spectroscopy (BDS) covering wide temperature and frequency ranges. Dielectric measurements of amorphous fenofibrate were performed after its vitrification by fast cooling from a few degrees above the melting point (Tm=354.11K) to deep glassy state. The sample does not show any crystallization tendency during cooling and reaches the glassy state. The temperature dependence of the structural relaxation has been fitted by single Vogel–Fulcher–Tamman (VFT) equation. From VFT fit, glass transition temperature (Tg) was estimated as 250.56K and fragility (m) was determined as 94.02. This drug is classified as a fragile glass former. Deviations of experimental data from Kohlrausch–Williams–Watts (KWW) fits on high-frequency flank of α-peak indicate the presence of an excess wing in fenofibrate. Based on Ngai׳s coupling model, we identified the excess wing as true Johari–Goldstein (JG) process. Below the glass transition temperature one can clearly see a secondary relaxation (γ) with an activation energy of 32.67kJ/mol.

An Ultrasonic Non-Contact Handling Device from Quartz Glass for Middle and High Temperature Applications

Ultrasonic non-contact handling is used to manipulate surface sensitive and fragile workpieces, e.g. wafers and glass plates, without mechanical contact. While the technology is available forapplications at room temperature, some of the manufacturing processes of products mentioned aboverequire handling at elevated temperatures. To enable this technology for handling in thermal processesan ultrasonic system for increased working temperatures is required. In order to adapt the ultrasonicsystem to the limited working temperature of the actuator, the handling system has to be operated attwo different temperatures. Due to the small change of the Young's modulus over temperature, quartzglass was chosen as material for the components in the high temperature region. The paper presentsthe design and manufacturing of a novel ultrasonic system operated at 790 °C while the actuator iskept at room temperature.

Role of fragility in the formation of highly stable organic glasses.

In situ dielectric spectroscopy has been used to characterize vapor-deposited glasses of methyl-m-toluate (MMT), an organic glass former with low fragility (m = 60). Deposition near 0.84T(g) produces glasses of very high kinetic stability; these materials are comparable in stability to the most stable glasses produced from more fragile glass formers. Highly stable glasses of MMT, when annealed above T(g), transform into the supercooled liquid by a heterogeneous mechanism. A constant velocity propagating front is initiated at the free surface and controls the transformation of thin films. The transition to a bulk-dominated transformation process occurs at 5 μm, the largest length scale reported for any glass. Contrary to recent conclusions, we find that physical vapor deposition can form highly stable organic glasses across the entire range of liquid fragilities.

The influence of dimension on the relaxation process of East-like models: Rigorous results

We study facilitated models which extend to arbitrary dimensions the one-dimensional East process and which are supposed to catch some of the main features of the complex dynamics of fragile glasses. We focus on the low-temperature regime (small density of the facilitating sites). In the literature the relaxation process has been assumed to be quasi–one-dimensional and the equilibration time has been computed using the relaxation time of the East model on the equilibrium length scale in d-dimension. This led to a super-Arrhenius scaling for the relaxation time of the form . In a companion paper, using renormalization group ideas and electrical networks methods, we rigorously establish that instead , contradicting the quasi–one-dimensional assumption. The above scaling confirms previous MCAMC simulations. Next we compute the relaxation time at finite and mesoscopic length scales, and show a dramatic dependence on the boundary conditions. Our final result is related to the out-of-equilibrium dynamics. Starting with a single facilitating site at the origin we show that, up to length scales , its influence propagates much faster (on a logarithmic scale) along the diagonal direction than along the axes directions.

Characterization of new Sb2O3-based multicomponent heavy metal oxide glasses

New Sb2O3-based multicomponent heavy metal oxide glasses in the Sb2O3–Na2O–WO3–PbO system were prepared using a conventional melt-quenching technique. Glass formation behavior of these glasses and their thermal, physical and structural properties were investigated using X-ray diffraction (XRD), scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM/EDS), differential scanning calorimetry (DSC), UV–Vis–NIR spectroscopy and Fourier transform infrared (FTIR) spectroscopy analyses according to the increasing PbO concentration by keeping the Sb2O3/WO3 ratio constant. Thermal analysis of the glasses were realized in terms of glass transition temperature (Tg), crystallization temperature (Tc/Tp), glass stability against crystallization (ΔT), activation energy of the glass transition reaction (Eg) and fragility parameter (m). Density (ρ), molar volume (VM), oxygen molar volume (VO), oxygen packing density (OPD), refractive index, band gap energy (Eg), average cross-link density (nc‾), number of bonds per unit volume (nb) and Poisson’s ratio (μcal) values were calculated for the interpretation of physical and structural properties of the glasses. FTIR spectra of the glasses were evaluated in terms of structural transformations on the glass network.

Nanocrystallization in Ni60Ta40 and Ni60Nb40 metallic glasses below calorimetric glass transition

Crystallization of Ni60Ta40 and Ni60Nb40 metallic glasses at temperatures well below their respective calorimetric glass transition temperatures has been studied by differential scanning calorimetry, nanodiffraction, and electron microscopies. Nanometer-scaled metastable FCC phases were found to grow out from the glass structures. The Z-contrast images reveal that the nanocrystals are enriched in Ta or Nb in comparison with the surrounded amorphous structures. The experimental evidence is suggestive of the decoupled cooperative diffusion of Ni atoms in these fragile glasses.

Structural and Topological Control on Physical Properties of Arsenic Selenide Glasses

The structures of Ge-doped arsenic selenide glasses with Se contents varying between 25 and 90 at. % are studied using a combination of high-resolution, two-dimensional (77)Se nuclear magnetic resonance (NMR) and Raman spectroscopy. The results indicate that, in contrast to the conventional wisdom, the compositional evolution of the structural connectivity in Se-excess glasses does not follow the chain-crossing model, and chemical order is likely violated with the formation of a small but significant fraction of As-As bonds. The addition of As to Se results in a nearly random cross-linking of Se chains by AsSe3 pyramids, and a highly chemically ordered network consisting primarily of corner-shared AsSe3 pyramids is formed at the stoichiometric composition. Further increase in As content, up to 40 at. % Se, results in the formation of a significant fraction of As4Se3 molecules with As-As homopolar bonds, and consequently the connectivity and packing efficiency of the network decrease and anharmonic interactions increase. Finally, in the highly As-rich region with <40 at. % Se, the relative concentration of the As4Se3 molecules decreases rapidly and large clusters of As atoms connected via Se-Se-As and As-Se-As linkages dominate. These three composition regions with distinct structural characteristics and the corresponding mixing entropy of the Se environments are reflected in the appearance of multiple extrema in the compositional variation of a wide range of physical properties of these glasses, including density, glass transition temperature, thermal expansivity, and fragility.

Polymer brushes: a controllable system with adjustable glass transition temperature of fragile glass formers.

We present results of molecular dynamics simulations for coarse-grained polymer brushes in a wide temperature range to investigate the factors that affect the glass transition in these systems. We focus on the influences of free surface, polymer-substrate interaction strength, grafting density, and chain length not only on the change of glass transition temperature Tg, but also the fragility D of the glass former. It is found that the confinement can enhance the dependence of the Tg on the cooling rate as compared to the bulk melt. Our layer-resolved analysis demonstrates that it is possible to control the glass transition temperature Tg of polymer brushes by tuning the polymer-substrate interaction strength, the grafting density, and the chain length. Moreover, we find quantitative differences in the influence range of the substrate and the free surface on the density and dynamics. This stresses the importance of long range cooperative motion in glass formers near the glass transition temperature. Furthermore, the string-like cooperative motion analysis demonstrates that there exists a close relation among glass transition temperature Tg, fragility D, and string length ⟨S⟩. The polymer brushes that possess larger string length ⟨S⟩ tend to have relatively higher Tg and smaller D. Our results suggest that confining a fragile glass former through forming polymer brushes changes not only the glass transition temperature Tg, but also the very nature of relaxation process.

Clearing Up the Mysteries of Glassy Dynamics

You might think all glasses are the same—that they are all viscous amorphous materials somewhere between solids and liquids. In fact, many glass-forming liquids fall into two categories: “strong” and “fragile.” As the temperature T is reduced, the viscosity of strong glasses like SiO2 increases as exp(∆/T ), where ∆ can be thought of as an energy barrier that particles have to overcome in order to move (Fig. 1). For fragile glasses, glucose for example, the increase of viscosity is even steeper, as if the effective energy barrier ∆ itself increases when the temperature is lowered.

Molecular Mobility of Amorphous S-Flurbiprofen: A Dielectric Relaxation Spectroscopy Approach

Amorphous S-flurbiprofen was obtained by the melt quench/cooling method. Dielectric measurements performed in the isochronal mode, conventional and temperature modulated differential scanning calorimetry (TMDSC) studies showed a glass transition, recrystallization, and melting. The different parameters characterizing the complex molecular dynamics of amorphous S-flurbiprofen that can have influence on crystallization and stability were comprehensively characterized by dielectric relaxation spectroscopy experiments (isothermal mode) covering a wide temperature (183 to 408 K) and frequency range (10(-1) to 10(6) Hz): width of the α-relaxation (βKWW), temperature dependence of α-relaxation times (τα), fragility index (m), relation of the α-relaxation with the β-secondary relaxation, and the breakdown of the Debye-Stokes-Einstein (DSE) relationship between the structural relaxation time and dc-conductivity (σdc) at deep undercooling close to Tg. The β-relaxation, observed in the glassy as well as in the supercooled state was identified as the genuine Johari-Goldstein process, attributed to localized motions and regarded as the precursor of the α-relaxation as suggested in the coupling model. A separation of about 6 decades between the α- and β-relaxation was observed at Tg; this decoupling decreased on increasing temperature, and both processes merged at Tαβ = 295 K. The temperature dependence of the α-relaxation time, τα, was described by two Vogel-Fulcher-Tammann-Hesse equations, which intercept at a crossover temperature, TB = 290 K, close to the splitting temperature between the α- and β-relaxation. From the low temperature VFTH equation, a Tg(DRS) = 265.2 was estimated (at τα =100 s) in good agreement with the calorimetric value (Tg,onset,TMDSC = 265.6 K), and a fragility or steepness index m = 113 was calculated allowing to classify S-flurbiprofen as a fragile glass former. The α-relaxation spectra were found to be characterized by a relatively large degree of nonexponentiality (βKWW = 0.52). A breakdown of the DSE log10 σdc - log10 τ relation was observed revealing an enhancement of translational ionic motions in comparison with the orientational molecular motions as the glass transition temperature Tg is approached from above.

Structural heterogeneity induced plasticity in bulk metallic glasses: From well-relaxed fragile glass to metal-like behavior

To reveal the structural origin responsible for the sharp change of the fracture mode on the as-cast and thermally-relaxed status, we use nanomechanical testing to measure the stresses for the onset of plasticity of a metallic glass and develop a stochastic statistical model, which can be used to characterize structural heterogeneity (defect density and strength) inside the metallic glass. Our experiments and calculations found that, with increasing the structural relaxation, the defect density drops by two orders of magnitude. Correspondingly, the fracture of metallic glasses changes from a significantly plastic (metal-like) mode to an extremely brittle (fragile glass) one.

12 ways to take a temperature

12 ways to take a temperature