Fragility correlates thermodynamic and kinetic properties of glass forming liquids

In our earlier communication we proposed a simple fragility determining function, (NBO]/(VmTg)-T-3), which we have now used to analyze several glass systems using available thermal data. A comparison with similar fragility determining function, Delta C-p/C-p(1), introduced by Chryssikos et al. in their investigation of lithium borate glasses has also been performed and found to be more convenient quantity for discussing fragilities. We now propose a new function which uses both Delta C-p and Delta T and which gives a numerical fragility parameter, F whose value lies between 0 and 1 for glass forming liquids. F can be calculated through the use of measured thermal parameters Delta C-p, C-p(1), T-g and T-m. Use of the new fragility values in reduced viscosity equation reproduces the whole range of viscosity curves of the Angell plot. The reduced viscosity equation can be directly compared with the Adam-Gibbs viscosity equation and a heat capacity function can be formulated which reproduces satisfactorily the Delta C-p versus In(T-r) curves and hence the configurational entropy. (C) 2014 Elsevier Ltd. All rights reserved.

Pyroelectric and second harmonic responses from LiTaO3 nanocrystallites evolved in a Li2O-B2O3-Ta2O5 glass system

Dendritic growth of trigonal and square bipyramidal structures of LiTaO3 nanocrystallites, of 19-30 nm size, was observed when 1.5Li(2)O-2B(2)O(3)-0.5Ta(2)O(5) glasses were subjected to controlled heat treatment between 530 degrees C and 560 degrees C/3 h. X-ray diffraction and Raman spectral studies carried out on the heat-treated samples confirmed the formation of a LiTaO3 phase along with a minor phase of ferroelectric Li2B4O7. The sample that was heat-treated at 550 degrees C/3 h was found to possess similar to 26 nm sized crystallites which exhibited a pyroelectric coefficient as high as 15 nC cm(-2) K-1 which is in the same range (23 nC cm(-2) K-1) as that of single crystalline LiTaO3 at room temperature. The corresponding figures of merit that were calculated for the fast pulse detector (F-i), the large area pyroelectric detector (F-v) and the pyroelectric point detector (F-D) were 0.517 x 10(-10) m V-1, 0.244 m(2) C-1 and 1.437 x 10(-5) Pa-1/2, respectively. Glass nanocrystal composites comprising similar to 30 nm sized crystallites exhibited broad Maker fringes and the second harmonic intensity emanated from these was 0.5 times that of KDP single crystals.

Mesoporous silica-chondroitin sulphate hybrid nanoparticles for targeted and bio-responsive drug delivery

This work proposes the fabrication of a novel targeted drug delivery system based on mesoporous silica-biopolymer hybrids that can release drugs in response to biological stimuli present in cancer cells. The proposed system utilizes mesoporous silica nanoparticles as a carrier to host the drug molecules. A bio-polymer cap is attached onto these particles which serves the multiple functions of drug retention, targeting and bio-responsive drug release. The biopolymer chondroitin sulphate used here is a glycosaminoglycan that can specifically bind to receptors over-expressed in cancer cells. This molecule also possesses the property of disintegrating upon exposure to enzymes over-expressed in cancer cells. When these particles interact with cancer cells, the chondroitin sulphate present on the surface recognizes and attaches onto the CD44 receptors facilitating the uptake of these particles. The phagocytised particles are then exposed to the degradative enzymes, such as hyaluronidase present inside the cancer cells, which degrade the cap resulting in drug release. By utilizing a cervical cancer cell line we have demonstrated the targetability and intracellular delivery of hydrophobic drugs encapsulated in these particles. It was observed that the system was capable of enhancing the anticancer activity of the hydrophobic drug curcumin. Overall, we believe that this system might prove to be a valuable candidate for targeted and bioresponsive drug delivery.

SIMULATION STUDY OF THE ADSORPTION DYNAMICS OF CYLINDRICAL SILICA GEL PARTICLES

The paper presents a simulation study of loose cylindrically shaped particles packed within a copper plate and aluminum fins. The model presented solves coupled heat and mass transfer equations using the finite volume method based on ANSY S FLUENT medium. Three different arrangements of cylindrical particles are considered. The model is validated with experimental data. It is found that the arrangements which represented monolayer configurations are only marginally better in heat transfer and uptake efficiency than the tri-layer configuration in the presence of fins. However, there is an appreciable difference in the uptake curve between monoand tri-layer configurations in the absence of fins. Finally, it is found that the fin pitch also plays an important role in determining the time constant for the adsorber design.

Direct measurements of growing amorphous order and non-monotonic dynamic correlations in a colloidal glass-former

The transformation of flowing liquids into rigid glasses is thought to involve increasingly cooperative relaxation dynamics as the temperature approaches that of the glass transition. However, the precise nature of this motion is unclear, and a complete understanding of vitrification thus remains elusive. Of the numerous theoretical perspectives(1-4) devised to explain the process, random first-order theory (RFOT; refs 2,5) is a well-developed thermodynamic approach, which predicts a change in the shape of relaxing regions as the temperature is lowered. However, the existence of an underlying `ideal' glass transition predicted by RFOT remains debatable, largely because the key microscopic predictions concerning the growth of amorphous order and the nature of dynamic correlations lack experimental verification. Here, using holographic optical tweezers, we freeze a wall of particles in a two-dimensional colloidal glass-forming liquid and provide direct evidence for growing amorphous order in the form of a static point-to-set length. We uncover the non-monotonic dependence of dynamic correlations on area fraction and show that this non-monotonicity follows directly from the change in morphology and internal structure of cooperatively rearranging regions(6,7). Our findings support RFOT and thereby constitute a crucial step in distinguishing between competing theories of glass formation.

Unusual Fragility and Cooperativity in Glass-Forming and Crystalline PVDF/PMMA Blends in the Presence of Multiwall Carbon Nanotubes

Poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) are completely miscible below 50 wt % PVDF in the blends. In this work, an attempt was made to understand the fragility/cooperativity relation in glass-forming and crystalline blends of PVDF/PMMA and in the presence of a heteronucleating agent, multiwall carbon nanotubes (CNTs). Hence, three representative blends were chosen: a completely amorphous (10/90 by wt, PVDF/PMMA), on the verge of amorphous miscibility (50/50 by wt, PVDF/PMMA), and crystalline (60/40 by wt, PVDF/PMMA) blends. The intermolecular cooperativity/coupling, fragility, and configurational entropy near the glass transition temperature (T-g) were studied using differential scanning calorimetry (DSC) and broadband dielectric relaxation spectroscopy (DRS). It was observed that the blends with higher concentration of PMMA were more fragile (fragility index m = 141) and those with higher concentration of PVDF were more strong (m = 78). Interestingly, the coupling was less in the glass-forming blends (10/90 by wt, PVDF/PMMA) than the crystalline blends as manifested from DRS. This observation was also supported by DSC measurements which reflected that the cooperative rearranging region (CRR) existed over a smaller length scales in fragile blends as compared to strong blends, possibly due to restricted amorphous mobility. This effect was more prominent in the presence of CNTs, in particular for 50/50 (by wt) and 60/40 (by wt) PVDF/PMMA blends. Further, the configurational entropy, as manifested from DRS, decreased significantly in the strong blends in striking contrast to the fragile blends, supported by DSC, which manifested in an increase in the volume of cooperativity in the strong blends. The higher coupling in the crystalline blends can be attributed to good packing of the amorphous regions. While this is understood for crystalline blends (60/40 by wt, PVDF/PMMA), it is envisaged that enhanced dynamic heterogeneity is accountable for increased coupling in the case of blends which are on the verge of amorphous miscibility (50/50 by wt, PVDF/PMMA). The latter is also supported by broad relaxations near the T-g in DRS. Interestingly, the intermolecular coupling in the blends in the presence of CNTs has reduced, though the potential energy barrier hindering the rearrangement of CRR is lower than the blends without CNTs. In addition, the amorphous packing is not as effective as the blends without CNTs. This is manifested from reduced volume of cooperativity in particular, for 50/50 (by wt) and 60/40 (by wt) blends.

TiO2 microcrystallized glass plate mediated photocatalytic degradation of estrogenic pollutant in water

Photocatalytic degradation of estriol (E3) in an aqueous medium was investigated in the presence of TiO2 microcrystallized glass plates. To begin with, transparent glasses associated with the composition 0.4BaO-0.4TiO(2)-B2O3 (BTBO) were fabricated by the conventional melt-quench technique and subsequently subjected to controlled heat treatment at an appropriate temperature to grow anatase TiO2 microcrystals in the glass matrix. The fabricated samples were subjected to differential scanning calorimetry. X-ray diffraction and scanning electron microscopy to obtain thermal, structural and microstructural details. The photocatalytic activity of glass samples for estriol degradation was monitored by fluorescence spectroscopy. The limit of detection for estriol using fluorescence spectroscopy was analyzed. The results showed that microcrystallized TiO2 glass composites have more photocatalytic activity than as quenched glass. The degradation rate coefficient of microcrystallized TiO2 glass composite (334.54 min(-1) m(-2)) was found to be ten times larger than that of the as-quenched BTBO glasses (37.74 min(-1) m(-2)) implying that the anatase phase of TiO2 in BTBO glasses was responsible for high photocatalytic activity of estriol degradation. (c) 2014 Elsevier B.V. All rights reserved.

Dynamics of Glass Forming Liquids with Randomly Pinned Particles

It is frequently assumed that in the limit of vanishing cooling rate, the glass transition phenomenon becomes a thermodynamic transition at a temperature T-K. However, with any finite cooling rate, the system falls out of equilibrium at temperatures near T-g(> T-K), implying that the very existence of the putative thermodynamic phase transition at T-K can be questioned. Recent studies of systems with randomly pinned particles have hinted that the thermodynamic glass transition may be observed for liquids with randomly pinned particles. This expectation is based on the results of approximate calculations that suggest that the thermodynamic glass transition temperature increases with increasing concentration of pinned particles and it may be possible to equilibrate the system at temperatures near the increased transition temperature. We test the validity of this prediction through extensive molecular dynamics simulations of two model glass-forming liquids in the presence of random pinning. We find that extrapolated thermodynamic transition temperature T-K does not show any sign of increasing with increasing pinning concentration. The main effect of pinning is found to be a rapid decrease in the kinetic fragility of the system with increasing pin concentration. Implications of these observations for current theories of the glass transition are discussed.

Studies on 12 V substrate-integrated lead-carbon hybrid ultracapacitors

A cost-effective 12 V substrate-integrated lead-carbon hybrid ultracapacitor is developed and performance tested. These hybrid ultracapacitors employ flexible-graphite sheets as negative plate current-collectors that are coated amperometrically with a thin layer of conducting polymer, namely poly-aniline to provide good adhesivity to activated-carbon layer. The positive plate of the hybrid ultracapacitors comprise conventional lead-sheet that is converted electrochemically into a substrate-integrated lead-dioxide electrode. 12 V substrate-integrated lead-carbon hybrid ultracapacitors both in absorbent-glass-mat and polymeric silica-gel electrolyte configurations are fabricated and characterized. It is possible to realize 12 V configurations with capacitance values of similar to 200 F and similar to 300 F, energy densities of similar to 1.9 Wh kg(-1) and similar to 2.5 Wh kg(-1) and power densities of similar to 2 kW kg(-1) and similar to 0.8 kW kg(-1), respectively, having faradaic-efficiency values of similar to 90 % with cycle-life in excess of 100,000 cycles. The effective cost of the mentioned hybrid ultracapacitors is estimated to be about similar to 4 US$/Wh as compared to similar to 20 US$/Wh for commercially available ultracapacitors.

Biocompatibility property of 100% strontium-substituted SiO2-Al2O3-P2O5-CaO-CaF2 glass ceramics over 26 weeks implantation in rabbit model: Histology and micro-Computed Tomography analysis

One of the desired properties for any new biomaterial composition is its long-term stability in a suitable animal model and such property cannot be appropriately assessed by performing short-term implantation studies. While hydroxyapatite (HA) or bioglass coated metallic biomaterials are being investigated for in vivo biocompatibility properties, such study is not extensively being pursued for bulk glass ceramics. In view of their inherent brittle nature, the implant stability as well as impact of long-term release of metallic ions on bone regeneration have been a major concern. In this perspective, the present article reports the results of the in vivo implantation experiments carried out using 100% strontium (Sr)-substituted glass ceramics with the nominal composition of 4.5 SiO2-3Al(2)O(3)-1.5P(2)O(5)-3SrO-2SrF(2) for 26 weeks in cylindrical bone defects in rabbit model. The combination of histological and micro-computed tomography analysis provided a qualitative and quantitative understanding of the bone regeneration around the glass ceramic implants in comparison to the highly bioactive HA bioglass implants (control). The sequential polychrome labeling of bone during in vivo osseointegration using three fluorochromes followed by fluorescence microscopy observation confirmed homogeneous bone formation around the test implants. The results of the present study unequivocally confirm the long-term implant stability as well as osteoconductive property of 100% Sr-substituted glass ceramics, which is comparable to that of a known bioactive implant, that is, HA-based bioglass. (c) 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 103B: 1168-1179, 2015.

Photosensitivity study of GeS2 chalcogenide glass under femtosecond laser pulses irradiation

The present study discusses the photosensitivity of GeS2 chalcogenide glass in response to irradiation with femtosecond pulses at 1047 nm. Bulk GeS2 glasses are prepared by conventional melt quenching technique and the amorphous nature of the glass is confirmed using X-ray diffraction. Ultrafast laser inscription technique is used to fabricate the straight channel waveguides in the glass. Single scan and multi scan waveguides are inscribed in GeS2 glasses of length 0.65 cm using a master oscillator power amplifier Yb doped fiber laser (IMRA mu jewel D400) with different pulse energy and translation speed. Diameters of the inscribed waveguides are measured and its dependence on the inscription parameters such as translation speed and pulse energy is studied. Butt coupling method is used to characterize the loss measurement of the inscribed optical waveguides. The mode field image of the waveguides is captured using CCD camera and compared with the mode field image of a standard SMF-28 fibers.

Dependence of shear yield strain and shear transformation zone on the glass transition temperature in thin film metallic glasses

The dependence of shear yield strain, the activation energy and volume of shear transformation zone on the glass transition temperature was investigated through the analysis of statistical distributions of the first pop-in events during spherical indentation of four different thin film metallic glasses. Only the Cu-Zr metallic glass exhibits a bimodal distribution of the first pop-in loads, whereas W-Ru-B, Zr-Cu-Ni-Al and La-Co-Al metallic glasses show an unimodal distribution. Results show that shear yield strain and activation energy of shear transformation zone decrease whereas the volume of shear transformation zone increases with increasing homologous temperature, indicating that it is the activation energy rather than the volume of shear transformation zone that controls shear yield strain. (C) 2015 Elsevier B.V. All rights reserved.

Performance evaluation of a two-stage silica gel plus water adsorption based cooling-cum-desalination system

The first objective of this paper is to show that a single-stage adsorption based cooling-cum-desalination system cannot be used if air cooled heat rejection is used under tropical conditions. This objective is achieved by operating a silica gel + water adsorption chiller first in a single-stage mode and then in a 2-stage mode with 2 beds/stage in each case. The second objective is to improve upon the simulation results obtained earlier by way of empirically describing the thermal wave phenomena during switching of operation of beds between adsorption and desorption and vice versa. Performance indicators, namely, cooling capacity, coefficient of performance and desalinated water output are extracted for various evaporator pressures and half cycle times. The improved simulation model is found to interpret experimental results more closely than the earlier one. Reasons for decline in performance indicators between theoretical and actual scenarios are appraised. (C) 2015 Elsevier Ltd and IIR. All rights reserved.

Deployment strategy for controlled morphologies in sessile, mixed colloidal droplets

Colloidal systems offer an effective medium to micro-engineer complex structures without involving sophisticated fabrication procedures. This article presents a deployment strategy of multiple droplets of different colloidal composition and utilizes the inherent capillary flow driven self assembly of nanoparticles to construct stacks of multiple materials on a given glass substrate. Here we used aqueous nano-crystalline titania and nano-amorphous silica solutions as the two materials. Initially, a pure nanotitania (nanosilica) droplet is deployed and allowed to dry partially. Subsequently, a second droplet of pure nanosilica (nanotitania) is deployed co-axially on the partially dried precipitate. The proposed deployment strategy allowed significant morphological differences when the deployment order of nanosilica and nanotitania were interchanged. Compositional analysis performed using EDX (Energy Dispersive X-ray spectroscopy) showed preferential deposition of nanosilica and nanotitania along the radial as well as the axial plane of the final deposit pattern. The underlying mechanism for such a phenomenon could be attributed to the contact line dynamics of a sessile double droplet. We also observe heteroaggregation of the nanosilica-nanotitania interaction along a narrow interface which resulted in nanotitania particles clustering into isolated islands embedded into a matrix of nanosilica particles. Overall, this work elucidates the evaporation driven dynamics of a mixed colloidal system which displays both macroscopic as well as microscopic phenomena. Such a system could be used to generate ordered arrays of functional materials with engineered micro to nano-scale properties.