Precision control of drying using rhythmic dancing of sessile nanoparticle laden droplets

This work analyses the unique spatio-temporal alteration of the deposition pattern of evaporating nanoparticle laden droplets resting on a hydrophobic surface through targeted low frequency substrate vibrations. External excitation near the lowest resonant mode (n = 2) of the droplet initially de-pins and then subsequently re-pins the droplet edge creating pseudo-hydrophilicity (low contact angle). Vibration subsequently induces droplet shape oscillations (cyclic elongation and flattening) resulting in strong flow recirculation. This strong radially outward liquid flow augments nanoparticle transport, vaporization, and agglomeration near the pinned edge resulting in much reduced drying time under certain characteristic frequency of oscillations. The resultant deposit exhibits a much flatter structure with sharp, defined peripheral wedge topology as compared to natural drying. Such controlled manipulation of transport enables tailoring of structural and topological morphology of the deposits and offers possible routes towards controlling the formation and drying timescales which are crucial for applications ranging from pharmaceutics to surface patterning. (C) 2014 AIP Publishing LLC.

Polyanhydrides of Castor Oil-Sebacic Acid for Controlled Release Applications

A family of high molecular weight castor oil (CO)-based biodegradable polyanhydrides was synthesized by a catalyst-free melt-condensation reaction between prepolymers of CO and sebacic acid (SA). The structure of the polymers was characterized by H-1 NMR and Fourier transform infrared spectroscopy, which indicated the formation of the anhydride bond along the polymer backbone. Thermal analysis and X-ray diffraction confirmed the semicrystalline nature of the polymers. Incorporation of SA enhanced the crystallinity of the polymer. The hydrophobic nature of these polymers was revealed by contact angle goniometry. Water wettability decreased with increase in SA content. Compressive tests demonstrated a sharp increase in strength and decrease in ductility with increasing SA content. In vitro hydrolytic degradation studies indicated surface-eroding behavior. The degradation rate decreased with an increase of SA content in the polymers because of increased crystallinity. The release studies of both hydrophobic and hydrophilic dyes followed zero-order kinetics. In vitro cell studies to assess the cytotoxicity of the polymer confirmed minimal toxicity of the degradation products. Thus, a family of CO-SA polyanhydrides have been synthesized and characterized for controlled release applications where the physical, mechanical, and degradation kinetics can be modulated by varying the weight fraction of the prepolymers.

Multimodal shape oscillations of droplets excited by an air stream

The shape dynamics of droplets exposed to an air jet at intermediate droplet Reynolds numbers is investigated. High speed imaging and hot-wire anemometry are employed to examine the mechanism of droplet oscillation. The theory that the vortex shedding behind the droplet induces oscillation is examined. In these experiments, no particular dominant frequency is found in the wake region of the droplet. Hence the inherent free-stream disturbances prove to be driving the droplet oscillations. The modes of droplet oscillation show a band of dominant frequencies near the corresponding natural frequency, further proving that there is no particular forcing frequency involved. In the frequency spectrum of the lowest mode of oscillation for glycerol at the highest Reynolds number, no response is observed below the threshold frequency corresponding to the viscous dissipation time scale. This selective suppression of lower frequencies in the case of glycerol is corroborated by scaling arguments. The influence of surface tension on the droplet oscillation is studied using ethanol as a test fluid. Since a lower surface tension reduces the natural frequency, ethanol shows lower excited frequencies. The oscillation levels of different fluids are quantified using the droplet aspect ratio and correlated in terms of Weber number and Ohnesorge number. (C) 2014 Elsevier Ltd. All rights reserved.

Oscillation dynamics of sessile droplets subjected to substrate vibration

Sessile droplets on a vibrating substrate are investigated focusing on axisymmetric oscillations with pinned contact line. Proper orthogonal decomposition is employed to identify the different modes of droplet shape oscillation and quantitatively assess the droplet oscillation and spectral response. We offer the first experimental evidence for the analogy of an oscillating sessile droplet with a non-linear spring mass damper system. The qualitative and quantitative agreement of amplitude response and phase response curves and limit cycles of the model dynamical system with that observed experimentally suggest that the bulk oscillations in the fundamental mode of a sessile droplet can be very well modeled by a Duffing oscillator with a hard spring, especially near the resonance. The red shift of the resonance peak with an increase in the glycerol concentration is clearly evidenced by both the experimental and predicted amplitude response curves. The influence of various operational parameters such as excitation frequency and amplitude and fluid properties on the droplet oscillation characteristics is adequately captured by the model. (C) 2014 Elsevier Ltd. All rights reserved.

Suppression of instabilities in burning droplets using preferential acoustic perturbations

Self-induced internal boiling in burning functional droplets has been observed to induce severe bulk shape oscillations in droplets with characteristic bubble ejection events that corrugate the droplet surface. Such bubble-droplet interactions are characterized by a distinct regime of a single bubble growing inside the droplet where evaporative Darrieus-Landau instability occurs at the bubble-droplet interface. In this regime the bubble-droplet system behaves as a self-excited coupled oscillator. In this study, we report the external flame-acoustic interaction with bubbles inside the droplet resulting in controlled droplet deformation. In particular, by exciting the droplet flame in a critical, responsive frequency range (80 Hz <= f(p) <= 120 Hz) the droplet deformation cycle could be altered through suppression of these self-excited instabilities and intensity/frequency of bubble ejection events. This selective acoustic tuning also enabled the control of bubble dynamics, bulk droplet-shape distortion and the final precipitate morphology even in burning nanoparticle laden droplets. (C) 2014 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Heat kernels on the AdS(2) cone and logarithmic corrections to extremal black hole entropy

We develop new techniques to efficiently evaluate heat kernel coefficients for the Laplacian in the short-time expansion on spheres and hyperboloids with conical singularities. We then apply these techniques to explicitly compute the logarithmic contribution to black hole entropy from an N = 4 vector multiplet about a Z(N) orbifold of the near-horizon geometry of quarter-BPS black holes in N = 4 supergravity. We find that this vanishes, matching perfectly with the prediction from the microstate counting. We also discuss possible generalisations of our heat kernel results to higher-spin fields over ZN orbifolds of higher-dimensional spheres and hyperboloids.

Agglomeration front dynamics: Drying in sessile nano-particle laden droplets

The drying of sessile, nano-silica laden water droplet is studied under ambient conditions, in the absence of any convection. The drying process can be divided into two distinct regimes. During regime 1, the outer edge of the droplet remains pinned and particles agglomerate at the droplet periphery similar to the traditional coffee ring. However in regime 2, with further evaporation, both the liquid contact line and the agglomeration front starts moving radially inwards from the initial contact edge. The contact between the liquid and the agglomerate is maintained throughout regime 2 and the vaporisation driven liquid edge recession essentially drives the inward growth of the particle deposition. Fast kinetics of particle aggregation results in rapid growth of this agglomeration front as seen from the experiments. A theoretical formulation involving a simplistic model of the agglomeration front growth based on particle mass balance has been proposed. (C) 2014 Elsevier Ltd. All rights reserved,

Sphere to ring morphological transformation in drying nanofluid droplets in a contact-free environment

Understanding the transients of buckling in drying colloidal suspensions is pivotal for producing new functional microstructures with tunable morphologies. Here, we report first observations and elucidate the buckling instability induced morphological transition (sphere to ring structure) in an acoustically levitated, heated nanosuspension droplet using dynamic energy balance. Droplet deformation featuring the formation of symmetric cavities is initiated by capillary pressure that is two to three orders of magnitude greater than the acoustic radiation pressure, thus indicating that the standing pressure field has no influence on the buckling front kinetics. With an increase in heat flux, the growth rate of surface cavities and their post-buckled volume increase while the buckling time period reduces, thereby altering the buckling pathway and resulting in distinct precipitate structures. However, irrespective of the heating rate, the volumetric droplet deformation exhibits a linear time dependence and the droplet vaporization is observed to deviate from the classical D-2-law.

Effect of viscosity and surface tension on breakup and coalescence of bicomponent sprays

This work deals with an experimental study of the breakup characteristics of liquids with different surface tension and viscosity from a hollow cone hydraulic injector nozzle induced by pressure-swirl. The experiments were conducted at Reynolds numbers Re-p=9500-23,000. The surface tension and viscosity of the surrogate fuels were altered from 72 to 30 mN/m and 1.1 to 1.6 mN s/m(2), respectively. High speed photography and Phase Doppler Particle Anemometry were utilized to study the atomization process. Velocity and drop size measurements of the spray using PDPA in both axial and radial directions indicate a dependency on surface tension. However, these effects are dominant only at low Reynolds numbers and are negligible at high Reynolds number. Downstream of the nozzle, coalescence of droplets due to collision was also found to be significant and the diameters were compared for different liquids. For viscous fluids up to 1.6 cP, the independent effects of viscosity and injection pressure are studied. In general, the spray cone angle increases with increase in pressure. At high pressures, an increase in viscosity leads to higher drop sizes following primary and secondary breakup compared to water. This study will extend our understanding of surrogate fuel film breakup and highlight the importance of long and short wavelength instabilities. (C) 2013 Elsevier Ltd. All rights reserved

Analysis on the atomization characteristics of aviation biofuel discharging from simplex swirl atomizer

The atomization characteristics of aviation biofuel discharging from a simplex swirl atomizer into quiescent atmospheric air are studied. The aviation biofuel is a mixture of 90% commercially available camelina-derived biofuel and 10% VonSol-53 (aromatics). The experiments are conducted in a spray test facility at varying fuel flow rate conditions. The measured characteristics include atomizer flow number, spray cone angle, breakup length of liquid sheet, wavelength of undulations on liquid sheet, and spray droplet size. The characteristics of biofuel sheet breakup are deduced from the captured images of biofuel spray. The measurements of spray droplet size distribution are obtained using Spraytec. The experimentally measured characteristics of the biofuel sheet breakup are compared with the predictions obtained from the liquid film breakup model proposed by Senecal et al. (1999). The measurements of wavelength and breakup length of the biofuel sheet discharging from the simplex swirl atomizer agree well with the model predictions. The model-predicted droplet size for the biofuel spray is significantly higher than the experimentally measured Sauter mean diameter (SMD). The spray droplets formed from the liquid sheet breakup undergo secondary atomization until 35-45 mm from the atomizer exit and thereafter the SMD increases downstream due to the combined effect of fuel evaporation and droplet coalescence. A good comparison is observed between the experimentally measured SMD of the biofuel spray and the predictions obtained using the empirical correlation reported in literature for sprays discharging from simplex swirl atomizers. (C) 2015 Elsevier Ltd. All rights reserved.

Copolyesters from Soybean Oil for Use as Resorbable Biomaterials

A family of soybean oil (SO) based biodegradable cross-linked copolyesters sourced from renewable resources was developed for use as resorbable biomaterials. The polyesters were prepared by a melt condensation of epoxidized soybean oil polyol and sebacic acid with citric acid (CA) as a cross-linker. D-Mannitol (M) was added as an additional reactant to improve mechanical properties. Differential scanning calorimetry revealed that the polyester synthesized using only CA as the cross-linker was semicrystalline and elastomeric at physiological temperature. The polymers were hydrophobic in nature. The water wettability, elongation at break and the degradation rate of the polyesters decreased with increase in M content or curing time. Modeling of release kinetics of dyes showed a diffusion controlled mechanism underlies the observed sustained release from these polymers. The polyesters supported attachment and proliferation of human stem cells and were thus cytocompatible. Porous scaffolds induced osteogenic differentiation of the stern cells suggesting that these polymers are well suited for bone tissue engineering. Thus, this family of polyesters offers a low cost and green alternative as biocompatible, bioresobable polymers for potential use as resorbable biomaterials for tissue engineering and controlled release.

EXPERIMENTAL STUDIES ON AIR-ASSISTED ATOMIZATION OF JATROPHA PURE PLANT OIL

The present study focuses on exploring air-assisted atomization strategies for effective atomization of high-viscosity biofuels, such as pure plant oils (PPOs). The first part of the study concerns application of a novel air-assisted impinging jet atomization for continuous spray applications, and the second part concerns transient spray applications. The particle/droplet imaging analysis (PDIA) technique along with direct imaging methods are used for the purpose of spray characterization. In the first part, effective atomization of Jatropha PPO is demonstrated at gas-to-liquid ratios (GLRs) on the order 0.1. The effect of liquid and gas flow rates on the spray characteristics is evaluated, and results indicate a Sauter mean diameter (SMD) of 50 mu m is achieved with GLRs as low as 0.05. In the second part of the study, a commercially available air-assisted transient atomizer is evaluated using Jatropha PPO. The effect of the pressure difference across the air injector and ambient gas pressure on liquid spray characteristics is studied. The results indicate that it is possible to achieve the same level of atomization of Jatropha as diesel fuel by operating the atomizer at a higher pressure difference. Specifically, a SMD of 44 mu m is obtained for the Jatropha oil using injection pressures of <1 MPa. A further interesting observation associated with this injector is the near constancy of a nondimensional spray penetration rate for the Jatropha oil spray.

Phenomenology and control of buckling dynamics in multicomponent colloidal droplets

Self-assembly of nano sized particles during natural drying causes agglomeration and shell formation at the surface of micron sized droplets. The shell undergoes sol-gel transition leading to buckling at the weakest point on the surface and produces different types of structures. Manipulation of the buckling rate with inclusion of surfactant (sodium dodecyl sulphate, SDS) and salt (anilinium hydrochloride, AHC) to the nano-sized particle dispersion (nanosilica) is reported here in an acoustically levitated single droplet. Buckling in levitated droplets is a cumulative, complicated function of acoustic streaming, chemistry, agglomeration rate, porosity, radius of curvature, and elastic energy of shell. We put forward our hypothesis on how buckling occurs and can be suppressed during natural drying of the droplets. Global precipitation of aggregates due to slow drying of surfactant-added droplets (no added salts) enhances the rigidity of the shell formed and hence reduces the buckling probability of the shell. On the contrary, adsorption of SDS aggregates on salt ions facilitates the buckling phenomenon with an addition of minute concentration of the aniline salt to the dispersion. Variation in the concentration of the added particles (SDS/AHC) also leads to starkly different morphologies and transient behaviour of buckling (buckling modes like paraboloid, ellipsoid, and buckling rates). Tuning of the buckling rate causes a transition in the final morphology from ring and bowl shapes to cocoon type of structure. (C) 2015 AIP Publishing LLC.

A sleep-inducing peptide from the venom of the Indian cone snail Conus araneosus

The marine snail Conus araneosus has unusual significance due to its confined distribution to coastal regions of southeast India and Sri Lanka. Due to its relative scarceness, this species has been poorly studied. In this work, we characterized the venom of C. araneosus to identify new venom peptides. We identified 14 novel compounds. We determined amino acid sequences from chemically-modified and unmodified crude venom using liquid chromatography-electrospray ionization mass spectrometry and matrix assisted laser desorption ionization time-of-flight mass spectrometry. Ten sequences showed six Cys residues arranged in a pattern that is most commonly associated with the M-superfamily of conotoxins. Four other sequences had four Cys residues in a pattern that is most commonly associated with the T-superfamily of conotoxins. The post-translationally modified residue (pyroglutamate) was determined at the N-terminus of two sequences, ar3h and ar3i respectively. In addition, two sequences, ar3g and ar3h were C-terminally amidated. At a dose of 2 nmol, peptide ar3j elicited sleep when injected intraperitoneally into mice. To our knowledge, this is the first report of a peptide from a molluscivorous cone snail with sleep-inducing effects in mice. The novel peptides characterized herein extend the repertoire of unique peptides derived from cone snails and may add value to the therapeutic promise of conotoxins. (C) 2015 Elsevier Ltd. All rights reserved.