Glycerol-water Mixtures Research Articles

Hydrogen Bonding and the Structural Properties of Glycerol-Water Mixtures with a Microwave Field: a Molecular Dynamics Study.

In a microwave field, the dielectric properties, molecular structures, and hydrogen bonding dynamics of glycerol in its mixtures with water were determined by the molecular dynamics simulation method. The dipole-dipole correlation of glycerol is linked to the field intensity of microwaves. The results show that as the field intensity is increased, even glycerol in the second coordination shell can become correlated with each other. The structures of up to 35 glycerol molecules are observed. More than that, it was observed that lifetimes of glycerol-glycerol hydrogen bonds were prolonged, while the average hydrogen bond number was also increased. Besides, the structures in a strong microwave field mimic the weak C-H⋯O hydrogen bonds seen in high-glycerol concentration mixtures, yet the concentration is lower. These results indicate that with the assistance of the microwave field, glycerol molecules become concentrated and are more likely to establish stable interactions with others. As a consequence, the spherical clusters composed by glycerol molecules in our nanosheet synthesis experiment are easier to form.

Integrated Width-Modulated SiN Long Period Grating Designed for Refractometric Applications

A novel integrated photonic structure based on Long Period Waveguide Gratings (LPWGs) relying on channel-width modulation is proposed and tested for refractometric applications. These LPWGs have been fabricated through a Silicon Nitride process and experimentally characterized in terms of both surface and bulk sensitivities. Surface sensing configuration is first achieved by propagating one of the coupling optical modes into an epoxy-based negative photoresist SU8 cladding region that is in contact with the analyte via its outer surface. We subsequently show that the proposed LPWGs cladding layer can be advantageously replaced by a gas-porous polymeric bulk layer such as Styrene-co-AcryloNitrile (SAN) as the cladding region to be directly sensed to anticipate future gas sensing applications. Here, bulk sensing is optimized by increasing the analyte's influence on the modal propagation constants as it is demonstrated to be currently the most promising solution to effectively enhance the figure of merit of long period gratings of given lengths. Using varying water-glycerol mixtures, the surface sensitivity of these LPWGs has been measured at up to 240 nm per RI unit (RIU) that is in agreement with simulation. In addition, the bulk sensitivity has been indirectly estimated to be <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"><tex-math notation="LaTeX">$\sim$</tex-math></inline-formula> 1900 nm/RIU via temperature measurements, which corroborates simulation results, thereby paving the way towards gas sensing applications.

Optimization of Glycerol-Water Extraction of Selected Bioactive Compounds from Peppermint and Common Nettle.

Current trends in the industry indicate that extraction solvents should conform with the ideals of so-called “green chemistry”. Therefore, the objective of the presented study was to optimize the conditions for the extraction of polyphenols, flavonoids and chlorophyll from peppermint leaves (Mentha × piperita L., Lamiaceae) and from common nettle leaves (Urtica dioica L., Urticaceae) via green chemistry. The obtained experimental results were subjected to modelling by means of the multiple regression method, while the optimization of the system was addressed via the application of the desirability function. As a result of the use of glycerol–water systems for the extraction of the tested active compounds from mint leaves and nettle leaves, extracts with higher concentrations of polyphenols, flavonoids and chlorophyll were most often obtained, when compared with the use of classical solvents such as water and ethanol. In this work, we demonstrate that the extraction temperature has significant influence on the concentration of the determined components in the extracts. To obtain the highest values of the analysed parameters, leaves of peppermint should be extracted with glycerol–water mixture at the proportions of 30.5:69.5 at a temperature of 50 °C, while the optimal conditions for the extraction of leaves of common nettle were the glycerol–water proportions of 12.5:87.5 and extraction temperature of 20 °C. Comparing the average percentage differences between the highest values of the analysed parameters obtained in the experiment and the approximated values for various temperatures with the level of desirability, one can note a high correlation that, in the analysed examples, amounted to 0.9681. The study showed that glycerol can be an alternative solvent in the extraction of polyphenols, flavonoids and chlorophyll, replacing, e.g., ethanol—which, for various reasons, cannot always be used.

Pool Boiling Heat Transfer Coefficients in Mixtures of Water and Glycerin

Heat transfer coefficients were investigated for saturated nucleate pool boiling of binary mixtures of water and glycerin at atmospheric pressure in a wide range of concentrations and heat fluxes. Mixtures with water mass fractions from 100% to 40% were boiled on a horizontal flat copper surface at heat fluxes from about 25 up to 270kWm−2. Experiments were carried out by static and dynamic method of measurement. Results of the static method show that the impact of mixture effects on heat transfer coefficient cannot be neglected and ideal heat transfer coefficient has to be corrected for all investigated concentrations and heat fluxes. Experimental data are correlated with the empirical correlation α=0.59q0.714+0.130ωw with mean relative error of 6%. Taking mixture effects into account, data are also successfully correlated with the combination of Stephan and Abdelsalam (1980) and Schlünder (1982) correlations with mean relative error of about 15%. Recommended coefficients of Schlünder correlation C0=1 and βL=2×10−4ms−1 were found to be acceptable for all investigated mixtures. The dynamic method was developed for fast measurement of heat transfer coefficients at continuous change of composition of boiling mixture. The dynamic method was tested for water–glycerin mixtures with water mass fractions from 70% down to 35%. Results of the dynamic method were found to be comparable with the static method. For water–glycerin mixtures with higher water mass fractions, precise temperature measurements are needed.

Numerical simulation of two-phase flow and droplet breakage of glycerin-water mixture and kerosene in the cyclone reactor

• The static pressure distribution conformed with the rules of the eddy field. • The vortex motion near the side wall was intense. • The droplet deformed, stretched, and broken. • The small surface tension and large Weber number promoted droplet breakage. A liquid-liquid cyclone reactor (LLCR) was designed to achieve mixing-reaction-separation integration during isobutane alkylation catalyzed by ionic liquids. However, studies of the droplets deformation and breakage in the kind of reactors are lacking. In this work, the research studied the velocity distribution, pressure field, and turbulent field to investigate the flow pattern and the main energy loss location in the LLCR through the computational fluid dynamics (CFD) method. The simulation results were verified by experiemnts to prove the correctness of the model. Then the deformation and breakage process of droplets, and the influencing factors of droplets breakage were studied by remodeling which was based on the tangential velocity distribution result of the three dimensional model. The three dimensional simulation results clearly showed that the pressure of the LLCR was mainly concentrated in the cone section and fluid turbulent motion was the most intense near the lateral wall. The reconstruct the results of the two dimensional model clearly showed that the deformation and breakage location of droplets were mainly occurred in the velocity boundary layer, while it was difficult to break in the mainstream region. In addition, low surface tension and high Weber number had a positive effect on droplet breakage.

Time-resolved rheometry of drying liquids and suspensions

From paints to food products, solvent evaporation is ubiquitous and critically impacts product rheological properties. It affects Newtonian fluids by concentrating any nonvolatile components and viscoelastic materials, which harden up. In both of these cases, solvent evaporation leads to a change in the volume of the sample, which makes any rheological measurements particularly challenging with traditional shear geometries. Here, we show that the rheological properties of a sample experiencing “slow” evaporation can be monitored in a time-resolved fashion by using a zero normal force controlled protocol in a parallel-plate geometry. Solvent evaporation from the sample leads to a decrease of the normal force, which is compensated at all times by a decrease of the gap height between the plates. As a result, the sample maintains a constant contact area with the plates, despite the significant decrease of its volume. We validate the method under both oscillatory and continuous shear by accurately monitoring the viscosity of water–glycerol mixtures experiencing evaporation and a relative volume decrease as large as 70%. Moreover, we apply this protocol to drying suspensions. Specifically, we monitor a dispersion of charged silica nanoparticles undergoing a glass transition induced by evaporation. While the decrease in gap height provides a direct estimate of the increasing particle volume fraction, oscillatory and continuous shear measurements allow us to monitor the evolving viscoelastic properties of the suspension in real time. Overall, our study shows that a zero normal force protocol provides a simple approach to bulk and time-resolved rheological characterization for systems experiencing slow volume variations.

Correlation between the toroidal modes of an elastic sphere and the viscosity of liquids

Vibration characteristics of elastic nanostructures embedded in fluid medium have been used for biological and mechanical sensing and also to investigate materials and mechanical properties. An analytical approach has been developed in this paper to accurately predict toroidal vibrations of an elastic nanosphere in water–glycerol mixture. The Maxwell and Kelvin–Voigt models are used to describe the viscoelasticity of this fluid. The influence of key parameters such as glycerol mass fraction, sphere radius, and angular mode number are studied. We demonstrate that the sphere radius plays a significant role on the quality factor. Results also highlight three behavior zones: viscous fluid, transition, and elastic solid. In addition, these investigations can serve as benchmark solution in design of liquid sensors.

Solar Hydrogen from Glycerol-Water Mixture

The photocatalytic activity of titania supported bimetallic Cu-Ni photocatalysts were assessed for hydrogen production from water and also a mixture of glycerol-water system under visible light illumination. Addition of 2.0 mL glycerol to 8.0 mL water enhanced the solar hydrogen production from 6.1 mL to 9.5 mL. If metal was not incorporated onto TiO2 , the hydrogen production was minimal, 2.0 mL after 2 hr reaction. The band gap for bimetallic Cu-Ni/TiO2 was 2.78 eV compared to 3.16 eV for TiO2 . Photooxidation of glycerol produced glyceraldehyde, glycolic acid and oxalic acid.

Dissolution of condensed tannin powder-based polyphenolic compound in water-glycerol-acid solution

Dissolution of polyphenolic compounds from condensed tannins powder from wattle species was carried out using water-glycerol mixtures and sulfuric acid (H2SO4) as a catalyst. The study focused on parameters that can be adjusted to maximize the dissolution. The parameters of the dissolution process (mass of glycerol, mass of tannin powder, temperature and stirring time) were screened using a one factor at a time (OFAT) technique, while the optimum conditions were obtained using response surface methodology (RSM). Effects of the mass of glycerol, mass of tannin powder, temperature, and stirring time used on the percentage of dissolved tannin residue was apparent. The amount of undissolved tannin was used as the direct measurement in this study since there is no established method available to test tannin dissolution in water-glycerol-acid solution. The result from RSM based on 30 experimental sets showed that the lowest undissolved tannin powder value was 10% when 75 grams of tannin powder was mixed with 13.56 grams of glycerol, 86.44 grams of water, and 1.00 grams of sulphuric acid, at 75 °C temperature and 44.13 minutes stirring time.

Effect of viscosity on the avalanche dynamics and flow transition of wet granular matter

The dynamic behaviour of granular flows is important in geo-mechanics and industrial applications, yet poorly understood. We studied the effects of liquid viscosity and particle size on the dynamics of wet granular material flowing in a slowly rotating drum, in order to detect the transition from the avalanching to the continuous flow regime. A discrete element method (DEM) model, in which contact forces and cohesive forces were considered, was employed to simulate this flow behaviour. The model was validated experimentally, using glass beads in a wooden drum and water–glycerol mixtures to tune the liquid viscosity. The DEM simulations showed comparable results to the experiments in terms of average slope angle and avalanche amplitude. We observed that the avalanche amplitude, flow layer velocity and granular temperature decrease as the liquid viscosity increases. This effect is more pronounced for smaller sized particles. The increase in viscous forces causes the flowing particles to behave as a bulk, pushing the free surface towards a convex shape. In addition, avalanches become less pronounced and the granular flow transitions from the avalanching regime to the continuous regime. The avalanching flow regime is marked by intermittent rigid body movement of the particulate bed and near-zero drops in the granular temperature, while no rigid body movement of the bed occurs in the continuous flow regime. We identified the avalanching-continuous flow transition region as a function of a dimensionless granular Galileo number.

Molecular dynamics of water and water activity in glycerol-water mixtures

Molecular dynamics of water and water activity in glycerol-water mixtures

Revisiting the glass transition temperature of water-glycerol mixtures in the bulk and confined in mesoporous silica.

In this work, we revisited the glass transition temperature (Tg) behavior of bulk and confined water-glycerol solutions as a function of the mixture composition and size of the confinement media, with the aim to shed some light on some controversies found in the literature. In the case of bulk mixtures, some discrepancies are observed due to the differences in the way of calculating Tg from the DSC experiments and differences in the protocols of cooling/reheating. However, unphysical behavior observed below the eutectic composition can be due to the crystallization of water during the cooling of the mixture. We also analyzed the effect of confinement on the glass transition of glycerol aqueous solutions, with glycerol mass fraction, wG, between 0.5 and 1.0, in silica mesoporous samples with pore diameters between 2 and 58 nm. Our results show that the the Tg dependence on pore size changes with the mixture composition. For glycerol-rich samples, Tg decreases with a decreasing pore size. This tendency changes with increasing water concentration below wG ∼ 0.6 for samples with dp between 2 and 8 nm, where two glass transition temperatures appear. We hypothesize that this effect is related to the existence of two liquid phases with different densities. The Tg composition dependence in confined glycerol-water mixtures was analyzed with the Gordon-Taylor equation modified for confined mixtures, which allowed us to calculate the Tg of the pure components as a function of the pore size. This analysis shows that for pores with dp > 20 nm, and for pure water and pure glycerol, Tg decreases with the pore size, attaining an almost constant value for samples with pore sizes between 2 and 8 nm. This Tg pore size dependence is explained considering the competition of two opposite effects: a reduction in Tg with a decreasing pore size given when the length scale of dynamics is comparable to the pore size, and an increment in Tg with a decreasing pore size as a result of increasing interactions of the confined liquid with the pore walls.

Rotational dynamics of magnetic nanoparticles in different matrix systems

Abstract Dynamic magnetic measurements on magnetic nanoparticle (MNP) samples have been widely used for the determination of structural MNP parameters as well as for the realization of bioassays. On the other hand, proposed that the MNPs are thermally blocked, i.e., that the dynamics are dominated by the Brownian rotation, and knowing the distribution of their hydrodynamic size, information on the matrix properties can be obtained. In contrast to conventional rheology, the local environment of the MNPs is sensed on the nanoscale so that important information on the embedding of MNPs in the matrix and thus the particle-matrix interaction is obtained. Depending on the characteristic length scales of the matrix and the size of the MNPs, rheological parameters, such as viscosity and shear modulus, derived from nanorheological measurements can differ from the values obtained from conventional rheology. To measure the MNP dynamics, different experimental techniques can be applied. In this contribution, the focus lies on ac susceptometry and fluxgate magnetorelaxometry. The analysis of the complex ACS spectra is generally carried out within a modified Debye model. Different approaches for the estimation of rheological parameters from the complex ACS spectra will be presented. Two model systems will exemplarily be discussed in detail. As a Newtonian matrix system, water-glycerol mixtures were studied. It is demonstrated that the dynamic viscosity can accurately be estimated from ACS measurements on well thermally blocked single-core as well as on multicore MNP systems, which include Brownian and Néel dynamics. As a viscoelastic matrix system, aqueous gelatin solutions were studied. Gelatin is known to be a Voigt-Kelvin model system, in which elastic and viscous forces are parallel. In particular, we studied the gelation dynamics by repetitive measurements of the complex ACS spectrum. Different approaches to derive viscosity and shear modulus are applied and compared. In order to identify magnetoviscous effects in dynamic magnetic measurements, the magnetic field dependence of the Brownian relaxation time has to be eliminated. ACS measurements on various sufficiently strongly diluted aqueous MNP suspensions were performed in dependence of ac field amplitude and superimposed dc field strength and compared to theory. Excellent agreement was found.

On the onset of instability in the wake of super-hydrophobic spheres

We report an experimental investigation of free falling super-hydrophobic (SH) spheres in glycerine-water mixtures over a wide range of Reynolds number. SH coatings have the ability to reduce the contact area between the surrounding liquid and the solid surface by entrapping an air layer in the surface roughness. We investigate the effect of this air plastron on the hydrodynamic performance of spheres, focusing our attention on the onset of wake instabilities. Our results emphasise the key role of the surface roughness properties on the triggering of wake instabilities. It is shown that, unlike what was reported in previous numerical studies on SH bluff-bodies, local deformation of the interface may act as a by-pass mechanism promoting earlier transition, yielding a decrease of the critical Reynolds number at which the wake becomes unstable. A scenario coupling the hydrodynamic instabilities (scaling with the Reynolds number) and the interface deformation (scaling with the roughness-based Weber number) is proposed to describe the different transition mechanisms in presence of SH surfaces. It is found that the promotion of wake instabilities over SH surfaces occurs when the roughness-based Weber number is larger than a critical threshold. These findings are of primary importance for guiding the design of resilient and efficient SH surfaces.

Assessing the effectiveness of colloidal microcrystalline cellulose as a suspending agent for black and white liquid dyes

SummaryThis study aimed to determine the effect of the concentration (1, 5, or 8 wt%) of colloidal microcrystalline cellulose (MCCS) as suspending agent on the long‐term stability and rheology of the vegetable carbon (C) and calcium carbonate (CC) suspended in water–glycerine mixture. These suspensions as ready‐to‐use black and white liquid dyes containing 10 wt% C or CC were assessed for particle size, Turbiscan stability index (TSI), steady shear, thixotropy and dynamic viscoelasticity. After 370 days, the black dyes showed excellent stability (TSI ≪ 0.5) at 4 °C and 25 °C already at 1 wt% MCCS, while the white dyes showed reasonable stability (TSI 1–3) only at 5 and 8 wt% MCCS. Dye formulations exhibited a relatively liquid‐like viscoelastic behaviour, while they showed extremely shear‐thinning behaviour with a network structure dependent on the concentration of the MCCS as exhibited by the increase in thixotropy and the existence of the measurable yield stress.

Turning a yield-stress calcite suspension into a shear-thickening one by tuning inter-particle friction

We show that a suspension of non-Brownian calcite particles in glycerol-water mixtures can be tuned continuously from being a yield-stress suspension to a shear-thickening suspension—without a measurable yield stress—by the addition of various surfactants. We interpret our results within a recent theoretical framework that models the rheological effects of stress-dependent constraints on inter-particle motion. Bare calcite particle suspensions are found to have finite yield stresses. In these suspensions, frictional contacts that constrain inter-particle sliding form at an infinitesimal applied stress and remain thereafter, while adhesive bonds that constrain inter-particle rotation are broken as the applied stress increases. Adding surfactants reduces the yield stress of such suspensions. We show that, contrary to the case of surfactant added to colloidal suspensions, this effect in non-Brownian suspensions is attributable to the emergence of a finite onset stress for the formation of frictional contacts. Our data suggest that the magnitude of this onset stress is set by the strength of surfactant adsorption to the particle surfaces, which therefore constitutes a new design principle for using surfactants to tune the rheology of formulations consisting of suspensions of adhesive non-Brownian particles.Graphical Impact of surfactants on the rheology of concentrated calcite suspensions. Black, schematic flow curve for bare particles. Low stress: adhesive contact, rolling and sliding between particles prevented (red). High stress: frictional contact, rolling allowed (green), constraints broken → shear thinning. Blue, with surfactant. Low stress: repulsion prevents contact, rolling and sliding allowed, removing yield stress entirely. High stress: surfactant displaced (see inset), particles bare and sliding prevented; constraints formed → shear thickening

Numerical study of water-glycerol BA-LIFT: Analysis and simulation of secondary effects

In Blister-Actuated Laser-Induced Forward Transfer (BA-LIFT), a laser pulse generates a blister in an intermediate polyimide layer to push away the fluid. In this work, a Phase Field model has been proposed to study the transference mechanisms. Simulations and experimental shadowgraphy images for BA-LIFT of water-glycerol mixtures have been compared. The transference mechanism in BA-LIFT is ideally only mechanical and does not explain some secondary effects in the jet expansion that have already been described in other LIFT techniques and associated with the cavitation of a thermally generated vapor bubble.The numerical model can reproduce the expansion of the main jet. The addition of a second push at 9 μs delay allows reproducing the secondary effects. Four possible causes of the second push have been studied: absorption of the laser pulse in the fluid, thermal conduction through the polyimide layer, a mechanical rebound of the elastically deformed blister, or pressure fall due to fluid velocity. After the analysis, the first three explanations have been rejected, and a hypothesis is proposed: the velocity field generated by the blister produces a cavitation bubble in the interface between the polyimide layer and the fluid, whose effects would be the same than the cavitation of the vapor bubble in other LIFT techniques.

Assessing Changes in Dielectric Properties Due to Nanomaterials Using a Two-Port Microwave System.

Detecting changes in the dielectric properties of tissues at microwave frequencies can offer simple and cost effective tools for cancer detection. These changes can be enhanced by the use of nanoparticles (NPs) that are characterised by both increased tumour uptake and high dielectric constant. This paper presents a two-port experimental setup to assess the impact of contrast enhancement on microwave signals. The study focuses on carbon nanotubes, as they have been previously shown to induce high microwave dielectric contrast. We investigate multiwall carbon nanotubes (MWNT) and their -OH functionalised version (MWNT-OH) dispersed in tissue phantoms as contrast enhancing NPs, as well as salt (NaCl) solutions as reference mixtures which can be easily dissolved inside water mixtures and thus induce dielectric contrast changes reliably. MWNT and MWNT-OH are characterised by atomic force microscopy, and their dielectric properties are measured when dispersed in 60% glycerol–water mixtures. Salt concentrations between 10 and 50 mg/mL in 60% glycerol mixtures are also studied as homogeneous samples known to affect the dielectric constant. Contrast enhancement is then evaluated using a simplified two-port microwave system to identify the impact on microwave signals with respect to dielectric contrast. Numerical simulations are also conducted to compare results with the experimental findings. Our results suggest that this approach can be used as a reliable method to screen and assess contrast enhancing materials with regards to a microwave system’s ability to detect their impact on a target.

Water content thresholds in glycerol/water system: Low- and high-wavenumber Raman spectroscopy study

Water structure is the key in such diverse processes as protein folding, catalysis of chemical reactions, and stability of pharmaceuticals and biopharmaceuticals. In the current investigation, glycerol-water mixtures are studied by low- and high-wavenumber Raman spectroscopy. Three water content regions, which are separated by two water content thresholds (WT), WT1 at 6.1 ± 0.7 wt% water and WT2 at 18.6 ± 4.4 wt% water, are identified, based on the trends in the hydrogen bond strength and the cage effect. It is hypothesized that WT1 corresponds to a transition from predominantly unclustered water molecules to small water clusters, and is associated with facilitation of proton transfer as water content exceeds WT1. The WT2 is proposed to mark formation of large (>100 molecules) water clusters, which can form stable nucleus of hexagonal ice at lower temperatures. These findings, if confirmed for other polyhydroxycompounds, could facilitate development of novel pharmaceuticals and vaccines, and also contribute to fundamental understanding of mechanisms of cryo- and lyo-protection of proteins, viruses, and cells.

Modelling Mechanically Induced Non-Newtonian Flows to Improve the Energy Efficiency of Anaerobic Digesters

In this paper, a finite volume based computational fluid dynamics (CFD) model has been developed for investigating the mixing of non-Newtonian flows and operating conditions of an anaerobic digester. A CFD model using the multiple reference frame has been implemented in order to model the mixing in an anaerobic digester. Two different agitator designs have been implemented: a design currently used in a full-scale anaerobic mixing device, SCABA, and an alternative helical ribbon design. Lab-scale experiments have been conducted with these two mixing device designs using a water-glycerol mixture to replicate a slurry with total solids concentration of 7.5%, which have been used to validate the CFD model. The CFD model has then been scaled up in order to replicate a full-scale anaerobic digester under real operating parameters that is mechanically stirred with the SCABA design. The influence of the non-Newtonian behaviour has been investigated and found to be important for the power demand calculation. Furthermore, the other helical mixing device has been implemented at full scale and a case study comparing the two agitators has been performed; assessing the mixing capabilities and power consumption of the two designs. It was found that, for a total solids concentrations of 7.5%, the helical design could produce similar mixing capabilities as the SCABA design at a lower power consumption. Finally, the potential power savings of the more energy efficient helical design has been estimated if implemented across the whole of the United Kingdom (UK)/Austria.