Pure Water Surface Research Articles

Promotion mechanism of carbon dioxide hydrate formation by l-Methionine and its competitive effects with NaCl

The growth kinetics and macroscopic morphology evolution of CO2 hydrate promoted by l-Methionine (L-Met) in NaCl aqueous solutions in a wide range of mass fractions were systematically investigated. 0.05 wt% was the threshold mass fraction of L-Met to have prominent promotion effects in a batch mode. The addition of NaCl could suppress its promotion performance, while it could be regained by further addition of L-Met to 1.0 wt%. Porous feature and wall-climbing phenomena of CO2 hydrate were obvious in the presence of L-Met while it could be suppressed by NaCl. The tangential (lateral) growth rate of the hydrate film on planar pure water surface was the highest while both L-Met and NaCl could decrease it. For L-Met, it was the highest at 0.05 wt%. Special ball-like, mosaic-like and sword-like appearances of CO2 hydrates were found. Both the adsorption-capillary effects of L-Met and the hydration effects of L-Met and NaCl were thought to account for all the phenomena and a detailed scenario was proposed and discussed. A macroscopic growth model based on the tangential growth rates of hydrate films was proposed and evaluated.

Effects of Sulfate Ions on Crude Oil Adsorption/Desorption on Carbonate Rocks: Experimental and Molecular Simulations.

In the background of the strong oil wettability and low production by water flooding in carbonate reservoirs, low-salinity water containing sulfate ions can significantly change the surface wettability of carbonate rocks and thus increase the sweeping area; however, the absorption and desorption mechanisms of the oil film in the carbonate rock surface remain unclear. This paper analyzed the wettability alternation of carbonate rocks' surface in pure water and sodium sulfate solution. At the same time, MD (Materials Studio) software was used to simulate the formation process of the oil film and the effect of sulfate ions on the desorption of the oil film on the surface of carbonate rocks. The experimental results showed that sodium sulfate solution could accelerate the rate from oil-wet to water-wet and the final contact angle (49°) was smaller than that in pure water. The simulation results showed that dodecane molecules moved to the surface of calcite to form a double layer of the oil film and that the oil film near the calcite surface had a high-density stable structure under the van der Waals and electrostatic action. The hydrating sulfate ions above the oil film broke through the double oil film to form a water channel mainly under the action of electrostatic force and a hydrogen bond and then adsorbed on the calcite surface. A large number of water molecules moved down the water channel based on a strong hydrogen bonding force and crowded out the oil molecules on the surface of the calcite, resulting in the oil film detachment. This work aims to explain the interaction of oil molecules, water molecules, and SO42- ions at the molecular scale and guide the practical application of low-salinity water flooding in carbonate reservoirs.

Experimental determination of the partitioning of representative organic pollutants to the air-water interface.

Using glancing-angle laser-induced fluorescence (GALIF) spectroscopy as a probe, the partitioning of naphthalene, fluoranthene, pyrene, umbelliferone, phenol red, and bisphenol A from bulk solution to the air-water interface was examined in both pure water and aqueous solutions of 6 mM octanol. Previous studies provided similar Langmuir adsorption isotherms for anthracene and imidazole 2-carboxaldehyde. The surface partitioning behaviour of each compound in both environments was well described using a Langmuir adsorption model; partitioning coefficients were derived from the fits to such isotherms. Only the PAH molecules, naphthalene, fluoranthene and pyrene, saw an enhancement in the surface partitioning in octanol solution compared to pure water. The surface partitioning to pure water surfaces could be fairly well described using a one parameter linear free energy relationship based on either solubility or KOW.

Environmentally Friendly Plastic Boats - A Facile Strategy for Cleaning Oil Spills on Water with Excellent Efficiency.

In this report, we demonstrate a novel plastic boat capable of selectively and efficiently collecting spilled oils while floatingon water. The boat has macroscopic openings in its vertical and curved sidewalls. It is easily, quickly, and inexpensively fabricated using an environmentally friendly polymer via a three-dimensional printing technique. Its surface is sequentially coated with nano-ceramic coating liquid and oil, which imparts favorable hydrophobic, oleophilic, and high oil-wettability properties. Using the boat prototype, a small pump system, and an oil boom-like device, we demonstrate that spilled oils with a wide range of viscosities (2.0-1000 cSt at 25-40°C) are rapidly collected from the surface of both pure water and seawater. Remarkably, it efficiently collects oil spills on seawater under wavy conditions, and the retrieved oil does not mix with any drop of water. Moreover, the boat can be scaled up to a large size easily and has a long-term usage. By exhibiting these characteristics, our developed boat is a prominent potential device for practical oil retrieval applications.

Dissolution of Forsterite Surface in Brine at CO2 Geo-storage Conditions: Insights from Molecular Dynamic Simulations

Evaluating the long-term security of geological deep saline aquifers to store CO2 requires a comprehensive understanding of mineral dissolution properties. Molecular dynamics simulations are performed to study the dissolution of forsterite in deep saline aquifers. The forsterite surface is found to be covered by three H2O molecular layers, hindering CO2 from directly contacting the surface. The dissolution rates at 350 K are increased by more than 1012 with the presence of Mg defects or salt ions in solutions. The more disordered surface in pure water caused by Mg defects accounts for the acceleration of dissolution, while absorbed Cl- ions on the surface in NaCl and KCl solutions accelerate the dissolution through electrostatic interactions. Comparatively, the frequent attacks from alkaline earth cations in MgCl2 and CaCl2 solutions to the surface contribute to the enhanced dissolution. In the acidic H3OCl solution, the electrostatic interactions between O atoms in H3O+ and the surface facilitate the dissolution. Interestingly, the ionic clusters of CO32-/HCO3- and Na+ in Na2CO3/NaHCO3 solution promote the dissolution process. This work provides molecular insights into forsterite dissolution in deep saline aquifers and guidance toward the optimization of CO2 geo-storage conditions.

Time-Resolved Measurements of Interfacial Tension and Flow Speed of the Inclined Water Surface around a Self-propelled Camphor Boat by the Quasi-elastic Laser Scattering Method.

An inclined liquid surface, such as a meniscus, plays an important role in advection and transport phenomena at a liquid's surface. However, there is no time-resolved measurement method for the interfacial tension of an inclined liquid-air interface. Here, a noninvasive method for simultaneous measurements of the interfacial tension and surface flow speed for an inclined water surface is described. This is an upgrade of the quasi-elastic laser scattering method with a closed-loop control system that introduces the dynamically tracked scattered and referential light into the detector. For the evaluation of the tilt compensation by dynamic tracking, the relationship between the apparent interfacial tension and surface inclination was examined for a water meniscus at 0-5° inclinations. It was also demonstrated that simultaneous measurements of the interfacial tension and surface flow speed around a self-propelled camphor boat on a pure water surface inclined by >3° at the back end of the boat are difficult to conduct accurately without dynamic tracking. Both the interfacial tension difference and the backward flow speed increased as the boat speed increased to 0.1 m/s; that had not been evaluated to date because of the high velocity of the boat and the surface inclination of the water around it. The direct experimental evaluation of the interfacial tension and the flow speed supported the model that the driving force of the camphor boat is the interfacial tension difference and the resistance force proportional to the boat velocity reduces its acceleration.

REMOTE SENSING IN THE WAVE COMPLEX WITH CRITICALLY SMALL SIZES: RESULTS OF MULTI-FREQUENCY REMOTE SENSING OF PURE WATER

The article presents the results of remote sensing of disturbances in the small-sizes wave complex. The term "small sizes" means that water surface is critically small for the energy-carrying waves and radar spot. The results are obtained by use of the multi-frequency Doppler radar for gravitational waves, wind waves, and their mixture on pure water surface. The agreement of presented results with theoretical and semi-empirical models is discussed. Observed anomalies of scattering are described and interpreted. The numerical modeling of the scattering was carried out to clarify the spectra structure. A degradation of resonant properties of scattering in this installation is considered and quantified. The space of compliance of the laboratory and in situ conditions is discussed.

Observation of Strong Synergy in the Interfacial Water Response of Binary Ionic and Nonionic Surfactant Mixtures.

Interfacial vibrational footprints of the binary mixture of sodium dodecyl sulfate (SDS) and hexaethylene glycol monododecyl ether (C12E6) were probed using heterodyne detected vibrational sum frequency generation (HDVSFG). Our results show that in the presence of C12E6 at CMC (70 μM) the effect of SDS on the orientation of interfacial water molecules is enhanced 10 times compared to just pure surfactants. The experimental results contest the traditional Langmuir adsorption model predictions. This is also evidenced by our molecular dynamics simulations that show a remarkable restructuring and enhanced orientation of the interfacial water molecules upon DS- adsorption to the C12E6 surface. The simulations show that the adsorption free energy of DS- ions to a water surface covered with C12E6 is an enthalpy-driven process and more attractive by ∼10 kBT compared to the adsorption energy of DS- to the surface of pure water.

Polymer-Grafted Graphene Oxide as a High-Performance Nanofiller for Modification of Forward Osmosis Membrane Substrates

A substrate with good physicochemical properties is essential for minimizing unpleasant internal concentration polarization phenomena in a forward osmosis (FO) process. In this study, graphene oxide-graft-poly(2-hydroxy ethyl methacrylate) (GO-g-PHEMA, GP) nanoplates with different weight ratios were prepared for the first time using a combination of click chemistry and reversible addition–fragmentation chain-transfer polymerization. Then, high-efficiency thin-film nanocomposite (TFN) FO membranes were fabricated using GP-modified polysulfone (PSf) substrates. The influence of the structure parameter and concentration of GP on the substrate and polyamide (PA) active layer properties were systematically studied using various characterization methods. The obtained results indicated that the morphologies of the GP-modified PSf substrates were more porous, and the pure water flux, surface hydrophilicity, and mean pore size of the substrates considerably improved. Furthermore, the GP/PSf-based TFN membranes showed thicker, rougher, and permeable PA active layers than the baseline PSf-based TFC membrane. In the case of TFN-FO membranes, the water permeability noticeably increased, and the structural parameter effectively declined. Additionally, the FO performance dramatically improved (e.g., the water flux of TFN-GP210.4 reached 32.6/15.6 LMH under PRO/FO configuration). According to the results, it can be concluded that 0.4 wt % of GP21 nanofiller (GO/PHEMA ratio of 2:1) was the optimal blend concentration. Also, the modified membranes showed a noticeable performance in Caspian seawater desalination.

Molecular dynamics simulations of interfacial structure, dynamics, and interfacial tension of tetrabutylammonium bromide aqueous solution in the presence of methane and carbon dioxide.

The interfacial behavior of tetrabutylammonium bromide (TBAB) aqueous solutions in the absence of gas and the presence of methane and carbon dioxide gases is studied by molecular dynamics simulations. The aqueous TBAB phase, at concentrations similar to the solid semiclathrate hydrate (1:38 molratio), has a smaller interfacial tension and an increase in the gas molecules adsorbed at the interface compared to that in pure water. Both these factors may contribute to facilitating the uptake of the gases into the solid phase during the process of semiclathrate hydrate formation. At similar gas pressures, CO2 is adsorbed preferentially compared to CH4, giving it a higher surface density, due to the stronger intermolecular interactions of CO2 molecules of the solution at the interface. The increase in relative adsorption of CH4 at the solution surface compared to that in pure water surface is due to the hydrophobic interactions between the n-alkyl chains of the TBA+ cation and methane gas.

Experimental and Theoretical Heterodyne-Detected Sum Frequency Generation Spectroscopy of Isotopically Pure and Diluted Water Surfaces.

The χ(2) (second-order nonlinear optical susceptibility) spectrum of the water surface has been a matter of debate for a few decades. Here, we report that we experimentally measured the isotopic dilution dependence of the χ(2) spectrum and theoretically reproduced it by employing the quantum/classical mixed approach with a new idea to subtract an artifact. The present theoretical framework allows for clarifying the effects of the intramolecular, intermolecular, and Fermi resonance couplings on the OH-stretch vibrational spectra of water at the surface as well as in the bulk.

Individual adsorption of low volatility pheromones: Amphiphilic molecules on a clean water-air interface.

Environmental conditions can alter olfactory scent and chemical communication among biological species. In particular, odorant molecules interact with aerosols. Thermodynamics variables governing the adsorption from air to water surface of bombykol, the most studied pheromone, and of three derivative molecules, bombykal, bombykoic acid, and bombykyle acetate, are computed by steered and un-biased molecular dynamics in order to compare the role of their polar head group on adsorption on aqueous aerosols. When adsorbed, the molecule center of mass stands at about 1.2 Å from the interface and oscillates on the same length scale, trapped in an energy well. Gibbs energy of adsorption and desorption time of bombykol are found to be 9.2 kBT and 59µs, respectively. The following ordering between the molecules is observed, reading from the more to the least adsorbed: bombykoic acid > bombykol > bombykoic acetate > bombykal. It originates from a complex interplay of entropy and enthalpy. The entropy and enthalpy of adsorption are discussed in the light of structural arrangement, H-bonding, and hydrophilic tail positioning of the molecules at the interface. Our results show that, when dispersed in the air, pheromones adsorb on aqueous aerosols. However, the individual residence time is quite short on pure water surfaces. Aerosols can, therefore, only have a decisive influence on chemical communication through collective effects or through their chemical composition that is generally more complex than that of a pure water surface.

Measurements of pressure during the forced water entry of a cone into pure and aerated water

The present paper aims at analyzing the pressure distribution arising during water entry of a rigid cone on the free surface of pure water and aerated water initially at rest. For this purpose, impact tests were carried out using a hydraulic machine for a cone with a deadrise angle of 7° and for several impact velocities (5, 7 and 9 m/s) and air volume fractions (0, 0.35 and 1.1%). The impact pressure was measured at four different locations on the cone surface. The evolution of the pressure and the pressure impulse, the pressure maxima and the wetted surface expansion velocity are analyzed. For pure water, the results are in good agreement with the predictions of existing model analytical models of water impact based on Wagner’s theory, with a relative difference smaller than 2% percent for the wetted surface expansion velocity and 8% for the pressure impulse. For aerated water, the measured pressure evolutions are much less repeatable than for pure water and the pressure distribution is no longer axisymmetric and self-similar, likely due to inhomogeneous distributions of the bubbles in the water. Aeration is shown to induce a significant reduction of the impact pressure. A decrease of about 25% (in comparison to pure water) for both the peak pressures and the rate of increase of the pressure impulse was observed for a void volume fraction of 1.1%.

Green synthesized nano-cellulose polyethylene imine-based biological membrane

In hemodialysis process, membrane serves as a barrier between blood and the dialysate. The barrier when contacted by blood accompanied activation of coagulation, immunity, and cellular passageways. In the recent years, hemodialysis membrane's biocompatibility has become a issue which leads to reduce the performance during the separation process. In previous work, we developed and evaluated a cellulose-based membrane blended with polyaziridine or polyetyleneimine in formic acid for hydrophilicity, pure water flux, surface morphology, and permeation efficiency. Biocompatibility was accessed, by conducting cellular viability and cellular attachments tests. In this study, the membrane compared to a non-treated control, and cell viability revealed active and growing cell cultures after 14 days. During the cellular attachment experiment, cell cultures attached to the fabricated membrane simulated the formation of cell junctions, proving that the membrane is non-toxic and biocompatible. CA + PEI + FA membrane tested with a blood mimic fluid having density identical to renal patient's blood. The BSA concentration in the feed solution was the same as that in the blood of the renal patient. The results revealed that the CA + PEI + FA membrane was able to reject 99% bovine serum albumin (BSA) and 69.6% urea. Therefore, from biocompatibility and blood mimic fluid testing, it is confirmed that the CA + PEI + FA membrane is the finest implant for dialysis applications.

Synthesis and properties of ethoxylated vicinal diol nonionic surfactants with double hydrophilic head groups

A series of nonionic surfactants with double hydrophilic head groups was synthesized from ethoxylation of aliphatic 1,2-vicinal diols (C8, C10, and C12) with ethylene oxide, and characterized by Fourier transform infrared spectroscopy (FT-IR) and 1H nuclear magnetic resonance spectroscopy (1HNMR). Compared with linear primary alcohols, the lower residual alcohol content of the products indicates that the ethoxylation activity of the 1,2-vicinal diols was higher. The physicochemical properties and surface properties of the vicinal diol polyoxyethylene surfactant (DCjEn) were studied. The DCjEn surfactants reduced the pure water surface tension to ~ 30 mN m−1 with low critical micelle concentration variations of ~ 0.32–0.92 mmol L−1. The surfactant wettability was superior to that of typical commercial surfactant fatty alcohol polyoxyethylene ether (AEO9). A higher foamability and stronger foam stability that is comparable with that of widely used commodities, fatty alcohol polyoxyethylene ether sulfate (AES) and sodium dodecyl sulfate (SDS), were the remarkable properties of the DCjEn for a C12 alkyl chain length. With regards to functional properties, these novel nonionic surfactants can be used as primary surfactants in personal-care products.

Direct Evidence for a Surface and Bulk Specific Response in the Sum-Frequency Generation Spectrum of the Water Bend Vibration.

We study the bending mode of pure water and charged aqueous surfaces using heterodyne-detected vibrational sum-frequency generation spectroscopy. We observe a low (1626 cm^{-1}) and a high (1656 cm^{-1}) frequency component that can be unambiguously assigned to an interfacial dipole and a bulk quadrupolar response, respectively. We thus demonstrate that probing the bending mode provides structural and quantitative information on both the surface and the bulk.

Oscillatory Reversible Osmotic Growth of Sessile Saline Droplets on a Floating Polydimethylsiloxane Membrane

We report a cyclic growth/retraction phenomena observed for saline droplets placed on a cured poly (dimethylsiloxane) (PDMS) membrane with a thickness of 7.8 ± 0.1 µm floating on a pure water surface. Osmotic mass transport across the micro-scaled floating PDMS membrane provided the growth of the sessile saline droplets followed by evaporation of the droplets. NaCl crystals were observed in the vicinity of the triple line at the evaporation stage. The observed growth/retraction cycle was reversible. A model of the osmotic mass transfer across the cured PDMS membrane is suggested and verified. The first stage of the osmotic growth of saline droplets is well-approximated by the universal linear relationship, whose slope is independent of the initial radius of the droplet. The suggested physical model qualitatively explains the time evolution of the droplet size. The reported process demonstrates a potential for use in industrial desalination.

Near-Field Probe of Thermal Fluctuations of a Hemispherical Bubble Surface.

We report measurements of resonant thermal capillary oscillations of a hemispherical liquid gas interface obtained using a half bubble deposited on a solid substrate. The thermal motion of the hemispherical interface is investigated using an atomic force microscope cantilever that probes the amplitude of vibrations of this interface versus frequency. The spectrum of such nanoscale thermal oscillations of the bubble surface presents several resonance peaks and reveals that the contact line of the hemispherical bubble is pinned on the substrate. The analysis of these peaks allows us to measure the surface viscosity of the bubble interface. Minute amounts of impurities are responsible for altering the rheology of the pure water surface.

Energy relaxation path of excited free OH vibration at an air/water interface revealed by nonequilibrium ab initio molecular dynamics simulation.

Nonequilibrium ab initio molecular dynamics (NE-AIMD) simulations are conducted at an air/water interface to elucidate the vibrational energy relaxation path of excited non-hydrogen-bonded (free) OH. A recent time-resolved vibrational sum frequency generation (TR-VSFG) spectroscopy experiment revealed that the relaxation time scales of free OH at the surface of pure water and isotopically diluted water are very similar to each other. In the present study, the dynamics of free OH excited at the surface of pure water and deuterated water are examined with an NE-AIMD simulation, which reproduces the experimentally observed features. The relaxation paths are examined by introducing constraints for the bonds and angles of water molecules relevant to specific vibrational modes in NE-AIMD simulations. In the case of free OH relaxation at the pure water surface, stretching vibrational coupling with the conjugate bond makes a significant contribution to the relaxation path. In the case of the isotopically diluted water surface, the bend (HOD)-stretching (OD) combination band couples with the free OH vibration, generating a relaxation rate similar to that in the pure water case. It is also found that the reorientation of the free OH bond contributes substantially to the relaxation of the free OH vibrational frequency component measured by TR-VSFG spectroscopy.

Energy relaxation path of excited free hydrogen oxide vibrational energy at the air/water interface

Different relaxation paths between the surfaces of pure water and isotopically treated water can produce similar relaxation rates.