Molecular Layers Of Water Research Articles

Controlling Frost Propagation on Polymeric Surfaces Using SI‐ATRP Chemical Micropatterning

AbstractMicropatterned surfaces with both hydrophilic and hydrophobic regions are relevant for a wide range of applications from fuel cells to water harvesting systems. The preferential nucleation of water on hydrophilic regions can also be used to control frost nucleation on chemically patterned surfaces. So far, this concept has been tested on brittle silicon surfaces with only a few different sizes and shapes of hydrophilic regions. In this work, the concept of controlled icing is investigated on five polymeric surfaces with different surface energies modified by micropatterning them with three types of hydrophilic polymer brushes. Frost formation and propagation on the resulting patterned surfaces with regions of varying wettability is monitored and quantified using high‐resolution thermal imaging. The study proves that control over frost nucleation and propagation using regions of varying wettability can be achieved on commodity polymers. In addition to influencing the time and location of ice nucleation, the local patterning affects the freezing propagation mode and rate due to its impact on the continuity and thickness of molecular water layers (MWL). These results show that local control over the state of MWLs is key to controlling both ice nucleation and propagation of freezing events on surfaces.

Role of Molecular Water Layer State on Freezing Front Propagation Rate and Mode Studied with Thermal Imaging.

In this work, we study the relationship between the molecular water layer (MWL) and frost freezing onset and propagation. The progression of frost has been reported to be governed by various localized icing phenomena, including interdroplet ice bridging, dry zones, and frost halos. Reports studying the state of water on surfaces have revealed the presence of a thin nanometer water layer on a range of surfaces. Regardless of further investigations that show environmental humidity, temperature, and surface energy to affect the thickness of the MWL on surfaces, the influence of the MWL on frost nucleation and propagation has not yet been previously addressed in the literature. To study the effect of the MWL on surface freezing events, a range of surface-functionalized glass substrates were prepared. In situ monitoring of freezing events with thermal imaging allowed studying the effect of surface chemistry and environmental relative humidity (RH) on the thickness and continuity of the MWL. We argue that the observed icing nucleation and propagation kinetics are directly related to the presence and continuity of the MWL, which can be manipulated by controlling the environmental humidity and surface chemistry.

Charging Effects in Inlet Capillaries.

Glass or metal inlet capillaries are commonly used for flow restriction in atmospheric pressure ionization mass spectrometers. They exhibit a high ion transmission rate and stability at most operating conditions. However, transferring unipolar currents of ions through inlet capillaries can lead to sudden signal dropouts or drifts of the signal intensity, particularly when materials of different conductivity are in contact with the capillary duct. Molecular layers of water and other gases such as liquid chromatography solvents always form on the surfaces of inlet capillaries at atmospheric pressure ionization conditions. These surface layers play a major role in ion transmission and the occurrence of charging effects, as ions adsorb on the capillary walls as well, charging the walls to electric potentials of up to kilovolts and eventually leading to a hindrance of ion transport into or through the capillary duct. In this work, surface charging effects are reported in dependence on the capillary material, i.e., borosilicate glass, (reduced) lead silicate, quartz, and metal. Low electrical conductance materials show a more pronounced long-term signal drift (e.g., quartz), while higher electrical conductance materials lead to stable long-term behavior.

Morphology of Ionic Micelles as Studied by Numerical Solution of the Poisson Equation.

The existing concepts of the ionic micelle structure were specified. It was noted that the composition of dispersed phase particles in a liquid dispersion medium should necessarily include adsorbed counterions rigidly bound to these particles. By numerical solution of the Poisson equation for the two most often used approximations, the Poisson–Boltzmann (PB) model and the Jellium-approximation (JA), the electric potential decay from the Stern potential of dispersed phase particles was defined. A new methodological approach to analyze the reaction of micelle potential decay based on small variability of the CMC value was proposed. It made possible to determine the dimension parameter, which in the presence of weak thermal effects approximately corresponds to the micelle hydrodynamic radius, and to calculate the electrokinetic potential of micelles. The results of theoretical calculations were compared with our previous experimental data on the thickness of the SDS micelle hydrophilic layer obtained by SAXS. A good agreement between the calculated and measured values was obtained, and it was noted that for low concentrations the experimental values are more correctly described by the PB model, but for concentrations greater than 100 mM the JA model is more preferable. It was found that the slipping plane is located near the outer Stern plane and is separated from it only by a few molecular layers of water. The influence stronger than the thermal one can shift the slipping plane closer to the micelle core. Accordingly, the smallest hydrodynamic micelle size is determined by the outer Stern plane. The results of our work allowed us to conclude that the micelle is not something soft and watery, but according to its specified structure, it is a more solid-like particle than was previously assumed. The proposed approach can be extended to investigate other effects of a physicochemical nature, in particular, those observed with the addition of an external electrolyte or nanoparticles.

Ordered Water Layer on the Macroscopically Hydrophobic Fluorinated Polymer Surface and Its Ultrafast Vibrational Dynamics.

Hydrophobic-like water monolayers have been predicted at the metal and some polar surfaces by theoretical simulations. However, direct experimental evidence for the presence of this water layer at surfaces, particularly at biomolecule and polymer surfaces, is yet to be validated at room temperature. Here we observe experimentally that an ordered molecular water layer is present at the hydrophobic fluorinated polymer such as polytetrafluoroethylene (PTFE) surface by using sum frequency generation vibrational spectroscopy. The macroscopic hydrophobicity of PTFE surface is actually hydrophilic at the molecular level. The macroscopically hydrophobic character of PTFE is indeed resulting from the hydrophobicity of the ordered two-dimension (2D) water layer, in which cyclic water tetramer structure is found. The water layer at humidity of ≤40% has a vibrational relaxation time of 550 ± 60 fs. The vibrational relaxation time in the frequency range of 3200-3400 cm-1 shows remarkable difference from the interfacial water at the air/H2O interface and the lipid/H2O interface. No discernible frequency dependence of the vibrational relaxation time is observed, indicating the homogeneous dynamics of OH groups in the water layer. These insights into the water layer at the macroscopically hydrophobic surface may contribute to a better understanding of the hydrophobic interaction and interfacial water dynamics.

Plumbing the depths of the graphene wetting controversy

Plumbing the depths of the graphene wetting controversy

The nano-scale viscoelasticity using atomic force microscopy in liquid environment

We measured viscoelasticity of two nanoscale systems, single protein molecules and molecular layers of water confined between solid walls. In order to quantify the viscoelastic response of these nanoscale systems in liquid environment, the measurements are performed using two types of atomic force microscopes (AFMs), which employ different detection schemes to measure the cantilever response. We used a deflection detection scheme, available in commercial AFMs, that measures cantilever bending and a fibre-interferometer based detection which measures cantilever displacement. The hydrodynamics of the cantilever is modelled using Euler–Bernoulli equation with appropriate boundary conditions which accommodate both detection schemes. In a direct contradiction with many reports in the literature, the dissipation coefficient of a single octomer of titin I278 is found to be immeasurably low. The upper bound on the dissipation coefficient is 5 × 10−7 kg s−1, which is much lower than the reported values. The entropic stiffness of single unfolded domains of protein measured using both methods is in the range of 10 mN m−1. We show that in a conventional deflection detection measurement, the phase of the bending signal can be a primary source of artefacts in the dissipation estimates. It is recognized that the measurement of cantilever displacement, which has negligibly small phase lag due to hydrodynamics of the cantilever at low excitation frequencies, is better suited for ensuring artefact-free measurement of viscoelasticity compared to the measurement of the cantilever bending. Further, it was possible to measure dissipation in molecular layers of water confined between the tip and the substrate using fibre interferometer based AFM with similar experimental parameters. It confirms that the dissipation coefficient of a single I278 is below the detection limit of AFM. The results shed light on the discrepancy observed in the measured diffusional dynamics of protein collapse measured using Force spectroscopic techniques and single-molecule optical techniques.

Reversible Switching of Charge Transfer at the Graphene-Mica Interface with Intercalating Molecules.

Understanding and controlling charge transfer through molecular nanostructures at interfaces is of paramount importance, particularly for electronic devices but also for contact electrification or in bioelectronics. We investigate the influence of intercalation and exchange of molecularly thin layers of small molecules (water, ethanol, 2-propanol, and acetone) on charge transfer at the well-defined interface between an insulator (muscovite mica) and a conductor (graphene). Raman spectroscopy is used to probe the charge carriers in graphene. While a molecular layer of water blocks charge transfer between mica and graphene, a layer of the organic molecules allows for it. The exchange of molecular water layers with ethanol layers switches the charge transfer very efficiently from off to on and back. We propose a charge transfer model between occupied mica trap states and electronic states of graphene, offset by the electrostatic potentials produced by the molecular dipole layers, as supported by molecular dynamics simulations. Our work demonstrates how intercalation of molecules of volatile liquids can reversibly affect charge transfer at interfaces. This implies its strong impact on the function of hybrid inorganic-organic electronic devices in different ambients and potential applications, including sensors and actuators.

Ion exchange selectivity in clay is controlled by nanoscale chemical–mechanical coupling

Ion exchange in nanoporous clay-rich media plays an integral role in water, nutrient, and contaminant storage and transport. In montmorillonite (MMT), a common clay mineral in soils, sediments, and muds, the swelling and collapse of clay particles through the addition or removal of discrete molecular layers of water alters cation exchange selectivities in a poorly understood way. Here, we show that ion exchange is coupled to the dynamic delamination and restacking of clay layers, which creates a feedback between the hydration state of the exchanging cation and the composition of the clay interlayer. Particles with different hydration states are distinct phases with unique binding selectivities. Surprisingly, equilibrium achieved through thermal fluctuations in cation concentration and hydration state leads to the exchange of both ions and individual MMT layers between particles, a process we image directly with high-resolution transmission electron microscopy at cryogenic conditions (cryo-TEM). We introduce an exchange model that accounts for the binding selectivities of different phases, which is likely applicable to many charged colloidal or macromolecular systems in which the structural conformation is correlated with the activities of water and counterions within spatially confined compartments.

Chirality and bound water in the hierarchical cellulose structure

The origins of the unique properties of natural fibres have remained largely unresolved because of the complex interrelations between structural hierarchy, chirality and bound water. In this paper, analysis of the melting endotherms for bleached hardwood pulps indicates that the amount of non-freezing bound water (0.21 g/g) is roughly half of the amount of freezing bound water (0.42 g/g). We link this result to the two smallest constitutive units, microfibrils and their bundles, using molecular dynamics simulations at both hierarchical levels. The molecular water layers found in the simulations correspond quite accurately to the measured amount of non-freezing and freezing bound water. Disorder that results from the microfibril twist and amphiphilicity prevents co-crystallisation, leaving routes for water molecules to diffuse inside the microfibril bundle. Moreover, the simulations predict correctly the magnitude of the right-handed twist at different hierarchical levels. Significant changes in hydroxymethyl group conformations are seen during twisting that compare well with existing experimental data. Our findings go beyond earlier modelling studies in predicting the twist and structure of the microfibril bundle.Graphic abstract

Extended Microprestress-Solidification Theory for Long-Term Creep with Diffusion Size Effect in Concrete at Variable Environment

The solidification theory has been accepted as a thermodynamically sound way to describe the creep reduction due to deposition of hydrated material in the pores of concrete. The concept of self-equilibrated nanoscale microprestress has been accepted as a viable model for marked multi-decade decline of creep viscosity after the hydration effect became too feeble, and for increase of creep viscosity after any sudden change of pore humidity or temperature. Recently, though, it appeared that the original microprestress-solidification theory (MPS) predicts incorrectly the diffusion size effect on drying creep and the delay of drying creep behind drying shrinkage. Presented here is an extension (XMPS) that overcomes both problems and also improves a few other features of the model response. To this end, different nano- and macro-scale viscosities are distinguished. The aforementioned incorrect predictions are overcome by a dependence of the macro-scale viscosity on the rate of pore humidity change, which is a new feature inspired by previous molecular dynamics (MD) simulations of a molecular layer of water moving between two parallel sliding C-S-H sheets. The aging is based on calculating the hydration degree, and the temperature change effect on pore relative humidity is taken into account. Empirical formula for estimating the parameters of permeability dependence on pore humidity from concrete mix composition are also developed. Extensive validations by pertinent test data from the literature are demonstrated.

Ab Initio Molecular Dynamics Simulations of the Influence of Lithium Bromide on the Structure of the Aqueous Solution-Air Interface.

We present the results of ab initio molecular dynamics simulations of the solution–air interface of aqueous lithium bromide (LiBr). We find that, in agreement with the experimental data and previous simulation results with empirical polarizable force field models, Br– anions prefer to accumulate just below the first molecular water layer near the interface, whereas Li+ cations remain deeply buried several molecular layers from the interface, even at very high concentration. The separation of ions has a profound effect on the average orientation of water molecules in the vicinity of the interface. We also find that the hydration number of Li+ cations in the center of the slab Nc,Li+–H2O ≈ 4.7 ± 0.3, regardless of the salt concentration. This estimate is consistent with the recent experimental neutron scattering data, confirming that results from nonpolarizable empirical models, which consistently predict tetrahedral coordination of Li+ to four solvent molecules, are incorrect. Consequently, disruption of the hydrogen bond network caused by Li+ may be overestimated in nonpolarizable empirical models. Overall, our results suggest that empirical models, in particular nonpolarizable models, may not capture all of the properties of the solution–air interface necessary to fully understand the interfacial chemistry.

Non-monotonous Wetting of Graphene-Mica and MoS2-Mica Interfaces with a Molecular Layer of Water.

Hydration of interfaces with a layer of water is a ubiquitous phenomenon, which has important implications for numerous natural and technologically important processes. Nevertheless, at the nanoscale, the understanding of the wetting process is still limited, since it is experimentally difficult to follow. Here, graphene and monolayers of MoS2 deposited on dry mica are used to investigate wetting of the two-dimensional (2D) material-mica interfaces with a molecularly thin layer of water employing scanning force microscopy in different modes. Wetting occurs non-monotonously in time and space for both types of interfaces. It starts at relative humidities (RH) of 10-17% for graphenes and 8-9% for MoS2 and concludes with a homogeneous layer at 25-30 and 15-20%, respectively. Investigation of the process at the graphene-mica interface indicates that up to about 25% RH, initially a highly compliant and unstable layer of water spreads, which subsequently stabilizes by developing labyrinthine nanostructures. Moreover, these nanostructures exhibit distinct mechanical deformability and dissipation, which is ascribed to different densities of the confined water layer. The laterally structured morphology is explained by the interplay of counteracting long-range dipole-dipole repulsion and short-range line tension, with the latter causing at least in part by the mechanical deformation of the 2D material. The proposed origins of the interactions are common for thin layers of polar molecules at interfaces, implying that the lateral structuring of thin wetting layers at submonolayer concentrations may also be a quite general phenomenon.

Interface-controlled growth of organic semiconductors on graphene

We have studied submonolayer coverages of N,N-1H,1H-perfluorobutyl dicyanoperylenecarboxydiimide (PDIF-CN2) on mechanically exfoliated graphene transferred onto SiO2 substrates. Our atomic force microscopy (AFM) data show that PDIF-CN2 forms irregularly-shaped 1.4 nm-high islands. From the selected area diffraction performed with transmission electron microscope (TEM) we conclude that this height corresponds to π−π stacks of molecules, which are inclined for 43° relative to the graphene surface. AFM also showed complete absence of PDIF-CN2 on single-layer graphene (SLG). Electric force microscopy revealed a marked difference in surface charge density between a single-layer graphene and bilayer graphene, with a higher surface charge on SLG than on the bilayer graphene. We associate this behavior with p−type doping of graphene due to the electrostatic dipole induced by the molecular water layer present at the graphene/SiO2 interface. The crucial role of the graphene/SiO2 interface in determining growth of PDIF-CN2 was further confirmed by TEM examination of PDIF-CN2 deposited onto unsupported SLG.

Structural and Electrochemical Properties of Physisorbed and Chemisorbed Water Layers on the Ceramic Oxides Y2O3, YSZ, and ZrO2.

A combination of operando Fourier transform infrared spectroscopy, operando electrochemical-impedance spectroscopy, and moisture-sorption measurements has been exploited to study the adsorption and conduction behavior of H2O and D2O on the technologically important ceramic oxides YSZ (8 mol % Y2O3), ZrO2, and Y2O3. Because the characterization of the chemisorbed and physisorbed water layers is imperative to a full understanding of (electro-)catalytically active doped oxide surfaces and their application in technology, the presented data provide the specific reactivity of these oxides toward water over a pressure-and-temperature parameter range extending up to, e.g., solid-oxide fuel cell (SOFC)-relevant conditions. The characteristic changes of the related infrared bands could directly be linked to the associated conductivity and moisture-sorption data. For YSZ, a sequential dissociative water ("ice-like" layer) and polymeric chained water ("liquid-like") water-adsorption model for isothermal and isobaric conditions over a pressure range of 10(-5) to 24 mbar and a temperature range from room temperature up to 1173 K could be experimentally verified. On pure monoclinic ZrO2, in contrast to highly hydroxylated YSZ and Y2O3, a high surface concentration of OH groups from water chemisorption is absent at any temperature and pressure. Thus, the ice-like and following molecular water layers exhibit no measurable protonic conduction. We show that the water layers, even under these rather extreme experimental conditions, play a key role in understanding the function of these materials. Furthermore, the reported data are supposed to provide an extended basis for the further investigation of close-to-real gas adsorption or catalyzed heterogeneous reactions.

Charge Transfer to LaAlO3/SrTiO3 Interfaces Controlled by Surface Water Adsorption and Proton Hopping

Electronic properties of low dimensional systems are particularly sensitive to surface adsorbates. Clear understanding of such phenomena can lead to highly effective and nondestructive material engineering techniques. In this work, water adsorption at the surface of LaAlO3/SrTiO3 heterostructures is systematically studied. The saturation of surface dangling bonds by spontaneous water chemisorptions is found to be a main enabler of the formation of the interface 2D electron gas. In particular, when imbalanced distributions of water based ions, namely protons and hydroxyls, are generated, interface electron doping or depletion becomes surface adsorbates dominant and independent of the LaAlO3 layer thickness. The investigations also reveal the importance of hydrogen bonding through molecular water layers, which provides an energetically feasible pathway for manipulating the surface‐bond protons and thus the interface electrical characteristics.

Cellulose nanocrystal interactions probed by thin film swelling to predict dispersibility.

The production of well-dispersed reinforced polymer nanocomposites has been limited due to poor understanding of the interactions between components. Measuring the cohesive particle-particle interactions and the adhesive particle-polymer interactions is challenging due to nanoscale dimensions and poor colloidal stability of nanoparticles in many solvents. We demonstrate a new cohesive interaction measurement method using cellulose nanocrystals (CNCs) as a model system; CNCs have recently gained attention in the composites community due to their mechanical strength and renewable nature. Multi-wavelength surface plasmon resonance spectroscopy (SPR) was used to monitor the swelling of CNC thin films to elucidate the primary forces between CNCs. This was achieved by measuring swelling in situ in water, acetone, methanol, acetonitrile, isopropanol, and ethanol and relating the degree of swelling to solvent properties. Films swelled the most in water where we estimate 1.2-1.6 nm spacings between CNCs (or 4-6 molecular layers of water). Furthermore, a correlation was found between film swelling and the solvent's Hildebrand solubility parameter (R(2) = 0.9068). The hydrogen bonding component of the solubility parameters was more closely linked to swelling than the polar or dispersive components. The films remained intact in all solvents, and using DLVO theory we have identified van der Waals forces as the main cohesive interaction between CNCs. The trends observed suggest that solvents (and polymers) alone are not sufficient to overcome CNC-CNC cohesion and that external energy is required to break CNC agglomerates. This work not only demonstrates that SPR can be used as a tool to measure cohesive particle-particle interactions but additionally advances our fundamental understanding of CNC interactions which is necessary for the design of cellulose nanocomposites.

Squeeze-out dynamics of nanoconfined water: A detailed nanomechanical study.

In this study, we present a detailed analysis of the squeeze-out dynamics of nanoconfined water confined between two hydrophilic surfaces measured by small-amplitude dynamic atomic force microscopy. Explicitly considering the instantaneous tip-surface separation during squeeze-out, we confirm the existence of an adsorbed molecular water layer on mica and at least two hydration layers. We also confirm the previous observation of a sharp transition in the viscoelastic response of the nanoconfined water as the compression rate is increased beyond a critical value (previously determined to be about 0.8 nm/s). We find that below the critical value, the tip passes smoothly through the molecular layers of the film, while above the critical speed, the tip encounters "pinning" at separations where the film is able to temporarily order. Preordering of the film is accompanied by increased force fluctuations, which lead to increased damping preceding a peak in the film stiffness once ordering is completed. We analyze the data using both Kelvin-Voigt and Maxwell viscoelastic models. This provides a complementary picture of the viscoelastic response of the confined water film.

Termination and hydration of forsteritic olivine (0 1 0) surface

Termination and hydration of the forsteritic (Fo90Fa10) olivine (010) surface have been investigated with high-resolution specular X-ray reflectivity and Atomic Force Microscopy. The surface was prepared by polishing a naturally grown {010} face, from which we found the polished surface in acidic (pH 3.5) alumina suspension exhibits regular steps while the basic (pH 9.5) silica polished surface is irregularly roughened, indicating there are two distinguishable mechanochemical processes for the surface dissolution. The quantitative interpretation of the regular steps from the alumina-polished surface suggests that the observed step heights correspond to multiples of crystallographic unit cell. Only this atomically terraced surface is investigated with the high-resolution X-ray reflectivity (HRXR) to determine the surface termination and hydration. The basic silica paste polished surface turned out too rough to measure with X-ray reflectivity. HRXR reveals that the alumina polished olivine (010) surface in pure water is terminated at a plane including half-occupied metal ion sites (M1), an oxygen vacancy site, and a silicate tetrahedral unit with one of its apices pointing outward with respect to the surface. An ideal termination with the oxygen vacancy would fulfill the stoichiometry of the formula unit; however, in the observation, the vacancy site is filled by an adsorbed water species and about a quarter of the remaining metal ions are further depleted. The terminating plane generates two distinct atomic layers in the laterally averaged electron density profile, on which two highly ordered adsorbed water layers are formed. The first layer formation is likely through the direct interaction with the M1 plane and the second layer is likely through the hydrogen bonding interaction with the first water layer. With this multilayered adsorbed water structure, the surface metal ion is partially hydrated by the vacancy-filling water species and adsorbed water molecules. The bulk water links to these distinct adsorbed water layers, with weak density oscillations that almost completely damp out after the first bulk water layer. The total thickness of the layered water structure including the two distinct adsorbed layers and the first layer of bulk water is slightly less than 1nm, which corresponds to roughly three molecular layers of water. These results describe the steric constraints of the surface metal ion hydration and the iron redox environment during water–olivine interactions in this particular crystallographic orientation.

The atmospheric structure and fundamental parameters of the red supergiants AH Scorpii, UY Scuti, and KW Sagittarii

We present the atmospheric structure and the fundamental properties of the red supergiants (RSGs) AH Sco, UY Sct, and KW Sgr based on VLTI/AMBER observations. We carried out spectro-interferometric observations of AH Sco, UY Sct, and KW Sgr in the near-infrared K band with the VLTI/AMBER instrument, and compared the data to a new grid of hydrostatic PHOENIX model atmospheres. In our visibility data, we observe molecular layers of water and CO in extended atmospheres. For a uniform disk modeling, we observe size increases at the water band of 10% to 25% and at the CO bandheads of 20%-35% with respect to the near continuum bandpass. The PHOENIX atmosphere models predict the spectra and the continuum visibility values, but cannot reproduce the large extensions of the molecular layers. This indicates that the opacities of the molecular bands are included, but that the model atmospheres are too compact compared to the observations. The observed extended layers may be levitated by processes such as pulsation or convection, which are not included in the hydrostatic atmospheric models. Comparing the continuum visibility values to PHOENIX models, we estimate the Rosseland-mean photospheric angular diameters. Together with the distance and the spectro-photometry, we calculate radii and effective temperatures. The location of the targets in the HR-diagram is confirmed to be close to, and possibly slightly to the right of, the Hayashi limit of recent evolutionary tracks corresponding to masses between about 20 Msun and 40 Msun