Water Vapor Uptake Research Articles

Sorbent Properties of Halide-Free Ionic Liquids for Water and CO2 Perfusion

Aqueous solutions of lithium halides are state-of-the-art sorbents in sorption-based heat pump and heat storage devices, with the drawbacks of high corrosivity and limited natural resources of lithium. Halide-free ILs could be well-suited alternative sorbents and have been explored with isothermal titration calorimetry showing superior thermochemical performance. Here, we have explored the performance of selected halide-free ILs in perfusion measurements monitoring the uptake of water vapor and CO2 from an air stream with well-defined flow and humidity as a model for open sorption processes. We have determined the saturation vapor pressure of water in the corresponding water–IL mixtures and moreover determined the diffusion coefficients of molecular species in binary [EMIM][Ac]–water mixtures via pulsed-field-gradient nuclear magnetic resonance (PFG NMR) measurements. These, together with variation of the absorption rates with calorimetric monitoring, indicate that diffusion is approximately 3 orders of m...

Noncovalent Surface Modification of Cellulose Nanopapers by Adsorption of Polymers from Aprotic Solvents.

Basic adsorption of hydrophobic polymers from aprotic solvents was introduced as a platform technology to modify exclusively the surfaces of cellulose nanopapers. Dynamic vapor sorption demonstrated that the water vapor uptake ability of the nanopapers remained unperturbed, despite strong repellency to liquid water caused by the adsorbed hydrophobic polymer on the surface. This was enabled by the fact that the aprotic solvents used for adsorption did not swell the nanopaper unlike water that is generally applied as the adsorption medium in such systems. As case examples, the adsorptions of polystyrene (PS) and poly(trifluoroethylene) (PF3E) were followed by X-ray photoelectron spectroscopy and water contact angle measurements, backed up with morphological analysis by atomic force microscopy. The resulting nanopapers are useful in applications like moisture buffers where repellence to liquid water and ability for moisture sorption are desired qualities.

Preparation and characterization of in situ chitosan/polyethylene glycol fumarate/thymol hydrogel as an effective wound dressing

In the present study, polyethylene glycol fumarate (PEGF) was synthesized as a component of blend solutions via polycondensation polymerization and characterized by different tests in order to determine its functional groups and its physical properties included melting and crystallization temperature, enthalpy of fusion and average molecular weights. Wound dressing films based on chitosan (Ch), PEGF and thymol (Th) were fabricated by solvent casting method with different formulations contained 80%(w/w) chitosan and 20%(w/w) PEGF as polymeric components and different amounts of thymol consisted of 0, 0.6, 1.2 and 1.8%(v/v) as pharmaceutical additives of blend solutions. These films were evaluated by different essential tests included Fourier transform infrared spectroscopy (FTIR), tensile testing, water vapor transmission rate (WVTR), water vapor uptake, equilibrium water uptake, water solubility, swelling, scanning electron microscopy (SEM) and antibacterial activity tests. The blend film contained 1.8%(v/v) thymol demonstrated optimal properties included acceptable mechanical properties, better absorption of water vapor or liquid water, higher water vapor transmission rate and air permeability, acceptable water solubility, superior swelling level, more porous structures and rough surfaces and the excellent antibacterial activity against both gram-negative and gram-positive bacteria which make it a suitable candidate for wound dressing applications.

Water uptake, ionic and hole transport in La0.9Sr0.1ScO3 − δ

The structure of dry and hydrated perovskite La0.9Sr0.1ScO3−δ has been studied by means of X-ray and neutron powder diffraction methods. Preferable positions for oxygen vacancies and deuterons in the oxide have been determined. Thermodynamics of water vapour uptake and transport phenomena have been experimentally investigated at pH2O=0.24atm and pO2=0.18atm in the temperature range from 300 to 950°С. The enthalpy and entropy of hydration reaction have been calculated. The oxidation enthalpy for two possible mechanisms of hole transfer (band conduction and small polaron hopping) have been estimated. The electrical conductivity has been investigated by means of impedance spectroscopy measurements in the temperature range from 500 to 900°С and at the oxygen partial pressures of 10−20atm<pO2<0.21atm. The oxygen surface exchange and diffusion coefficients have been obtained by means of the isotope exchange method with gas phase equilibration in the temperature range of 600–900°С and at the oxygen partial pressure 0.01atm. The dependences of the transference numbers of protons, oxygen ions and holes on external conditions have been determined. The La0.9Sr0.1ScO3−δ oxide was found to be a pure protonic conductor at temperatures below 600°С under reducing conditions.

Sensitivity of transatlantic dust transport to chemical aging and related atmospheric processes

Abstract. We present a sensitivity study on transatlantic dust transport, a process which has many implications for the atmosphere, the ocean and the climate. We investigate the impact of key processes that control the dust outflow, i.e., the emission flux, convection schemes and the chemical aging of mineral dust, by using the EMAC model following Abdelkader et al. (2015). To characterize the dust outflow over the Atlantic Ocean, we distinguish two geographic zones: (i) dust interactions within the Intertropical Convergence Zone (ITCZ), or the dust–ITCZ interaction zone (DIZ), and (ii) the adjacent dust transport over the Atlantic Ocean (DTA) zone. In the latter zone, the dust loading shows a steep and linear gradient westward over the Atlantic Ocean since particle sedimentation is the dominant removal process, whereas in the DIZ zone aerosol–cloud interactions, wet deposition and scavenging processes determine the extent of the dust outflow. Generally, the EMAC simulated dust compares well with CALIPSO observations; however, our reference model configuration tends to overestimate the dust extinction at a lower elevation and underestimates it at a higher elevation. The aerosol optical depth (AOD) over the Caribbean responds to the dust emission flux only when the emitted dust mass is significantly increased over the source region in Africa by a factor of 10. These findings point to the dominant role of dust removal (especially wet deposition) in transatlantic dust transport. Experiments with different convection schemes have indeed revealed that the transatlantic dust transport is more sensitive to the convection scheme than to the dust emission flux parameterization. To study the impact of dust chemical aging, we focus on a major dust outflow in July 2009. We use the calcium cation as a proxy for the overall chemical reactive dust fraction and consider the uptake of major inorganic acids (i.e., H2SO4, HNO3 and HCl) and their anions, i.e., sulfate (SO42−), bisulfate (HSO4−), nitrate (NO3−) and chloride (Cl−), on the surface of mineral particles. The subsequent neutralization reactions with the calcium cation form various salt compounds that cause the uptake of water vapor from the atmosphere, i.e., through the chemical aging of dust particles leading to an increase of 0.15 in the AOD under subsaturated conditions (July 2009 monthly mean). As a result of the radiative feedback on surface winds, dust emissions increased regionally. On the other hand, the aged dust particles, compared to the non-aged particles, are more efficiently removed by both wet and dry deposition due to the increased hygroscopicity and particle size (mainly due to water uptake). The enhanced removal of aged particles decreases the dust burden and lifetime, which indirectly reduces the dust AOD by 0.05 (monthly mean). Both processes can be significant (major dust outflow, July 2009), but the net effect depends on the region and level of dust chemical aging.

Effect of Leaf Water Potential on Internal Humidity and CO2 Dissolution: Reverse Transpiration and Improved Water Use Efficiency under Negative Pressure.

The pull of water from the soil to the leaves causes water in the transpiration stream to be under negative pressure decreasing the water potential below zero. The osmotic concentration also contributes to the decrease in leaf water potential but with much lesser extent. Thus, the surface tension force is approximately balanced by a force induced by negative water potential resulting in concavely curved water-air interfaces in leaves. The lowered water potential causes a reduction in the equilibrium water vapor pressure in internal (sub-stomatal/intercellular) cavities in relation to that over water with the potential of zero, i.e., over the flat surface. The curved surface causes a reduction also in the equilibrium vapor pressure of dissolved CO2, thus enhancing its physical solubility to water. Although the water vapor reduction is acknowledged by plant physiologists its consequences for water vapor exchange at low water potential values have received very little attention. Consequences of the enhanced CO2 solubility to a leaf water-carbon budget have not been considered at all before this study. We use theoretical calculations and modeling to show how the reduction in the vapor pressures affects transpiration and carbon assimilation rates. Our results indicate that the reduction in vapor pressures of water and CO2 could enhance plant water use efficiency up to about 10% at a leaf water potential of −2 MPa, and much more when water potential decreases further. The low water potential allows for a direct stomatal water vapor uptake from the ambient air even at sub-100% relative humidity values. This alone could explain the observed rates of foliar water uptake by e.g., the coastal redwood in the fog belt region of coastal California provided the stomata are sufficiently open. The omission of the reduction in the water vapor pressure causes a bias in the estimates of the stomatal conductance and leaf internal CO2 concentration based on leaf gas exchange measurements. Manufactures of leaf gas exchange measurement systems should incorporate leaf water potentials in measurement set-ups.

Eco-friendly biorefractory films of gelatin and TEMPO-oxidized cellulose ester for food packaging application.

In recent years, many types of food-packaging films and composites have been prepared using gelatin because of its good film-forming ability, non-toxic nature and cost-effectiveness. However, the relatively weak thermal stability, poor mechanical properties and easily-degradable quality limit the potential application of gelatin as a practical material. Microcrystalline cellulose (MCC), which comprises one of the most abundant biomass resources, has been regarded as a safe and reliable food additive because it has the same ingredients as the cellulose in people's daily intake. Food-packaging films with the excellent properties provided by gelatin and oxidized-cellulose represent a topic of great interest. MCC was modified by 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation and chosen as the base of the macromolecule cross-linker (TMN). After modification of gelatin film by TMN, the minimum amount of free -NH2 in solution was 4.8 × 10-4 mol g-1 ). The thermal property obviously increased (from 322.31 o C to 352.63 o C) and was crucial for usage in the food industry. The highest water contact value 123.09° (η = 25%) indicated a better surface hydrophobicity. The higher Eab (58.88%) and lower Em (77.16%) demonstrated that a more flexible and shatter-proof material was obtained. Water vapor uptake studies suggested increased moisture absorption and greater swelling ability. The film material obtained in the present study was safe, stable, eco-friendly and biorefractory and could also be decomposed completely by the environment after disposal as a result of the properties of the ingredients gelatin and cellulose. The incorporation of a cellulosic cross-linker to gelatin-based films was an ideal choice with respect to developing a packaging for the food industry. © 2016 Society of Chemical Industry.

Influence of polyfurfuryl alcohol (PFA) loading on the properties of Nafion composite membranes

ABSTRACTComposite membranes based on Nafion (N115) loaded with furfuryl alcohol (FA) were prepared by in situ acid-catalyzed polymerization technique, with the aim to improve the ionic conductivity of Nafion membranes. The functionalization, thermal stability, electrical properties and mechanical strength of N115-PFA composites was analyzed by means of Fourier transform infrared (FT-IR) attenuated total reflection (ATR) spectroscopy, small- and wide-angle X-ray scattering (SAXS/WAXS), thermogravimetric analysis (TGA), electrical impedance spectroscopy, dynamic vapor sorption (DVS) and dynamic mechanical analyser (DMA). The FA loading in the resultant composites had a positive correlation with the water uptake (Wu), water vapor uptake (Wvu), ionic conductivity and thermo-mechanical stability. At low polyfurfuryl alcohol (PFA) loading, these membranes displayed higher Wu and improved ionic and electrical properties. Further, the thermo-mechanical stability also gradually increased with the PFA loading. All the composites showed a well-defined glass transition temperature in DMA, which shifted to higher temperature with repeated PFA loading. Overall, the results indicate that the developed composite membrane are promising for low temperature polymer electrolyte membrane (PEM) fuel cells.

Hydrogen interstitial defects in acceptor-type CuO-doped PbTiO3—Uptake and dissolution of water vapor and formation of (CuTi″−(OH)O•)′ defect complexes

The defect structure of CuO-doped PbTiO3 has been analyzed using the Hyperfine Sublevel Correlation Experiment to identify hydrogen interstitials. The formation of (CuTi″−(OH)O•)′ defect complexes has been observed, which exist in addition to the (CuTi″−VO••)× complexes. On this basis, modified reorientation characteristics are proposed due to a change in hopping mechanism from an oxygen-vacancy mediated migration mechanism to a proton hopping process. Furthermore, mobile hydrogen interstitials are generated that increase conductivity in terms of a “Grotthuss”-type charge-transport mechanism.

Thermal modification of wax-impregnated wood to enhance its physical, mechanical, and biological properties

Abstract Thermal modification is the most important commercial modification procedure. Thermally modified (TM) wood has improved durability, but its performance does not meet expectations predominately under moist conditions. To reduce water uptake of TM wood, Norway spruce specimens were treated with suspensions of a natural wax by dipping impregnation (DipI) or by vacuum-pressure impregnation (VPI). Wax-treated specimens were subsequently TM at 185, 200, 215, and 230°C. Control specimens were heated up to 100°C only. Contact angle (CA), short-term and long-term water uptake, bending strength, and performance against wood decay fungi of the resulting material were determined. The results show that a combination of wax treatment and thermal modification have a synergistic effect that considerably improves hydrophobicity, reduces liquid water uptake, slows down water vapor uptake, and improves the resistance against fungal decay of the treated material.

What Determines the Ice Polymorph in Clouds?

Ice crystals in the atmosphere nucleate from supercooled liquid water and grow by vapor uptake. The structure of the ice polymorph grown has strong impact on the morphology and light scattering of the ice crystals, modulates the amount of water vapor in ice clouds, and can impact the molecular uptake and reactivity of atmospheric aerosols. Experiments and molecular simulations indicate that ice nucleated and grown from deeply supercooled liquid water is metastable stacking disordered ice. The ice polymorph grown from vapor has not yet been determined. Here we use large-scale molecular simulations to determine the structure of ice that grows as a result of uptake of water vapor in the temperature range relevant to cirrus and mixed-phase clouds, elucidate the molecular mechanism of the formation of ice at the vapor interface, and compute the free energy difference between cubic and hexagonal ice interfaces with vapor. We find that vapor deposition results in growth of stacking disordered ice only under conditions of extreme supersaturation, for which a nonequilibrium liquid layer completely wets the surface of ice. Such extreme conditions have been used to produce stacking disordered frost ice in experiments and may be plausible in the summer polar mesosphere. Growth of ice from vapor at moderate supersaturations in the temperature range relevant to cirrus and mixed-phase clouds, from 200 to 260 K, produces exclusively the stable hexagonal ice polymorph. Cubic ice is disfavored with respect to hexagonal ice not only by a small penalty in the bulk free energy (3.6 ± 1.5 J mol(-1) at 260 K) but also by a large free energy penalty at the ice-vapor interface (89.7 ± 12.8 J mol(-1) at 260 K). The latter originates in higher vibrational entropy of the hexagonal-terminated ice-vapor interface. We predict that the free energy penalty against the cubic ice interface should decrease strongly with temperature, resulting in some degree of stacking disorder in ice grown from vapor in the tropical tropopause layer, and in polar stratospheric and noctilucent clouds. Our findings support and explain the evolution of the morphology of ice crystals from hexagonal to trigonal symmetry with decreasing temperature, as reported by experiments and in situ measurements in clouds. We conclude that selective growth of the elusive cubic ice polymorph by manipulation of the interfacial properties can likely be achieved at the ice-liquid interface but not at the ice-vapor interface.

Experimental evidence supporting the insensitivity of cloud droplet formation to the mass accommodation coefficient for condensation of water vapor to liquid water

AbstractThe mass accommodation coefficient for uptake of water vapor to liquid water, αM, has been constrained using photoacoustic measurements of aqueous absorbing aerosol. Measurements performed over a range of relative humidities and pressures were compared to detailed model calculations treating coupled heat and mass transfer occurring during photoacoustic laser heating cycles. The strengths and weaknesses of this technique are very different to those for droplet growth/evaporation experiments that have typically been applied to these measurements, making this a useful complement to existing studies. Our measurements provide robust evidence that αM is greater than 0.1 for all humidities tested and greater than 0.3 for data obtained at relative humidities greater than 88% where the aerosol surface was most like pure water. These values of αM are above the threshold at which kinetic limitations are expected to impact the activation and growth of aerosol particles in warm cloud formation.

Water Vapor Adsorption on Biomass Based Carbons under Post-Combustion CO₂ Capture Conditions: Effect of Post-Treatment.

The effect of post-treatment upon the H2O adsorption performance of biomass-based carbons was studied under post-combustion CO2 capture conditions. Oxygen surface functionalities were partially replaced through heat treatment, acid washing, and wet impregnation with amines. The surface chemistry of the final carbon is strongly affected by the type of post-treatment: acid treatment introduces a greater amount of oxygen whereas it is substantially reduced after thermal treatment. The porous texture of the carbons is also influenced by post-treatment: the wider pore volume is somewhat reduced, while narrow microporosity remains unaltered only after acid treatment. Despite heat treatment leading to a reduction in the number of oxygen surface groups, water vapor adsorption was enhanced in the higher pressure range. On the other hand acid treatment and wet impregnation with amines reduce the total water vapor uptake thus being more suitable for post-combustion CO2 capture applications.

Mimicking the Humidity Response of the Plant Cell Wall by Using Two-Dimensional Systems: The Critical Role of Amorphous and Crystalline Polysaccharides.

Of the composite materials occurring in nature, the plant cell wall is among the most intricate, consisting of a complex arrangement of semicrystalline cellulose microfibrils in a dissipative matrix of lignin and hemicelluloses. Here, a biomimetic, two-dimensional cellulose system of the cell wall structure is introduced where cellulose nanocrystals compose the crystalline portion and regenerated amorphous cellulose composes the dissipative matrix. Spectroscopic ellipsometry and QCM-D are used to study the water vapor uptake of several two-layer systems. Quantitative analysis shows that the vapor-induced swelling of these ultrathin films can be controlled by varying ratios of the chemically identical ordered and unordered cellulose components. Intriguingly, increasing the share of crystalline cellulose appeared to increase the vapor uptake but only in cases for which the interfacial area between the crystalline and amorphous area was relatively large and the thickness of an amorphous overlayer was relatively small. The results show that a biomimetic approach may occasionally provide answers as to why certain native structures exist.

The effect of F−-doping on the conductivity of proton conductor Ba4Ca2Nb2O11

The fluorine-doped solid solution with double perovskite structure Ba4Ca2Nb2O11-0.5xFx was synthesized using the solid state method. It was found that the homogeneity region was limited by the composition Ba4Ca2Nb2O10.6F0.8. Structure and electrical properties of the solid solution have been investigated. Electrical conductivities were measured by varying the temperature in dry (pH2O=1.910−4atm) and wet (pH2O=1.4210−2atm) air. These phases are capable of dissociative dissolution of water vapour and water uptake decreases with increasing x as a result of decreasing the concentration of oxygen vacancies. Fluorine doping increases the conductivity of Ba4Ca2Nb2O11 proton conductor over the investigated temperature range of 200–1000°C, and a maximum of conductivity is observed for the fluorine content of x=0.3−0.6. The difference between un- and fluorine-doped samples is more than 0.5 order of magnitude. The effect of F−-doping on ionic conductivities of double perovskite Ba4Ca2Nb2O11 deals with an increase in mobility of oxygen (dry air) and protons (wet air), the increase in the mobility (consequently, conductivity) is accompanied by decrease in activation enthalpy.

Tunable Water and CO2 Sorption Properties in Isostructural Azine-Based Covalent Organic Frameworks through Polarity Engineering

The use of covalent organic frameworks (COFs) in environmental settings such as atmospheric water capture or CO2 separation under realistic pre- and post-combustion conditions is largely unexplored to date. Herein, we present two isostructural azine-linked COFs based on 1,3,5-triformyl benzene (AB-COF) and 1,3,5-triformylphloroglucinol (ATFG-COF) and hydrazine building units, respectively, whose sorption characteristics are precisely tunable by the rational design of the chemical nature of the pore walls. This effect is particularly pronounced for atmospheric water harvesting, which is explored for the first time using COFs as adsorbents. We demonstrate that the less polar AB-COF acts as a reversible water capture and release reservoir, featuring among the highest water vapor uptake capacity at low pressures reported to date (28 wt % at <0.3 p p0−1). Furthermore, we show tailored CO2 sorption characteristics of the COFs through polarity engineering, demonstrating high CO2 uptake at low pressures ( <1 bar)...

Water Vapor Uptake of Ultrathin Films of Biologically Derived Nanocrystals: Quantitative Assessment with Quartz Crystal Microbalance and Spectroscopic Ellipsometry.

Despite the relevance of water interactions, explicit analysis of vapor adsorption on biologically derived surfaces is often difficult. Here, a system was introduced to study the vapor uptake on a native polysaccharide surface; namely, cellulose nanocrystal (CNC) ultrathin films were examined with a quartz crystal microbalance with dissipation monitoring (QCM-D) and spectroscopic ellipsometry (SE). A significant mass uptake of water vapor by the CNC films was detected using the QCM-D upon increasing relative humidity. In addition, thickness changes proportional to changes in relative humidity were detected using SE. Quantitative analysis of the results attained indicated that in preference to being soaked by water at the point of hydration each individual CNC in the film became enveloped by a 1 nm thick layer of adsorbed water vapor, resulting in the detected thickness response.

Porous Cd-carboxylate frameworks tuned by the bulk of linker: Interpenetrated nets, selective CO2 uptakes and high water vapor adsorption

Reported herein are two porous interpenetrated anionic Cd-carboxylate frameworks tuned by the length of organic linker. Shorter BDC linker and [Cd(COO)4] building blocks in 1 generate a rare 4-connected 2-fold interpenetrating qtz network. But longer NDC linker in 2 produces a self-penetrated 8-connected bcu framework with [Cd3(COO)8] SBUs. 1 and 2 both show selective CO2 adsorption and significantly, 2 exhibits the highest water vapor uptake performance (281cm3·g−1 at 298K and P/P0=0.95) among all the interpenetrated MOFs.

Sorption and thermal characterization of composite materials based on chlorides for thermal energy storage

Thermochemical heat storage is a promising technology towards efficient use of renewable energy resources. Materials based on salts and their hydrates have a high potential for a good energy storage density and the benefit of long-term storage ability. However, the process has not yet been successfully implemented due to limitations in mass and heat transfer. This paper investigates how to improve the less desirable properties of CaCl2 and its hydrates such as low melting points, agglomeration, low cycle stability and low sorption rates. The optimization of CaCl2 properties was achieved by mixing with KCl and impregnation in carrier materials to obtain a composite material. The tests show at first that, with the admixtures of KCl, water uptake during hydration is 2 times higher than that of CaCl2. Water release during dehydration is 1.3 times higher than that of CaCl2. Secondly, the use of compacted expanded natural graphite (ENG) or activated carbon foam (ACF) increases the cycle stability, thermal conductivity and the water sorption performance. Due to their hydrophobic nature those matrices have no influence on the reaction scheme, thus the total amount of water molecules sorbed by the salt-in-matrix is close to the value of CaCl2. The degree of impregnation varies from 31to90wt% depending on the host matrix and the impregnating medium used. The water vapour uptake is up to 0.61gg−1 and the water released ranges from 0.12 to 0.72gg−1. The thermal conductivity of CaCl2-in-matrixis is 3 times higher than that of sole CaCl2.

Performance investigation of an advanced multi-effect adsorption desalination (MEAD) cycle

This article presents the development of an advanced adsorption desalination system with quantum performance improvement. The proposed multi-effect adsorption desalination (MEAD) cycle utilizes a single heat source i.e., low-temperature hot water (as low as 55°C). Passive heating of the feed water (no direct heating) is adopted using total internal heat recovery from the kinetic energy of desorbed vapor and water vapor uptake potential of the adsorbent. Thus, the evaporation in the MEAD cycle ensues at low temperatures ranging from 35°C to 7°C yet providing significantly high performance ratio. The energy from the regenerated vapor is recovered for multiple evaporation/condensation of saline water by a water-run-around circuit between the top brine temperature (TBT) effect and the AD condenser. The adsorbent material is the hydrophilic mesoporous silica gel with high pore surface area. Numerical simulation for such a cycle is developed based on experimentally verified model extending to multi-effect cycle. The system is investigated under several operation conditions such as cycle time allocation, heat source temperature and the number of intermediate effects. It is observed that most of the evaporating–condensing effects operate at low temperature i.e., below 35°C as opposed to conventional multi-effect distillation (MED) cycle. For a MEAD cycle with 7 intermediate effects, the specific water production rate, the performance ratio and the gain output ratio are found to be 1.0m3/htonne of silica gel, 6.3 and 5.1, respectively. Low scaling and fouling potentials being evaporation at low temperatures yet high recovery ratio makes the cycle suitable for effectively and efficiently handling highly concentrated feed water such as produced water, brine rejected from other desalination plants and zero liquid discharge (ZLD) system.