Water Vapor Desorption Isotherms Research Articles

A quantitative and mechanistic model for the coupling between chemistry and clay hydration

It is proposed here to describe smectite water vapor desorption isotherms using an exchange formalism that quantitatively accounts for the different hydration states and thus different water contents. This approach makes it possible to reproduce both desorption isotherms and relative proportions of the different hydration states as determined by X-ray diffraction. The method is numerically robust and easy to implement in most reactive transport codes. The formalism is satisfactory from a phenomenological point of view and accounts for the influence of external parameters such as interlayer cation composition and solution cation composition and salinity on clay hydration. Furthermore, in contrast to most solid solution models, this approach focuses on the clay reactivity according to the charge and type of interlayer cation rather than on its solubility and therefore does not require the overall thermodynamic properties of the clay. In addition, such an explicit distinction of the hydration/cation exchange processes from the thermodynamic stability of smectite 2:1 layer allows the use of kinetics driving slow dissolution/precipitation rates if the number of exchange sites is related to the amount of clay minerals.

Influence of layer charge on hydration properties of synthetic octahedrally-charged Na-saturated trioctahedral swelling phyllosilicates

Smectite hydration impacts dynamical properties of interlayer cations and thus the transfer and fate of H2O, contaminants, and nutriments in surficial environments where this ubiquitous clay mineral is often one of the main mineral components. The influence of key crystal-chemical parameters, such as the amount of charge or the presence of fluorine, rather than hydroxyl groups, in smectite anionic framework, on hydration, organization of interlayer species, and related properties has been described for tetrahedrally substituted trioctahedral smectites (saponites). Despite the ubiquitous character of octahedrally substituted smectites, that make most of the world bentonite deposits, the influence of charge location on smectite hydration properties has not received similar attention. A set of octahedrally substituted trioctahedral smectites (hectorites) with a common structural formula NaxMg6-xLixSi8.0O20(OH)4 and a layer charge (x) varying from 0.8 to 1.6 was thus synthesized hydrothermally. The distribution of charge-compensating Na+ cations and of associated H2O molecules was determined experimentally from the modeling of X-ray diffraction data obtained along water vapor desorption isotherms. Consistent distributions of charge-compensating cations and of associated H2O molecules were also computed from GCMC simulations as a function of layer charge. Interlayer H2O contents [2.5–5.5 and 8.0–10.0 H2O molecules per O20(OH)4 for 1W and 2W hydrates, respectively] are similar in all Na-saturated smectite samples, independent of the location and amount of their layer charge. In contrast to synthetic saponite, for which stability of most hydrated layers was increased by increasing layer charge, the stability of synthetic hectorite hydrates is only marginally affected by layer charge. Consistently, the layer-to-layer distance of Na-saturated hectorite 2W (and 1W) layers is independent of layer charge (15.10–15.65 Å and 12.0–12.6 Å, respectively). The contrasting hydration behavior of synthetic Na-saturated saponite and hectorite is likely due to different electrostatic attraction between the 2:1 layer and interlayer cation, the charge undersaturation of O atoms at the surface of hectorite 2:1 layer being more diffuse compared to saponite. Combined with previous results on saponites, the present data and sample set provides key constraints to assess the validity of force fields simulating clay-water interactions for an unmatched variety of smectite with contrasting locations and amounts of layer charge deficits.

Specific surface area of strongly swelling polymer hydrogels for agriculture

The study is the first attempt in soil physics to estimate the effective specific surface area of strongly swelling polymer hydrogels as soil conditioners of a new generation. Along with the standard assessment of water vapor desorption isotherms by the BET method, a new method for determining the specific surface area deduced from the slope of water retention curves was used. Water desorption isotherms and water retention curves were obtained by a dynamic sorption equilibrium method and by a new method of thermodesorption. The specific surface area values of synthetic polymer hydrogels ranged from 468 to 1029 m2/g. An innovative Russian product VM-P with amphiphilic filler in the form of dispersed peat had the maximum specific surface area among all studied types of hydrogels. Water absorption properties and dispersion of gels have a hysteresis caused, presumably, by the dynamics of dispersion in the cycles of wetting-drying.

Moisture transport and sorption in cement based materials containing slag or silica fume

This paper presents the moisture dependency of moisture transport and moisture fixation in mortars with OPC, slag and silica fume. Water vapor desorption isotherms were measured with gravimetric methods and the moisture dependency of moisture transport was investigated with cup-tests. The results show an ongoing evolution of water vapor desorption isotherms from eight months to four years. The evolution is more pronounced for mortars containing slag. The results also show that there is a significant difference in moisture dependency of the moisture transport properties above 70% relative humidity; some mortars exhibit a clear moisture dependency in moisture transport whereas others do not. At a relative humidity below 70%, the water to binder ratio is more decisive for moisture transport than the type of binder. These results are of value for service-life models, where they represent important input data, and for understanding the evolution of the microstructure at later ages.

Aging and durability of concrete in lab and in field conditions – pore structure and moisture content gradients between inner and surface zones in RC structural elements

In real structures, gradients between inner and surface zones, which depend on the mix-design, as well as on curing and environmental conditions, are critical issues for durability, in particular when the mixture incorporates supplementary cementitious material (e.g. fly ash (FA)). This paper deals with pore structure and moisture content gradients, investigated not only on concrete samples in lab conditions, but also on reinforced concrete (RC) structural elements exposed for several years to three different outdoor environments (temperate climate, tidal zone in marine environment, as well as road and cold environment) and on full-scale structures (bridges). The experimental study was launched a lot of years ago within the framework of the large-scale and long-term “BHP 2000” French national project. The various mixtures studied (28-day cylinder compressive strengths ranging from 20 to 130 MPa) include high-performance concretes (HPCs) with or without silica fume (SF), as well as normal strength FA concretes. MIP pore size distributions obtained on the RC structural elements have been compared to lab results. In addition, in order to investigate the long-term drying(-wetting) behavior of the various types of materials studied here, water vapor desorption isotherms, internal relative humidity (RH), and degree of saturation profiles have been measured, respectively, by the saturated salt solution method, RH sensors, and gamma-ray attenuation on lab samples or on cores extracted from the elements and bridges at various times. The data have been analyzed as a function of the exposure conditions and of the mix-parameters. For example, the impact of early age external drying, carbonation, as well as freezing and thawing cycles in the presence of deicing salts has been highlighted on the field data. In addition, good performance of SF-HPCs and mature FA-concretes has been pointed out in the outdoor conditions considered.

Smectite fluorination and its impact on interlayer water content and structure: A way to fine tune the hydrophilicity of clay surfaces?

In addition to isomorphic cation substitutions, smectite layers may present anionic substitutions with fluorine replacing the structural hydroxyl groups and inducing a reduced number of H2O molecules hydrating interlayer cations. The resulting additional versatility of smectite layers could be used to fine-tune the hydrophilicity of pure or intercalated smectite pending a detailed understanding of interlayer water organization. The present article thus reports on the hydration of (fluoro-)hectorite samples exhibiting similar charge density (structural formulae: [Na0.8·nH2O]inter[Mg5.2Li0.8]oct[Si8.0]tetO20(OH,F)4). Water sorption isotherms and PIGE/PIXE analyses allowed constraining the water content over the probed range of relative humidity and the bulk chemistry, respectively. Modeling of X-ray diffraction (XRD) profiles obtained along water vapor desorption isotherms allowed gaining additional insights in the distribution of interlayer H2O molecules. Compared to hydroxylated smectites of similar charge, fluorinated hectorites contain ∼30% less interlayer H2O molecules although transitions between discrete hydration states are observed for similar values of relative humidity. These molecules (3–4 and 6–8 H2O molecules per cation in the mono- and bi-hydrated states, respectively) predominantly belong to the hydration sphere of interlayer cations, although additional H2O molecules are present in the bi-hydrated state. As a consequence, the positional disorder of interlayer H2O molecules is much reduced in fluorinated samples, thus increasing the minimum distance from an interlayer H2O molecule to the smectite layer, most likely owing to the hydrophobicity of fluorinated layers. Finally, the distribution of layers with a given hydration state is more heterogeneous within smectite crystals for fluorinated smectites, compared to hydroxylated ones, possibly as the result of the improved crystallinity.

Effect of randomly methylated beta-cyclodextrin on physical properties of soils.

The application of cyclodextrins in several soil remediation technologies has been increasingly studied, but little is known about their effects on soil physical properties. One of the popular soil remediation additives, randomly methylated beta-cyclodextrin (RAMEB), was found to significantly alter surface and pore properties of soil clay minerals. Therefore, in this paper we studied the effect of various RAMEB doses on physical properties of selected soils, representing a wide range of clay content (3-49%). The results showed that soil physical properties were greatly modified by RAMEB treatment. Analysis of water vapor adsorption isotherms revealed that RAMEB increased water adsorption and surface area in sandy soils and decreased them in clayey soils. An increase in adsorption energy of water in RAMEB-treated soils indicated that desorption of nonpolar pollutants can be enhanced. Water vapor desorption isotherms showed that the volumes and radii of micropores (nanometers range) increased above 1% RAMEB concentration. The micropores became more rough and complex after RAMEB treatment as deduced from an increase in fractal dimensions. The volume of soil mesopores measured by mercury intrusion porosimetry (micrometers range) gradually decreased in most soils with an increase in RAMEB concentration whereas the average mesopore radius increased, indicating that finer mesopores were blocked by RAMEB. Measurements of the granulometric composition of soils by sedimentation analysis showed that the amount of coarse-size soil fractions increased on the expense of finer fractions due to aggregation of smaller particles. Behavior of the studied soils after RAMEB treatment depended on their clay content and the dose of cyclodextrin. In clay-rich soils, strong interactions of cyclodextrins with the soil solid phase governed the resulting soil properties. In clay-poor soils, the cyclodextrin excess (not interacted with clays) played a dominant role. Modification of surface, pore, and aggregation properties of soils by RAMEB can have a significant effect in soil remediation technologies.

Water vapor equilibrium relationships of potato slices

The water vapor desorption isotherms of blanched and sulfited Norchip and Norland potato slices have been determined for the temperature range 10 ≤T ≤40°C, and the water activity, 0.11 ≤aw ≤1.00. Monolayer sorption values together with isosteric heat of sorption, spreading pressure, molar entropy and equilibrium heat of sorption have been estimated from the isotherms, and an attempt to relate the values of these functions to the way water is bound to the solid matrix has been made