Thermodynamics of water confined in porous calcium-silicate-hydrates

Water within pores of cementitious materials plays a crucial role in the damage processes of cement pastes, particularly in the binding material comprising calcium-silicate-hydrates (C-S-H). Here, we employed Grand Canonical Monte Carlo simulations to investigate the properties of water confined at ambient temperature within and between C-S-H nanoparticles or "grains" as a function of the relative humidity (%RH). We address the effect of water on the cohesion of cement pastes by computing fluid internal pressures within and between grains as a function of %RH and intergranular separation distance, from 1 to 10 ?. We found that, within a C-S-H grain and between C-S-H grains, pores are completely filled with water for %RH larger than 20%. While the cohesion of the cement paste is mainly driven by the calcium ions in the C-S-H, water facilitates a disjoining behavior inside a C-S-H grain. Between C-S-H grains, confined water diminishes or enhances the cohesion of the material depending on the intergranular distance. At very low %RH, the loss of water increases the cohesion within a C-S-H grain and reduces the cohesion between C-S-H grains. These findings provide insights into the behavior of C-S-H in dry or high-temperature environments, with a loss of cohesion between C-S-H grains due to the loss of water content. Such quantification provides the necessary baseline to understand cement paste damaging upon extreme thermal, mechanical, and salt-rich environments.     

Effect of hydration on the dielectric properties of C-S-H gel

The behavior of water dynamics confined in hydrated calcium silicate hydrate (C-S-H) gel has been investigated using broadband dielectric spectroscopy (BDS; 10(-2)-10(6) Hz) in the low-temperature range (110-250 K). Different water contents in C-S-H gel were explored (from 6 to 15 wt%) where water remains amorphous for all the studied temperatures. Three relaxation processes were found by BDS (labeled 1 to 3 from the fastest to the slowest), two of them reported here for the first time. We show that a strong change in the dielectric relaxation of C-S-H gel occurs with increasing hydration, especially at a hydration level in which a monolayer of water around the basic units of cement materials is predicted by different structural models. Below this hydration level both processes 2 and 3 have an Arrhenius temperature dependence. However, at higher hydration level, a non-Arrhenius behavior temperature dependence for process 3 over the whole accessible temperature range and, a crossover from low-temperature Arrhenius to high-temperature non-Arrhenius behavior for process 2 are observed. Characteristics of these processes will be discussed in this work.     

Water structure in nanopores of agarose gel by Raman spectroscopy

The evolution of water structure during the gelation process is examined in aqueous solution of agarose using Raman spectroscopy of the O-H stretching band. The measurements have been performed at room temperature for different concentrations of agarose, which yields different dimensions of nanopores in the network of the created gel. Our results show that water confined in the gel pores exhibits evident changes in the local order of molecules in comparison with bulk water and water in the sol state. During the sol-gel transition the number of molecules that participate in the regular tetrahedral H-bond structure increases, and the effect is stronger for higher concentration of the biopolymer.     

石墨烯狭缝受限孔道中水分子的分子动力学模拟

石墨烯是一种具有广泛应用前景的纳米材料,特别是由石墨烯片层自组装形成的二维纳米通道能够应用于物质的过滤分离.本文采用分子动力学模拟方法研究了原态石墨烯/羟基改性石墨烯狭缝孔道中水分子的微观行为,模拟计算了水的界面结构性质和扩散动力学性质,所研究的石墨烯孔宽为0.6-1.5 nm.模拟结果表明,在石墨烯狭缝孔道中,水分子受限结构呈现层状分布,在超微石墨烯孔道(0.6-0.8 nm)中水分子可形成特殊的环状有序结构,石墨烯表面可诱导产生特殊的水分子界面取向.在石墨烯孔道中,水分子的扩散运动低于主体相水分子的扩散运动,羟基化石墨烯孔道可以促使水分子的扩散能力降低.对于改性石墨烯狭缝孔道,由于羟基的作用,水分子可以自发渗入0.6 nm的石墨烯孔道内.模拟所得到的受限水分子的动力学性质与水分子在石墨烯孔道内的有序结构有关.本文研究结果将有助于分析理解水分子通过石墨烯纳米通道的渗透机理,为设计基于石墨烯的纳米膜提供理论指导.     

The three-dimensional structure of water confined in nanoporous vycor glass

Neutron diffraction data, in conjunction with isotopic substitution of deuterium (D) for hydrogen (H), have been analyzed to determine the three-dimensional structure of water confined in vycor, an archetypal hydrophilic porous silica glass containing channels or pores of approximately 40 A diameter. The data have been incorporated into a Monte Carlo computer simulation of the confined water system, and the site-site potentials have been iteratively refined in order to produce a model ensemble which is consistent with both the neutron diffraction data and two possible geometries of the vycor pores (cylindrical and spherical). This approach has allowed us to investigate in detail the contributions to the experimentally accessible partial pair correlation functions, and ascertain whether particular features arise from interactions of the water molecules with the substrate surface, or from purely geometrical confinement effects. We observe a significant decrease in the first shell water oxygen-oxygen co-ordination number, and a decrease in the number of hydrogen bonds per water molecule from approximately 3.6 in bulk water to approximately 2.2 in confinement. In addition, we observe a significant shift inward of the second peak in the water oxygen-water oxygen coordination shell. Overall, we therefore find that the structure of the water in vycor is strongly perturbed relative to the bulk.     

Structure of methanol confined in MCM-41 investigated by large-angle X-ray scattering technique

Large-angle X-ray scattering (LAXS) measurements over a temperature range from 223 to 298 K have been made on methanol confined in mesoporous silica MCM-41 with two different pore diameters, 28 A (C14) and 21 A (C10), under both monolayer and capillary-condensed adsorption conditions. To compare the structure of methanol in the MCM-41 pores with that of bulk methanol, X-ray scattering intensities for bulk methanol in the same temperature range have also been measured. The radial distribution functions (RDFs) for the monolayer methanol samples showed that methanol molecules are strongly hydrogen bonded to the silanol groups on the MCM-41 surface, resulting in no significant change in the structure of adsorbed methanol with respect to the pore size and temperature. On the other hand, the RDFs for the capillary-condensed methanol samples showed that hydrogen-bonded chains of methanol molecules are formed in both pores. However, the distance and number of hydrogen bonds estimated from the RDFs suggested that hydrogen bonds between methanol molecules in the pores are significantly distorted or partly disrupted. It has been found that the hydrogen bonds are more distorted in the smaller pores of MCM-41. With decreasing temperature, however, the hydrogen-bonded chains of methanol in the pores were gradually ordered. A comparison of the present results on methanol in MCM-41 pores with those on water in the same pores revealed that the structural change with temperature is less significant for confined methanol than for confined water.     

Ultrafast optical Kerr effect spectroscopy of water confined in nanopores of the gelatin gel

We report on the investigation of a short-time collective dynamics of water confined in the pores of the gelatin gel, using the femtosecond optical Kerr effect spectroscopy. The ultrafast responses of water molecules obtained in bulk liquid and in three concentrations of gelatin gels are explained theoretically, both in a long time and in a short time regime, taking into account all molecular motions. We prove that the contribution of molecules involved in tetrahedral, strongly H-bonded structures stabilizing the gel network increases with the gel concentration. On the other hand the long-time relaxation of water molecules is significantly slowed down in the gel pores.     

Distinct dynamic behaviors of water molecules in hydrated pores

Water molecules confined inside narrow pores are of great importance in understanding the structure, stability, and function of water channels. Here we report that besides the H-bonding water that structures the pore, the permanent presence of a significant, fast-moving fraction of incompletely H-bonded water molecules inside the pore should control the free entry and exit of water. This is achieved by means of complementary DSC and solid-state NMR studies. We also present compelling evidence from X-ray diffraction data that the cluster formed by six water molecules in the most stable cage-like structure is sufficiently hydrophobic to be stably adsorbed in a nonpolar environment.     

Experimental study and thermodynamic modelling of methane clathrate hydrate dissociation conditions in silica gel porous media in the presence of methanol aqueous solution

In this work, the phase equilibria of clathrate hydrates of methane in the presence of pure water and 0.035 mass fraction of methanol aqueous solution in confined silica gel pores with (10 and 15) nm mean diameters are measured and reported. A thermodynamic model is also developed for prediction of the obtained experimental hydrate dissociation data. The Valderrama–Patel–Teja (VPT-EoS) equation of state (EoS) accompanied with the non-density dependent (NDD) mixing rules coupled with a previously developed activity model are applied to evaluate the fugacity of the species present and the activity coefficient of water in methanol aqueous solution. Acceptable agreement between the reported data and the predicted results using the proposed model and an existing method reported in the literature demonstrates the reliability of the presented model.     

3-D-electron microscopy configuration of TMOS wet silica gels prepared by the quick-freeze,deep-etching-rotary-replication technique

Silica gel provides a useful medium for crystal growth; solution growth is confined to pores left free by the polymer during its development. All growth steps depend on the gel structure, which is not completely known for crystal growth conditions. Therefore, a three-dimensional (3-D) visualization has been performed for two TMOS aqueous gels, which are rather fragile: the quick-freeze, deep-etching, rotary-replication method has been applied for sample preparation. An original surface labeling technique has been used for surface recognition. The results concern the distribution of macropores that are responsible for crystal nucleation; micropores whose total volume is larger have not been visualized due to the limits of the method. These results are discussed in comparison with previous data performed by light scattering.     

Properties of Water Confined in Periodic Mesoporous Organosilicas: Nanoimprinting the Local Structure

The properties of materials confined in porous media are important in scientific and technological aspects. Topology, size, and surface polarity of the pores play a critical role in the confinement effects, however, knowledge regarding the guest–pore interface structure is still lacking. Herein, we show that the molecular mobility of water confined in periodic mesoporous organosilicas (PMOs) is influenced by the polarity of the organic moiety. Multidimensional solid‐state NMR spectroscopy directly probes the spatial arrangement of water inside the pores, showing that water interacts either with only the silicate layer or with both silicate and organic layers depending on the alternating surface polarity. A modulated and a uniform pore filling mode are proposed for different types of PMOs.     

Incorporation of aluminum in the calcium silicate hydrate (C-S-H) of hydrated portland cements: a high-field 27Al and 29Si MAS NMR investigation

The calcium silicate hydrate (C-S-H) phase resulting from hydration of a white Portland cement (wPc) in water and in a 0.3 M NaAlO(2) solution has been investigated at 14 and 11 hydration times, respectively, ranging from 6 h to 1 year by (27)Al and (29)Si MAS NMR spectroscopy. (27)Al MAS NMR spectra recorded at 7.05, 9.39, 14.09, and 21.15 T have allowed a determination of the (27)Al isotropic chemical shift (delta(iso)) and quadrupolar product parameter (P(Q) = C(Q)) for tetrahedrally coordinated Al incorporated in the C-S-H phase and for a pentacoordinated Al site. The latter site may originate from Al(3+) substituting for Ca(2+) ions situated in the interlayers of the C-S-H structure. The spectral region for octahedrally coordinated Al displays resonances from ettringite, monosulfate, and a third aluminate hydrate phase (delta(iso) = 5.0 ppm and P(Q) = 1.20 MHz). The latter phase is tentatively ascribed to a less-crystalline aluminate gel or calcium aluminate hydrate. The tetrahedral Al incorporated in the C-S-H phase has been quantitatively determined from (27)Al MAS spectra at 14.09 T and indirectly observed quantitatively in (29)Si MAS NMR spectra by the Q(2)(1Al) resonance at -81.0 ppm. A linear correlation is observed between the (29)Si MAS NMR intensity for the Q(2)(1Al) resonance and the quantity of Al incorporated in the C-S-H phase from (27)Al MAS NMR for the different samples of hydrated wPc. This correlation supports the assignment of the resonance at delta(iso)((29)Si) = -81.0 ppm to a Q(2)(1Al) site in the C-S-H phase and the assignment of the (27)Al resonance at delta(iso)((27)Al) = 74.6 ppm, characterized by P(Q)((27)Al) = 4.5 MHz, to tetrahedrally coordinated Al in the C-S-H. Finally, it is shown that hydration of wPc in a NaAlO(2) solution results in a C-S-H phase with a longer mean chain length of SiO(4) tetrahedra and an increased quantity of Al incorporated in the chain structure as compared to the C-S-H phase resulting from hydration of wPc in water.     

Hydration energies and structures of alkaline earth metal ions, M2+(H2O)n, n = 5-7, M = Mg, Ca, Sr, and Ba

The evaporation of water from hydrated alkaline earth metal ions, produced by electrospray ionization, was studied in a Fourier transform mass spectrometer. Zero-pressure-limit dissociation rate constants for loss of a single water molecule from the hydrated divalent metal ions, M(2+)(H(2)O)(n) (M = Mg, Ca, and Sr for n = 5-7, and M = Ba for n = 4-7), are measured as a function of temperature using blackbody infrared radiative dissociation. From these values, zero-pressure-limit Arrhenius parameters are obtained. By modeling the dissociation kinetics using a master equation formalism, threshold dissociation energies (E(o)) are determined. These reactions should have a negligible reverse activation barrier; therefore, E(o) values should be approximately equal to the binding energy or hydration enthalpy at 0 K. For the hepta- and hexahydrated ions at low temperature, binding energies follow the trend expected on the basis of ionic radii: Mg > Ca > Sr > Ba. For the hexahydrated ions at high temperature, binding energies follow the order Ca > Mg > Sr > Ba. The same order is observed for the pentahydrated ions. Collisional dissociation experiments on the tetrahydrated species result in relative dissociation rates that directly correlate with the size of the metals. These results indicate the presence of two isomers for hexahydrated magnesium ions: a low-temperature isomer in which the six water molecules are located in the first solvation shell, and a high-temperature isomer with the most likely structure corresponding to four water molecules in the inner shell and two water molecules in the second shell. These results also indicate that the pentahydrated magnesium ions have a structure with four water molecules in the first solvation shell and one in the outer shell. The dissociation kinetics for the hexa- and pentahydrated clusters of Ca(2+), Sr(2+), and Ba(2+) are consistent with structures in which all the water molecules are located in the first solvation shell.     

Modelling adsorption of a water molecule into various pore structures of silica gel

Silica gel is widely used in commercial applications as a water adsorbent due to its properties including hydrothermally stable, high water sorption capacity, low regeneration temperature, low cost and wide range of pore diameters. Since the water sorption capacity of silica gel strongly depends on the pore size and structure, which can be controlled during synthesis, this paper study the effect of pore shapes and dimensions of silica gel upon the adsorption of a water molecule aiming at maximising the water sorption capacity. In particular, we consider three types of pore structures, namely cylindrical, square prismatic and conical pores. On using the Lennard-Jones potential and a continuum approximation, we find that the minimum radii for a water molecule to be accepted into cylindrical, square prismatic and conical pores are 4.009, 3.7898 and 4.4575 Å, respectively. For cylindrical and square prismatic pores, the critical radii which maximise the adsorption energy are 4.5189 and 4.1903 Å, respectively. Knowledge of these critical pore sizes may be useful for the manufacturing process of silica gel that will maximise the water sorption capacity.     

Molecular Mechanisms Causing Anomalously High Thermal Expansion of Nanoconfined Water

Anomalously high thermal expansion is measured in water confined in nanoscale pores in amorphous silica and the molecular mechanisms are identified by molecular dynamics (MD) simulations using an accurate dissociative water potential. The experimentally measured coefficient of thermal expansion (CTE) of nanoconfined water increases as pore dimension decreases. The simulations match this behavior for water confined in 30 Å and 70 Å pores in silica. The cause of the high expansion is associated with the structure and increased CTE of a region of water ～6 Å thick adjacent to the silica. The structure of water in the first 3 Å of this interface is templated by the atomically rough silica surface, while the water in the second 3 Å just beyond the atomically rough silica surface sits in an asymmetric potential well and displays a high density, with a structure comparable to bulk water at higher pressure.     

Acrylamide-based magnetic nanosponges: a new smart nanocomposite material

Nanocomposite materials consisting of CoFe2O4 magnetic nanoparticles and a polyethylene glycol-acrylamide gel matrix have been synthesized. The structure of such materials was studied by means of small-angle scattering of X-rays and polarized neutrons, showing that the CoFe2O4 nanoparticles were successfully and homogeneously embedded in the gel structure. Magnetic, viscoelastic, and water retention properties of the nanocomposite gel confirm that the properties of both nanoparticles and gel are combined in the resulting nanomagnetic gel. Scanning electron microscopy highlights the nanocomposite nature of the material, showing the presence of a gel structure with different pore size distributions (pores with micron and nano-size distributions) that can be used as active sponge-like nanomagnetic container for water-based formulations as oil-in-water microemulsions.     

Activation of water on the TiO2 (110) surface: the case of Ti adatoms

Using first-principles calculations we have studied the reactions of water over Ti adatoms on the (110) surface of rutile TiO(2). Our results provide fundamental insights into the microscopic mechanisms that drive this reaction at the atomic level and assess the possibility of using this system to activate the water dissociation reaction. In particular, we show that a single water molecule dissociates exothermically with a small energy barrier of 0.17 eV. After dissociation, both H(+) and OH(-) ions bind strongly to the Ti adatom, which serves as an effective reactive center on the TiO(2) surface. Finally, clustering of Ti adatoms does not improve the redox activity of the system and results in a slightly higher energy barrier for water dissociation.     

Density minimum of confined water at low temperatures: a combined study by small-angle scattering of X-rays and neutrons

A simple explanation is given for the low-temperature density minimum of water confined within cylindrical pores of ordered nanoporous materials of different pore size. The experimental evidence is based on combined data from in-situ small-angle scattering of X-rays (SAXS) and neutrons (SANS), corroborated by additional wide-angle X-ray scattering (WAXS). The combined scattering data cannot be described by a homogeneous density distribution of water within the pores, as was originally suggested from SANS data alone. A two-step density model reveals a wall layer covering approximately two layers of water molecules with higher density than the residual core water in the central part of the pores. The temperature-induced changes of the scattering signal from both X-rays and neutrons are consistent with a minimum of the average water density. We show that the temperature at which this minimum occurs depends monotonically on the pore size. Therefore we attribute this minimum to a liquid-solid transition of water influenced by confinement. For water confined in the smallest pores of only 2 nm in diameter, the density minimum is explained in terms of a structural transition of the surface water layer closest to the hydrophilic pore walls.     

Mechanism of freezing of water in contact with mesoporous silicas MCM-41, SBA-15 and SBA-16: role of boundary water of pore outlets in freezing

The freezing mechanism of water contacted with mesoporous silicas with uniform pore shapes, both cylindrical and cagelike, was studied by thermodynamic and structural analyses with differential scanning calorimetry (DSC) and X-ray diffraction (XRD) together with adsorption measurements. In the DSC data extra exothermic peaks were found at around 230 K for water confined in SBA-15, in addition to that due to the freezing of pore water. These peaks are most likely to be ascribed to the freezing of water present over the micropore and/or mesopore outlets of coronas in SBA-15. Freezing of water confined in SBA-16 was systematically analysed by DSC with changing the pore size. The freezing temperature was found to be around 232 K, close to the homogeneous nucleation temperature of bulk water, independent of the pore size when the pore diameter (d) < 7.0 nm. Water confined in the cagelike pores of SBA-16 is probably surrounded by a water layer (boundary water) at the outlets of channels to interconnect the pores and of fine corona-like pores, which is similar to that present at the outlet of cylindrical pores in MCM-41 and of cylindrical channels in SBA-15. The presence of the boundary water would be a key for water in SBA-16 to freeze at the homogeneous nucleation temperature. This phenomenon is similar to those well known for water droplets in oil and water droplets of clouds in the sky. The XRD data showed that the cubic ice I(c) was formed in SBA-16 as previously found in SBA-15 when d < 8.0 nm.