Effect of added salt on the depletion attraction caused by non-adsorbing clay particles

Total internal reflection microscopy (TIRM) has been used to study the effect of a model clay colloid (laponite) on the interparticle forces acting between a 6 μm polystyrene sphere and a glass slide when the two are separated by 50–350 nm of an aqueous solution containing up to 1 mM of NaCl. In the absence of clay, the Brownian sphere samples elevations in the vicinity of the secondary minimum formed by gravitational attraction, van der Waals attraction and double-layer repulsion. The addition of clay induces a discernible depletion attraction at concentrations greater than 100 ppm and for separation distances as large as 200 nm, which greatly exceeds the diameter of the laponite disks (25 nm). Increasing the clay concentration increases the magnitude of this attraction without changing the range (defined as the largest separation distance at which the attractive potential is 1 kT). Increasing the concentration of an indifferent electrolyte (NaCl) reduces both the magnitude and range of the depletion attraction. These observations are in quantitative agreement with the primitive theory in which depletion attraction is computed as the product of the osmotic pressure of the polyelectrolyte (calculated from Donnan’s equation) and the area of overlap of the depletion layers. Besides the effect of the polyelectrolyte on the Debye length, the only adjustable parameter is the depletion layer thickness or ‘effective radius’ of the platelets which is found to be the radius of the laponite disks plus five Debye lengths.     

澄清溶液体系二次生长法NaA型沸石膜的生长机制及膜厚的控制合成

用晶种涂层二次生长成膜法研究了在含水量不同的澄清溶液合成体系中NaA型沸石膜的生长及沸石膜厚度的控制合成.用SEM,TEM和XRD表征手段分析了沸石膜的形成过程和微结构.在载体表面不涂晶种而直接合成则不易形成连续沸石膜;用晶种涂层二次法可以很容易形成均匀的连续膜.合成液中水量的高低强烈影响沸石膜的生长速率、形成结构和膜的厚度.在高水量(水硅摩尔比为2000)的合成体系中沸石生长速率慢,膜主要通过晶种层中的晶粒长大,交织成膜,且膜只有一层结构;而在低水量(水硅摩尔比为750)的合成体系中沸石生长速率快,膜则通过晶种层表面晶粒向外生长、交织成膜,而膜具有两层结构.通过调变合成液的水量可有效地控制沸石膜层的厚度,并能制得非常均匀、连续的膜.     

Removal of diphenhydramine from water by swelling clay minerals

Frequent detection of pharmaceuticals in surface water and wastewater attracted renewed attention on studying interactions between pharmaceuticals and sludge or biosolids generated from wastewater treatment. Less attention was focused on studying interactions between pharmaceuticals and clay minerals, important soil and sediment components. This research targeted on investigating interactions between diphenhydramine (DPH), an important antihistamine drug, and a montmorillonite, a swelling clay, in aqueous solution. Stoichiometric desorption of exchangeable cations accompanying DPH adsorption confirmed that cation exchange was the most important mechanism of DPH uptake by the swelling clay. When the solution pH was below the pK(a) of DPH, its adsorption on the swelling clay was less affected by pH. Increasing solution pH above the pK(a) value resulted in a decrease in DPH adsorption by the clay. An increase in d(001) spacing at a high DPH loading level suggested interlayer adsorption, thus, intercalation of DPH. The results from this study showed that swelling clays are a good environmental sink for weak acidic drugs like DPH. In addition, the large cation exchange capacity and surface area make the clay a good candidate to remove cationic pharmaceuticals from the effluent of wastewater treatment facilities.     

Fractal structure in natural gels: effect on carbon sequestration in volcanic soils

Allophanic soils are interesting in terms of environmental properties especially because of their potentialities as sinks for “greenhouse gases” by the way of C sequestration. These volcanic soils contain amorphous clays (allophanes) and exhibit higher organic carbon content than the one measured in other clay soils. We measured the C content of a set of allophanic soils and showed that the C content is positively correlated to the allophane content. We also measured the part of organic matter transformed into CO₂ during a respiration experiment and showed that the decomposition is lowered as the soils allophane content increases. Allophane aggregates are very close to the synthetic gels: high specific surface area large pore volume, fractal structure, large water content and important irreversible shrinkage during drying. In this work we characterized by Small Angle X-Ray Scattering (SAXS) the fractal structure of the allophane aggregates at the nano scale. We hypothesized that the peculiar structure and the associated low accessibility of the allophanic soils could explain the high organic carbon content and the associated poor transformation into CO₂. The tortuous structure of the allophane aggregates plays the role of a labyrinth which fix and traps soil organic carbon.     

Behavior of some macroelements,trace elments and RE in the water-sediment system

The aim of this work was to estimate the processes of sorption or desorption which take place when water of slightly higher temperature and elevated concentrations of some elements, compared to groundwater, comes into contact with aquifer sediments under aerobic conditions. The behavior of some macro-elements, trace elements and RE in the water/sediment systems, prepared as five different granulometric fractions of the sediment, was followed by INAA, AAS and titrimetric methods, under simulated natural conditions. It was found that, for the majority of elements, desorption takes place. Opposite to this, Mg and Zn are sorbed from water on all sediment granulometric fractions. The concentration of Ca as a major cation is lingering about its initial value. Na, K, Ba, Sr, Fe, Hg, Au, Sc, Sb, U, La and Ce are desorbed from all sediment fractions. The desorption from finer sediment phase was less pronounced for Fe, Hg, Au, Sc, Sb and Ce. Sorption of some elements (like Co, Cr and Zr) on smallest sediment fraction (<90 m) appears. Sorption-desorption processes, as well as water pH changes, are time dependent, continuing for some weeks, especially in the coarse sediment system. The extents of sorption and desorption for most of the determined elements indicate that the specific surface area is not a key parameter     

GEOCHEMISTRY OF SEDIMENTS AND ENVIRONMENT IN XIHU LAKE OF GREAT WALL STATION OF CHINA, ANTARCTICA

The determined results in this paper, which were obtained by the multielement analysis of the 260 cm-deep core sediments under the water of Xihu Lake in the Great Wall Station area, are as follows: The Cenozoic volcanic rocks around Xihu Lake are the main source of sediments in the lake. The chemical differentiation in very fine particles is still detectable. From the variation of ratios of the Cs/Rb, Br/CI and La/Yb in the clay fraction with depth and from the variation or CaCO_3 contained in the sediments, cation replacing amount in the clay grains and the sediment grain sizes in time, it can be seen that since 3600 a. B. P., there has existed the climatic variation of warm-cold-warm, which embodies the advance and retreat history of the ice sheet in this area.     

Nanostructure development in nylon 6-Cloisite® 30B composites. Effects of the preparation conditions

PA6 composites with Cloisite® 30B (30B), prepared by different procedures, i.e., melt compounding, static annealing and solution blending, have been characterized by X-ray diffraction and microscopic analyses (TEM, SEM, POM) in order to shed more light on the mechanism of nanostructure development. It has been demonstrated that intercalation of the PA6 chains within the 30B galleries takes place very rapidly, in the absence of applied stresses, even when the size of the clay particles is relatively large (tens of microns) and the clay loading is very high (even 50 wt.%). It has also been shown that, if, conversely, the filler content is low (∼10 wt.% or less) and the particles are tiny (e.g., as for polymer/clay mixtures prepared by precipitation from a common solution), intercalation continues, under quiescent conditions, and leads in reasonable times to complete destruction of the silicate platelets stacking order. The composites with higher filler contents display a mixed exfoliated/intercalated morphology, with the intercalated silicate stacks characterized by an interlayer distance of about 3.7 nm. Contrary to statically annealed composites, the melt kneaded ones are characterized by a homogeneous dispersion of the filler particles and a local parallel orientation of the silicate platelets that induces, during polymer crystallization, an orientation of the polymer crystallites parallel to the faces of the compression molded specimens. Experiments carried out using 30B samples previously treated at 250 °C for 4 h under vacuum (30Bdegr) indicate that this treatment, probably due to the collapsed interlayer spaces, lowers the extent of PA6 chains intercalation. Thus, the relevant PA6/30Bdegr composites are characterized by the coexistence of unintercalated clay tactoids/agglomerates and individual silicate layers formed as result of intercalation on the edges of the filler particles.     

Preparation,application and water reducing mechanism of a novel fluorescent superplasticizer with improved flow retaining ability and clay tolerance

Abstract

Novel fluorescent polycarboxylate superplasticizer modified by anhydride naphthalene groups was prepared, and characterized by ^1?H NMR and FTIR. Fluidity behaviors of cement suspensions mixed with the polycarboxylate indicated that the superplasticizer not only exhibited good fluidity maintaining properties but also demonstrated stable performance in the coexistence of clay. The addition of quaternary ammonium salt polymer can inhibit the water absorption and expansion of clay. Adsorption amounts, adsorption layer thickness and zeta potential were determined to elucidate the water reducing mechanism. The adsorbed layer thickness was linked to the steric hindrance, deciding the dispersing ability and dispersing retention ability.     

Geochemical Conditions Enhancing the Solubilization of Arsenic into Groundwater in Japan

The geochemical behavior of arsenic-bearing groundwaters from four areas—Fukuoka, Kumamoto, Fukui, and Takatsuki—has been reviewed and considered from the viewpoints of the chemical composition of the water, the geological setting of the host formation, and the arsenic content in sediments and rocks. In all the areas except Fukui, arsenic-bearing water is concluded to have come from a specific aquifer during water–sediment interactions. Stagnant groundwater, having reducing and alkaline properties, played a significant role in the release of arsenic from such Quaternary sediments as silt–clay layers and brownish-colored gravel beds.     

The use of thermo-XRD-analysis in the study of organo-smectite complexes

Summary Thermo-XRD-analysis is applied to identify whether or not the adsorbed organic species penetrates into the interlayer space of the smectites mineral. In this technique an oriented smectite sample is gradually heated to temperatures above the irreversible dehydration of the clay, and after each thermal treatment is diffracted by X-ray at ambient conditions. In the thermal treatment of organo-clays, under air atmosphere at temperatures above 250°C, the organic matter is in part oxidized and charcoal is formed from the organic carbon. In inert atmosphere e.g. under vacuum above 250°C the organic matter is pyrolyzed and besides small molecules, charcoal is formed. If the adsorbed organic compound is located in the interlayer space, the charcoal is formed in that space, preventing the collapse of the clay. A basal spacing of above 1.12 nm suggests that during the adsorption the organic compound penetrated into the interlayer space. Thermo-XRD-analyses of montmorillonite complexes with anilines, fatty acids, alizarinate, protonated Congo red and of complexes of other smectites with acridine orange are described. To obtain information about spacings of the different tactoids that comprise the clay mixture, curve-fitting calculations on the X-ray diffractograms were adapted.     

Hydration of a synthetic clay with tetrahedral charges: a multidisciplinary experimental and numerical study

The interaction of water with a synthetic saponite clay sample, with a layer charge of 1 per unit cell (0.165 C m(-2)), was investigated by following along water adsorption and desorption in the relative pressure range from 10(-6) to 0.99 (i) the adsorbed amount by gravimetric and near-infrared techniques, (ii) the basal distance and arrangement of water molecules in the interlayer by X-ray and neutron diffraction under controlled water pressure, and (iii) the molecular structure and interaction of adsorbed water molecules by near-infrared (NIR) and Raman spectroscopy under controlled water pressure. The results thus obtained were confronted with Grand Canonical Monte Carlo (GC/MC) simulations. Using such an approach, various well-distinct hydration ranges can be distinguished. In the two first ranges, at low water relative pressure, adsorption occurs on external surfaces only, with no swelling associated. The next range corresponds to the adsorption of water molecules around the interlayer cation without removing it from its position on top of the ditrigonal cavity of the tetrahedral layer and is associated with limited swelling. In the following range, the cation is displaced toward the mid-interlayer region. The interlamellar spacing thus reached, around 12.3 A, corresponds to what is classically referred to as a "one-layer hydrate," whereas no water layer is present in the interlayer region. The next hydration range corresponds to the filling of the interlayer at nearly constant spacing. This leads to the formation of a well-organized network of interlayer water molecules with significant interactions with the clay layer. The structure thus formed leads to a complete extinction of the d001 line in D2O neutron diffraction patterns that are correctly simulated by directly using the molecular configurations derived by GC/MC. The next range (0.50 < P/P0 < 0.80) corresponds to the final swelling of the structure to reach d spacing values of 15.2 A (usually referred to the "two-layer hydrate"). It is associated with the development of a network of liquidlike water molecules more structured than in bulk water. The final hydration range at high relative pressure mainly corresponds to the filling of pores between clay particles.     

Underwater sediment analyses by laser induced breakdown spectroscopy and calibration procedure for fluctuating plasma parameters

Laser Induced Breakdown Spectroscopy (LIBS) was applied on sediments directly under water. The aim of the research was to develop a method for measuring the sediment elemental composition, including minor elements, which could be implemented in-situ. The plasma was generated by a double-pulse, Q-Switched Nd:YAG laser operated at 1064 nm. For signal detection, both ICCD and non-gated, compact detectors were used. The major difficulties in underwater sediment analyses are related to the natural and laser induced surface roughness, and to the sample softness. The latter is responsible for the formation of particle clouds above the surface, which scatter both the laser and plasma radiation, and often results in breakdown formation above the analyzed surface. In such cases, a broad sonoluminescence emission from water, formed during the gas bubble collapse was sometimes registered. Under optimized experimental conditions, even by using a non-gated detector and single shot acquisition, it was possible to detect several minor sediment constituents, such as titanium, barium, manganese and others. A crude estimation of the Limit of Detection (LODs) for these elements was performed by underwater measurements on certified soils/sediments. Due to strong shot-to-shot fluctuations in the plasma temperature, well correlated calibration curves, aimed for quantitative analyses, could only be obtained after applying an appropriate data processing procedure. The latter selects automatically only the spectra characterized by similar plasma parameters, which are related to their continuum spectral distribution. Application of such a procedure improves the measurement accuracy also in other surroundings and on samples different from the ones analyzed here.     

Adsorption — Desorption equilibria of some radionuclides in sediment — Sea water system

Chemical and physical properties of Suez Canal bottom sediments (SCBS) and sea water at port Tawfeek area, the south entrance of Suez canal, have been studied. The SCBS was separated into its size fractions (natural sediment, sand, silt and clay). These different sediment fractions were allwed to be in equilibrium with⁸⁹Sr,⁶⁰Co and¹³⁴Cs solutions. Desorption studies were carried out on these contaminated sediments.     

羟甲基化木质素磺酸盐添加剂对钻井液性能的影响

为了进一步优化木质素磺酸盐作为钻井液处理剂的效能,利用其与甲醛的羟甲基化反应制备了羟甲基化木质素磺酸盐;采用红外光谱仪、X射线粉末衍射仪、扫描电镜等分析了其结构;测定了改性前后的木质素磺酸盐对钻井液流变性、降滤失性、黏土水化膨胀抑制性等性能的影响.结果显示,改性后的羟甲基化木质素磺酸盐的整体结构变化不大,但羟基数量增加,与水的相溶性增强.与木质素磺酸盐相比,羟甲基化木质素磺酸盐在室温下对基浆有较强的提黏作用,经180℃高温老化后降黏、降滤失作用有所增强,形成的泥饼厚度降低,对黏土水化膨胀的抑制作用增强.     

Dominating reactions in the degradation of HDPE during long term ageing in water

A Phillips type high density polyethylene was extruded six times without additives and the compression molded plates prepared from the granules were stored in distilled water for 12 months. Specimens withdrawn from the containers at regular intervals were thoroughly characterized with various methods including the determination of weight changes, color, MFI, functional group content (FTIR), molecular weight (GPC), thermal (DSC) and mechanical (tensile) properties. The results proved that all reactions taking place during the storage of HDPE in distilled water are related to each other; the correlation of all functional groups formed or consumed in them is surprisingly close. The amount of oxygen present determines the direction of reactions, larger oxygen content leads to chain scission, to an increase of methyl content and to the formation of carbonyl groups. Most of these reactions go through double bonds, their number decreases during storage. In spite of the large number of reactions proposed in the literature, only one or two dominating reactions determine the changes in the chain structure of the polymer and thus the properties of the final product under the conditions of this study. Any variation in the conditions of storage is reflected in the properties of the polymer. Stabilizers used under extractive conditions must be stable against hydrolysis and should trap oxygen centered radicals.     

Thermogravimetric analysis of different molar mass ammonium cations intercalated different cationic forms of montmorillonite

Different cationic forms of montmorillonite, mainly K-, Na-, Ca- and Mg-montmorillonites were intercalated in this study via ion exchange process with mono-, di-, and triethanolammonium cations. The developed samples were characterized by TG, XRD, and CHNS techniques. Thermogravimetric study of ammonium-montmorillonites shows three thermal transition steps, which are attributable to the volatilization of the physically adsorbed water and dehydration, followed by the decomposition of the intercalated ammonium cations and dehydroxylation of the structural water of the modified clay, respectively, while untreated and cationic forms of montmorillonite showed only two decomposition steps. The type of ammonium cation has affected both desorption temperature (Position) and the amount of the adsorbed water (intensity). XRD results show a stepwise change in the crystallographic spacings of montmorillonite with the molar mass of ammonium cation, reflecting a change in the structure of the clay. CHNS data confirm the intercalation of ammonium cations into the interlayer space of montmorillonite and corroborate the effect of the molar mass of ammonium cation on the amount adsorbed by the clay.     

Formation of silica nanoparticles in microemulsions

Silica nanoparticles for controlled release applications have been produced by the reaction of tetramethylorthosilicate (TMOS) inside the water droplets of a water-in-oil microemulsion, under both acidic (pH 1.05) and basic (pH 10.85) conditions. In-situ FTIR measurements show that the addition of TMOS to the microemulsion results in the formation of silica as TMOS, preferentially located in the oil phase, diffuses into the water droplets. Once in the hydrophilic domain, hydrolysis occurs rapidly as a result of the high local concentration of water. Varying the pH of the water droplets from 1.05 to 10.85, however, considerably slows the hydrolysis reaction of TMOS. The formation of a dense silica network occurs rapidly under basic conditions, with IR indicating the slower formation of more disordered silica in acid. SAXS analysis of the evolving particles shows that approximately 11 nm spheres are formed under basic conditions; these are stabilized by a water/surfactant layer on the particle surface during formation. Under acidic conditions, highly uniform approximately 5 nm spheres are formed, which appear to be retained within the water droplets (approximately 6 nm diameter) and form an ordered micelle nanoparticle structure that exhibits sufficient longer-range order to generate a peak in the scattering at q approximately equal to 0.05 A-1. Nitrogen adsorption analysis reveals that high surface area (510 m2/g) particles with an average pore size of 1 nm are formed at pH 1.05. In contrast, base synthesis results in low surface area particles with negligible internal porosity.     

TG characterization of organically modified montmorillonite

Montmorillonite was modified with octadecyltrimethylammonium chloride, under different reaction conditions, as evidenced by TG and XRD. TG curves presented two degradation peaks (295 and 395°C). At low salt concentrations, only the 395°C-degradation appeared, which increased with reaction time to the limit of 9 g of salt/100 g of clay. The second peak presented a limit at 17/100 m/m of salt/clay ratio. XRD analysis confirmed clay organic modification as the basal distance increased, showing greater reaction time effect than the salt mass effect, and with only one d-spacing. This suggested that an intercalation complex was formed but also that octadecyltrimethylammonium was adsorbed on the external surfaces of clay particles. This revised version was published online in August 2006 with corrections to the Cover Date.     

Hydrolytic behavior of enantiomeric poly(lactide) mixed monolayer films at the air/water interface: stereocomplexation effects

The Langmuir film balance technique was used to determine the hydrolytic kinetics of monolayers of the stereocomplex formed from mixtures of enantiomeric polylactides, poly(L-lactide) (L-PLA) and poly(D-lactide) (D-PLA), spread at the air-water interface. The present study investigated parameters such as degradation medium, mixture composition, and time on the relative degradation rate. The pi-A isotherms of monolayers of the mixtures provide clear evidence for the presence of a stereocomplex; the isotherms of monolayers of individual polyenantiomer show a transition at about 8.5 mN/m, whereas the transition of monolayers containing a stereocomplex formed from the equimolar mixture shifted to higher surface pressure, about 11 mN/ m. The rate of hydrolysis was recorded by a change in occupied area when the monolayer is maintained at a constant surface pressure. The hydrolysis of the mixture monolayers under basic conditions was slower than that of individual polyenantiomer monolayers, depending on the composition or the degree of complexation. In the presence of proteinase K, the enzymatic hydrolysis rate of mixture monolayers with >50 mol % l-PLA was much slower than that of the single-component L-PLA monolayer. The monolayers formed from mixtures with < or =50 mol % L-PLA did not show any change of occupied areas. This result is explained by the inactivity of D-PLA and stereocomplexed chains to the enzyme. From both results, it can be concluded that the retardation of the hydrolysis of mixture monolayers is mainly due to a strong interaction between D- and L-lactide unit sequences, which prevents the penetration of water or enzyme into the bulk.     

Formability and properties of self-standing clay film by montmorillonite with different interlayer cations

Influences of exchangeable interlayer cations were investigated on self-standing film formability, film morphology, and properties of the clay films such as flexibility and gas barrier property. Ion-exchanged montmorillonite samples were prepared by a cation exchange from naturally bearing cation, mostly Na⁺, to Li⁺, Mg²⁺, Ca²⁺, Al³⁺, and Fe^{2+, 3+}. Self-standing films were prepared from aqueous colloidal dispersions of these montmorillonite samples with no additives. The montmorillonite samples with monovalent or divalent cation formed flat self-standing films while the Al-montmorillonite sample produced a distorted film. The Fe-montmorillonite sample formed many separated reddish-brown rod-shaped pieces. Clay film microstructures were different with interlayer cations. The films with monovalent interlayer cations were constructed by the stacking of units with delicately waved thin clay sheets in the whole film, but other films show different morphologies between the upper side and lower side; the upper side is laminated with thin sheets; the lower side is laminated with large thick sheets.The self-standing films’ flexibility and gas barrier property differed according to the interlayer cations. These properties were good in cases of samples with monovalent cations. The innumerable short wave and sheet thinness are considered to foster good flexibility and gas barrier properties. The differences in film formability and properties of the films are attributable to different swellability among samples with different interlayer cations. The montmorillonite samples with monovalent cations swell sufficiently by water, but those with polyvalent cations swell poorly. In the latter case, clay crystals aggregate in water, then the aggregate grows into large particles, creating a film with large particles.