Effect of clay mineralogy on the feasibility of electrokinetic soil decontamination technology

To evaluate the effect of clay mineralogy on the feasibility of electrokinetic soil remediation technology, we contaminated six soils with Cu(II), Zn(II) and Pb(II) and performed electroremediation for 570 h. Cation exchange resin saturated with H⁺ was placed between soil and cathode to prevent soil alkalinization and trap the migrated heavy metal cations. After the treatment, the heavy metal cations were sequentially extracted with water, 1 M MgCl₂ and hot 6 M HCl. In soils dominated by crystalline clay minerals, Cu(II) and Zn(II) significantly migrated from anode end and accumulated at the cathode end forming sparingly soluble hydroxides. Removal rates of Cu(II) and Zn(II) were highest in a soil dominated with kaolinite and crystalline hematite. In humic–allophanic and allophanic soils, the high pH-buffering capacity of allophane kept the soil pH above 5, even at the anode end, and Cu(II) and Zn(II) did not migrate significantly. In all soils, the migration of Pb(II) was infinitesimal due to the formation of insoluble PbSO₄ and very strong surface complexation at the mineral surfaces. These results show that the reactivity of component clay minerals to H⁺ and heavy metal cations has a crucial effect on the efficiency of the electrokinetic remediation technology and it is not effective for remediation of allophanic soils. The results also indicate that allophanic soils may be useful as a barrier material in landfill sites.     

Smectite organofunctionalized with thiol groups for adsorption of heavy metal ions

The structural characteristics as well as the binding capacity of the functionalized bentonite from Campina Grande (PB), Brazil, were investigated. The sample was modified by acid treatment followed by immobilization of ligands containing thiol (–SH) groups by covalent grafting with surface and interlayer silanol groups. The modification was carried out under anhydrous conditions with (3-mercaptopropyl)trimethoxysilane. The functionalization process changed the hydrophilic nature of the clay mineral into hydrophobic. X-ray diffraction indicated that their original structure had been preserved. The DRIFT spectra demonstrated the presence of organic chains and thiol groups. The BET results indicated decreased porosity and specific surface area after grafting. Organic loading, calculated from TG data was 1.76 mmol g^− 1 of bentonite. The thiol-functionalized bentonite presented binding capacity of Ag⁺ ions about ten times higher compared to the ungrafted sample. These results support a mechanism of adsorption involving primarily ion complexation by the thiol groups (specific) instead of cation exchange (unspecific). The accessibility to the reactive centers was 60–75%. Thus, the adsorption capacity of bentonite can be enhanced by surface modification using organo-functional silane coupling agents. This new hybrid organic–inorganic material may be a good alternative for separation and pre-concentration of heavy metal ions.     

Formation and characteristics of cationic-polymer/bentonite complexes as adsorbents for dyes

The adsorption of cationic polymer, i.e., epicholorohydrin-dimethylamine polyamine (EPI-DMA), on bentonite particles was investigated under various conditions of bulk polymer concentration, pH, inorganic salts, and temperature. The resulting high adsorption rate and alkaline solution (pH = 7–11) effect indicated a strong electrostatic interaction between the clay particles and EPI-DMA molecules. Addition of salt can also influence the adsorption of EPI-DMA onto bentonite by affecting the clay particle sizes, the polymer zeta potential and etc. The Freundlich and Langmuir isotherm models were employed and fit the experimental data well in the low EPI-DMA concentration range 0.5–5.0 mg L^− 1. The enthalpy implied by the temperature dependence of adsorption of EPI-DMA on bentonite is 7.93 kJ mol^− 1, suggesting that neither coordination exchange nor chemical bond forces exit in this system. In addition, at high temperatures, larger amounts of EPI-DMA were adsorbed by bentonite, which indicated that increased entropy in the dissolved EPI-DMA molecules contributes to adsorption. The X-ray diffraction (XRD) analysis showed that besides the EPI-DMA molecules intercalated between the layers of bentonite, excess polymer molecules were adsorbed onto polymer loops protruding from the surface of the complex. The TGA and corresponding DSC plots demonstrated that the EPI-DMA polymer had intercalated into the clay layers and thus the EPI-DMA/bentonite was more hydrophobic than natural bentonite. With the addition of EPI-DMA polymer, the negatively charged clay particles increased to a net positive charge and the capacity for dye removal also went up with increasing polymer contents in EPI-DMA/bentonite complexes.     

Refractory Plastic Masses Based on Highly Concentrated Ceramic Binding Suspensions (HCBS). II. Structural and Mechanical Properties of Plasticized HCBS in the System SiO2 – Clay

Rheological properties of individual suspensions of quartz sand, quartz glass, and Nizhne-Uvel'skoe (NU) clay and compound suspensions of these components containing 20 – 80% NU clay are studied. The effect of NU content on rheological properties of the compound suspensions is considered. Structural and mechanical properties of plastic masses (with a moisture content of 10 – 20%) based on compound suspensions using a Tolstoi plastometer are studied. The data obtained are used to determine the main elastoplastoviscous and structural-mechanical properties of the plastic masses. The effect of the added HCBS on the rheological characteristics is considered.     

Influence of clay addition on the properties of olive oil in water emulsions

The behaviour of olive oil-in-water emulsions (O/W) was studied in the presence of smectite particles. The distribution of these particles in the emulsions and the effect of their interaction with the surfactant on the stability of the emulsions were investigated. Whereas the variation of surfactant and/or clay content did not seem to affect the nature of the emulsion, it had a significant influence on emulsion stability. This observation led to two main assumptions on the distribution of clay particles within the emulsion, either exclusively in the continuous phase, or also at the oil-water interface.In the absence of clay, the variation of surfactant concentration (from 0 to 17% (w/w)) allowed to distinguish 3 domains. In the first concentration domain (0–4.2%) emulsions stability increased with the content of surfactant. Within the second domain (4.2–8.5% (w/w)), a slight decrease in stability was observed due to flocculation by depletion. For surfactant concentrations equal or higher than 8.5% (3rd domain), emulsion stability increased sharply, probably due to the development of interactions between surfactant molecules as they came closer to their gelling concentration. The effect of clay addition to the aqueous phase (up to 10% (w/w)) on the physicochemical properties of the studied emulsions was assessed from stability, drop size, interfacial tension, rheological and acido-basic analyses. A model based on the location of clay particles either in the bulk or at the interface could be proposed, in which clay particles would interact with surfactant molecules in the bulk phase, and form a mechanical barrier around the oil droplets, thus increasing emulsion stability.     

Long-term consolidation mechanisms based on micro–macro behavior and in situ XRD measurement of basal spacing of clay minerals

An important issue in the area of geological disposal of high-level radioactive waste (HLW) is to demonstrate the long-term mechanical stability of the buffer. In particular, it has to be clarified whether a waste package would continue to sink in the buffer over a long time period, resulting in a significant decrease in the buffer thickness. The candidate buffer material in Japan is a mixture of silica sand and bentonite. Consolidation tests have revealed that the bentonite shows secondary consolidation phenomena similar to clay in general. Therefore, it is important to investigate the mechanism of secondary consolidation behavior.Bentonite is a microinhomogeneous material consisting of clay minerals, macrograins (mainly quartz) and others. The unique combination of molecular dynamics (MD) and homogenization analysis (HA) procedures, termed the unified MD/HA method, has been proposed for estimating the micro to macro behavior of such an inhomogeneous material (Ichikawa, Y., Kawamura, K., Nakano, M., Kitayama, K., Kawamura, H., 1998. Unified molecular dynamics/homogenization analysis for water flow in bentonite. Proc. 1998 Int. High-Level Radioactive Waste Management Conf., Las Vegas. American Nuclear Society, La Grange Park, IL, pp. 422–428). In this study, the unified MD/HA method is applied to bentonite in order to understand its long-term consolidation mechanism. Thus, it was found that the permeability decreases significantly with a decrease in the void ratio due to the evolution of consolidation. It was therefore assumed that secondary consolidation is governed by drainage from the interlayer pores (micropores) with very low permeability, and that this is the reason why secondary consolidation is very slow.This paper also documents the result of an X-ray diffraction (XRD) experiment on bentonite under consolidation (in situ XRD), which was performed in order to validate the assumption mentioned above. It was observed that interlayer space starts to decrease after the latter half of primary consolidation. This finding strongly supports the long-term consolidation mechanism presumed above from a microscopic point of view.One-dimensional consolidation analyses of the bentonite, into which the relationship between the void ratio and the permeability determined using the unified MD/HA method was introduced, were performed for comparison with a long-term consolidation test. The good agreement between the analytical result and the test result including secondary consolidation behavior also supports the long-term consolidation mechanism presumed above.     

Influence of nonionic polymers on the rheological and electrical properties of Egyptian bentonite

The rheological properties of Egyptian bentonite suspensions in the presence of nonionic polymers were investigated. Two different types of nonionic polymers were studied: poly(ethylene glycol) (molecular weight = 6000 g/mol) and poly(vinyl pyrrolidone) (molecular weight = 40,000 g/mol). The rheological properties (plastic viscosity, apparent viscosity, and yield point) of concentrated clay suspensions (6–8% w/w) at different temperatures after 24 h were determined. As the nonionic polymer concentrations increased, the rheological properties of the bentonite suspensions showed a slight increase, especially at an 8% clay content. The electrical properties (electrophoretic mobility and ζ potential) of Egyptian bentonite in the presence of different nonionic polymers were measured with a ζ meter. The results showed that the ζ potential of this bentonite was higher with 200 mg/L poly (vinyl pyrrolidone) than with 1000 mg/L poly(ethylene glycol). Potential energy profiles for bentonite suspensions for these nonionic polymers were constructed to show that the net energy barrier for bentonite suspensions followed repulsion or attraction between particles. These profiles showed that the potential energy profile of a bentonite suspension with 200 mg/L poly(vinyl pyrrolidone) produced a high repulsion potential energy between clay surfaces; that is, the suspension stability improved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal loading of smectite-rich rocks: Natural processes vs. laboratory experiments

Changes of physico-chemical properties of smectite-rich rocks (used as an engineered barrier in the nuclear waste repository) are studied. Two different genetic types of clays are evaluated—bentonite representing the residual weathering type and sedimentary montmorillonite-rich clay. Cation exchange capacity and specific surface area were determined for bulk samples (after heating experiments) and results were compared to a natural analogue (Ishirini deposit, Libya).Structural changes of clay minerals were studied using XRD, TG and DTA. Two main transformation processes (illitization and kaolinization) of smectite-rich rocks followed by deterioration of physico-chemical properties were observed after heat treatment. Cation exchange capacity drops significantly with increasing temperature and so does S_micro. However, S_BET values increased when heat treatment was applied.     

Hydrothermal alteration of “La Serrata” bentonite (Almeria, Spain) by alkaline solutions

Bentonite and concrete are considered as backfilling and sealing materials in a deep geologic repository of high-level radioactive waste (HLRW). The pH of the pore waters leached during concrete degradation is >11 for a long period of time. Under these alkaline conditions, bentonite is susceptible to dissolution–precipitation reactions. The aim of this work is to study mineralogical changes in bentonite in contact with synthetic pore waters of cements. The temperature effect has been taken into account in order to consider the thermal impact of radioactive decay.The bentonite used comes from “La Serrata de Níjar” (Almería, Spain) and is mainly composed of montmorillonite. Bentonite was submitted to alkaline solutions at 35, 60 and 90 °C up to 365 days. Alkaline solutions were similar to the pore waters leached in the first stage of cement degradation.The zeolite crystallization and the increase of magnesium in a non-exchangeable form in the smectitic clay fraction are the main mineralogical changes detected in the bentonite. Both processes are enhanced with the duration time and temperature of reaction.     

蒙脱石和高岭石吸附水溶液中重金属离子的实验研究

综述了近几年研究人员以蒙脱石、高岭石和膨润土作为吸附材料,去除水溶液中的砷、镉、铬、铜、铅几种重金属离子。通过酸性活化改性,有机分子嫁接改性,纳米氧化物涂层和柱撑等手段,提高了粘土矿物的吸附性能,达到更好的吸附效果。结果表明有机改性更有利于蒙脱石等粘土矿物对于重金属离子的吸附,同时指出pH是影响吸附效果的关键因素。     

Behavior of kaolinite and illite-based clays as landfill barriers

The technical requirements for the landfill of municipal wastes in the European Union (EU) are given in the Council Directive 1999/31/EC. A geological barrier of at least 1 m thickness with a hydraulic conductivity (HC) of 1 · 10^− 9 m/s is required. Where the geological barrier does not naturally meet the above conditions, a geological barrier of at least 0.5 m thick must be artificially established. We studied at controlled conditions, the ability of some clays (kaolinite or illite based) to act as landfill barriers. Several Spanish ceramic clays were compacted in columns (0.5 m length) and characterized for mineralogical, physical–chemical and heavy metal ions adsorption properties after 10 months leaching experiments. Zn, Cd, Pb and Cr salts were dosed in the synthetic leachates in order to test their in-depth retention. The specific surface area decreased in the material located near the clay–leachate interface region (< 6 cm) due to biofilm formation around clay particles, but bulk mineralogical properties were not affected. Although all the clays fulfilled the HC requirements, the diffusion of anions (chloride) reached more than 30 cm in kaolinite–illite or pure illite clays. The presence of significant traces of smectite (< 5%) was critical in anion transport retardation. Heavy metal ions were generally retained in the first 10 cm but in high surface-area illitic clays, the anions and heavy metal ions transport was stopped at < 6 cm. The clay mineralogy and the presence of carbonates and soluble salts greatly influenced the behavior of the barrier materials. Carbonate dissolution and precipitation affected < 6 cm depth. Divalent cations of carbonates selectively occupied the exchangeable positions and inhibited the retention of Na⁺, NH₄⁺ and K⁺, in the leachates. Sulphate was reduced at a depth of 20–30 cm. This biogeochemical process contributed to cadmium retention, presumably precipitated as sulphide.     

Interaction of urea with triple superphosphate in a simulated fertilizer band

Fertilizer nutrient diffusion from fertilizer bands and transformations in soil can affect fertilizer nutrient availability to crops and knowledge of the transformations is necessary for proper management. The interaction of urea and triple superphosphate (TSP) on urea hydrolysis and P transformations during diffusion processes from a fertilizer band was evaluated in a laboratory incubation experiment with two eastern Canadian soils (Ste Rosalie clay, Modifiers Typic Humaquept, pH 5.0; Ormstown silty clay loam, Modifiers Typic Humaquept, pH 6.0). Two fertilizer sources (urea and TSP) and three N and P rates (0, 100 and 200 kg ha^–1) were combined in a factorial arrangement. Fertilizer combinations were placed on segmented soil columns, incubated and segments were analyzed for N and P content. Acidification from dissolution of TSP retarded urea hydrolysis, and curtailed the rise in soil pH surrounding the fertilizer band. Urea hydrolysis caused dissolution of organic matter in soils, which might inhibit precipitation of insoluble phosphates. Banding urea with TSP increased 1M KCl extractable soil P, soil solution P, sorbed P concentration and total P diffused away from the band. Urea decreased 0.01M CaCl₂ extractable P, indicating probable precipitation of calcium phosphates with CaCl₂ extraction. Banding urea with TSP could benefit P diffusion to plant roots in low Ca soils and increase fertilizer P availability.     

Defluoridation of drinking water using chemically modified bentonite clay

Adsorption potential of metal oxide (lanthanum, magnesium and manganese) incorporated bentonite clay was investigated for defluoridation of drinking water using batch equilibrium experiments to gain insight of adsorption behavior, kinetics and mechanisms of adsorption of fluoride ion. The effect of various physico-chemical parameters such as pH, adsorbent dose, initial fluoride concentration and the presence of interfering co-ions on adsorption of fluoride has been investigated. The 10%La-bentonite shows higher fluoride uptake capacity for defluoridation of drinking water as compared to Mg-bentonite, Mn-bentonite and bare bentonite clay. The uptake of fluoride in acidic pH was higher as compared to alkaline pH. The equilibrium adsorption data fitted reasonably well in both Langmuir and Freundlich isotherm models. It was also observed that in the presence of certain co-existing ions can have positive effect on removal of fluoride, while carbonate and bicarbonate anions show deleterious effect. The rate of adsorption was reasonably rapid and maximum fluoride uptake was attained within 30 min. The modified adsorbent material shows better fluoride removal properties for actual field water, which could be due to the positive effect of other co-ions present in the field water.     

Electrokinetic remediation of lead‐, zinc‐ and cadmium‐contaminated soil

Electrokinetic remediation of lead‐, zinc‐ and cadmium‐contaminated sand and clayey soils has been investigated under laboratory‐scale conditions. Soil extracts of heavy metals (by 1 M HCl solution) were analysed by optical emission spectrometry. The efficiency of electrochemical remediation was partially dependent on the pH of the soil media. With pH increase, the migration of heavy metal ions toward the cathode was limited. When acetic acid was added to the sandy soil, almost complete remediation was achieved. A clay layer inserted in the cathode area did enhance the remediation rate. The most effective clean‐up was achieved for zinc and cadmium, with less effective clean‐up being achieved for lead. The effectiveness of the electrokinetic remediation of heavy metal‐contaminated clayey soil was low. The appropriate acidity was not achieved using acetic acid because of the high buffering capacity of clay, and metal ion migration was impeded by its sorption onto some clay components. The conclusion was made that clays could be used as immobilizing media for heavy metal ions by electrokinetic remediation of various soils. © 2001 Society of Chemical Industry     

Rationale of lead immobilization by ball milling in synthetic soils and remediation of heavy metals contaminated tailings

In this work, the use of mechanical milling for the remediation of heavy metals in synthetic soils and tailings sampled from the mining area of “Barraxiutta”, SW of Sardinia, Italy is investigated. Specifically, Pb(II) contaminated synthetic soils of sandy, bentonitic and kaolinitic type are taken into account following the results obtained in previous works. Suitable sequential extraction procedures have been performed on both untreated and treated synthetic soils. It is found that mechanical loads which occur during collisions among milling media and soils are able to modify the distribution of Pb(II) onto the different solid fractions of contaminated synthetic soils. Specifically, for sandy soils the milling treatment induces a significant increase in Pb(II) content in the Fe–Mn oxides fraction. On the other hand, for bentonitic and kaolinitic soils, Pb(II) content in both carbonate and Fe–Mn oxide fractions is augmented after treatment. Such phenomena may contribute to Pb(II) immobilization efficiency since the heavy metal trans-speciation occurs in favor of fractions characterized by stronger bonds and lower solubility.As for the heavy metals contaminated tailings, their immobilization is obtained using both ball and attrition milling devices under specific ball to powder ratio values. The degree of metals immobilization is evaluated by analyzing the corresponding leachable fraction obtained through the Synthetic Precipitation Leaching Procedure (SPLP) proposed by EPA. X-ray diffraction and granulometric analyses revealed no significant alterations of the intrinsic character of the tailings after milling except for a relatively small increase in particles size.The increase in immobilization efficiency when tailings are mechanically treated may be due to specific phenomena induced during milling such as entrapment of heavy metals into aggregates, solid diffusion of metals into the crystalline reticulum of soil particles, the formation of new fresh surfaces onto which heavy metals may be irreversibly adsorbed as well as metal trans-speciation onto tailings fractions characterized by stronger bonds and lower solubility.     

Influence of interlayer cations on the water sorption and swelling–shrinkage of MX80 bentonite

The potential of water sorption and swelling–shrinkage in the expansive clays is practically defined by the nature of interlayer cations. The purpose of this paper is to estimate the effects of the cation saturation (Mg⁺, Ca⁺, Li⁺, Na⁺, and K⁺) on the swelling–shrinkage behaviour of the MX80 bentonite.The MX80 bentonite (a “commercial clay”) was treated with concentrated solutions (1 N) of sodium, calcium, magnesium, potassium, and lithium chlorides. This treatment was made three times with constant agitation for 1 h. Then, the clay was washed three times with distilled water. The scanning transmission electron microscopy (STEM) and inductively coupled plasma atomic emission microscopy (ICP-AES) analyses were used to verify the efficiency of the cation saturation.Finally, two techniques were employed to estimate the effect of the cation saturation on the swelling–shrinkage behaviour of the bentonite: the first one uses an isothermal system of water adsorption, where the water activity is controlled by a supersaturated salt solution. In the second, environmental scanning electron microscopy (ESEM), coupled with a digital image analysis (DIA) program, was used to estimate the swelling–shrinkage potential at different water activities. The swelling–shrinkage isotherms were always estimated on isolated aggregates.The isotherms of water adsorption and swelling–shrinkage of the bentonite MX80 show that the amount of adsorbed water and the swelling–shrinkage potential depend directly on the interlayer cation. For example, the sodium bentonite presents an excellent capacity to swell while the lithium bentonite does not swell significantly at the aggregate scale. In addition, other textural properties may be modified by the cation saturation, such as the specific surface, the particle size, porosity, etc.     

Effect of hydroxy-aluminium species on the sorption and interlayering of albumin onto montmorillonite

Proteins interact with soluble OH–Al species or Al precipitation products forming organo-mineral complexes with different chemical and physico-chemical properties. We studied the effect of pH, cation saturating the clays, presence of OH–Al species and order of component (OH–Al species, albumin and montmorillonite) addition on the amounts of proteinic molecules adsorbed on montmorillonite and the possible interlayering of OH–Al–protein complexes. Albumin molecules were very well intercalated into the interlayers of Na-montmorillonites, but very poor or no intercalation was observed for Mg-saturated montmorillonite and for an Al(OH)_x-montmorillonite (chlorite-like) complex.We have found that the amount of albumin sorbed on the external and interlamellar spaces of montmorillonite in the presence of OH–Al species was influenced by the sequence of addition of albumin (Alb), OH–Al species (Al) and montmorillonite (Mt). Complexes were prepared by mixing: (i) Al+Mt before Alb; (ii) Al+Alb before Mt; and (iii) Alb+Mt before Al. When albumin was added to montmorillonite before OH–Al species (Alb+Mt before Al complexes) proteinic molecules were able to penetrate more easily into the interlayers of montmorillonite. On the contrary, when OH–Al species were initially added to the clay (Al+Mt before Alb complexes), they were previously interlayered and consequently prevented the intercalation of the proteinic molecules. Finally, when OH–Al species and proteins were added to the clay as a mixture (Al+Alb before Mt complexes), large OH–Al–protein polymers formed, which were only partially intercalated into the interlamellar spaces of the clay. In all the complexes, the amounts of proteinic molecules sorbed usually increased by increasing the pH.     

Electrochemical behaviour of cadmium in NaOH solution

The electrochemical behaviour of cadmium in 1 M NaOH solution was studied. Different electrochemical methods such as potentiodynamic measurements, polarization techniques and electrochemical impedance spectroscopy (EIS) were used. During the course of polarization, several characteristic features were observed, including prepassivation and a relatively wide passive range extending over 1.4 V. Equivalent circuit models for the electrode–electrolyte interface under different applied potentials were proposed. The impedance data measured at steady state were fitted to calculated data according to proposed equivalent circuits. The relevance of the proposed equivalent circuits to the different phenomena occurring at the electrode–solution interface was discussed. The passive film formed on Cd is composed of two layers: a barrier layer in contact with metal and a deposit on the barrier layer. The barrier layer appears to form directly from the metal through a solid state reaction, rather than by a dissolution–precipitation mechanism. For an applied potential >+0.7 V the relative passive film thickness and resistance decrease to lower values indicating transpassive dissolution at this potential.     

Efficiency of Egyptian drilling muds in the presence of cationic polyethylene imine and anionic polyacrylamide

The flow properties of Egyptian bentonite were studied using a combination of anionic polyacrylamide (MW = 1,000,000 g mol^?1) and cationic polyethylene imine (MW = 700,000 g mol^?1). This combination gave a significant effect on the clay suspensions to be qualified in the field of drilling mud depending on the sequence their addition. It was found that, by adding 50 mg/L cationic polyethylene imine followed by 10 mg/L anionic polyacrylamide, the rheological properties were improved using 6% Egyptian bentonite suspension, especially at 20°C. But, by reversing this addition sequence, the rheological properties of bentonite suspension were declined. The zeta‐potential value of bentonite suspension in the presence of 50 mg/L polyethylene imine was ?47 mV, while at 10 mg/L polyacrylamide was ?55 mV. But, on addition of 10 mg/L polyacrylamide to bentonite suspension followed by 50 mg/L polyethylene imine induced a reduction of the zeta‐potential value to ?51 mV when compared with that of polyacrylamide alone. By reversing the addition sequence, a very high stable suspension having zeta‐potential values of ?82 mV was obtained. Potential energy profiles were constructed to investigate the relation between rheological and electrical properties. Potential energy profile at 50 mg/L polyethylene imine followed by 10 mg/L polyacrylamide to bentonite suspension produced a high repulsion potential energy between clay surfaces, i.e. the suspension stability improved. By reversing that sequence, a significant decrease in the energy barrier was observed. The most reliable clay suspension as a drilling mud could be obtained by using 6% clay suspension concentration, with 50 mg/L polyethylene imine followed by 10 mg/L polyacrylamide, at 20°C up to 24 h aging time. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1487–1495, 2007     

Influence of layer charge and charge distribution of smectites on the flow behaviour and swelling of bentonites

The influence of layer charge and charge distribution of dioctahedral smectites on the rheological and swelling properties of bentonites is examined. Layer charge and charge distribution were determined by XRD using the LayerCharge program [Christidis, G.E., Eberl, D.D., 2003. Determination of layer charge characteristics of smectites. Clays Clay Miner. 51, 644–655.]. The rheological properties were determined, after sodium exchange using the optimum amount of Na₂CO₃, from free swelling tests. Rheological properties were determined using 6.42% suspensions according to industrial practice. In smectites with layer charges of − 0.425 to − 0.470 per half formula unit (phfu), layer charge is inversely correlated with free swelling, viscosity, gel strength, yield strength and thixotropic behaviour. In these smectites, the rheological properties are directly associated with the proportion of low charge layers. By contrast, in low charge and high charge smectites there is no systematic relation between layer charge or the proportion of low charge layers and rheological properties. However, low charge smectites yield more viscous suspensions and swell more than high charge smectites. The rheological properties of bentonites also are affected by the proportion of tetrahedral charge (i.e. beidellitic charge), by the existence of fine-grained minerals having clay size, such as opal-CT and to a lesser degree by the ionic strength and the pH of the suspension. A new method for classification of smectites according to the layer charge based on the XRD characteristics of smecites is proposed, that also is consistent with variations in rheological properties. In this classification scheme the term smectites with intermediate layer charge is proposed.