Stabilization of swelling clays by Mg(OH)2. Changes in clay properties after addition of Mg-hydroxide

Stabilization of the swelling clay structure is attempted by intercalation of Mg(OH)₂ and the development of a brucite interlayer between the clay layers. The properties of the product obtained by applying the technique, formulated as described in a previous work, are considered here. The materials used were Wyoming bentonite (USA), Fuller's Earth (UK), kaolinite, illite, lignite, and silica gels. The Mg(OH)₂-clay products were examined by the methylene blue dye test, X-ray diffraction analysis (XRD), differential thermal analysis (DTA), and derivative thermogravimetry analysis (DTGA). From the results obtained it is concluded that: the Mg-hydroxide is adsorbed by swelling clays both on their external and internal surface, whereas it is adsorbed on the external surface by non-swelling clays. The internally adsorbed phase of Mg-hydroxide forms an ill-defined interlayer of brucite, retarding swelling, whereas the external phase covers the particles modifying drastically their surface properties, like the adsorption of the MB dye. The material produced after precipitation of Mg-hydroxide on swelling clays (smectites) did not re-expand on wetting or after glycolation. The adsorption of MB dye was also reduced by some 80–90%, due to coating effect, preventing the measurements of the external surface area of the clay by polar molecules. The principal forces involved in the process are believed to be physical adsorption on the external surface, along with chemisorption and some chemical bonding, mostly in the internal surface. Cementation due to crystallization and, in the long term, some pozzolanic reactions take also place. Internal adsorption of the Mg-hydroxide is postulated to be in the form of positively charged mono- and/or small polymers and it is, chiefly, diffusion controlled. Since Mg-hydroxide is internally adsorbed by swelling clays, whereas Ca-hydroxide(lime) is not, and the (Mg, Ca)-clay aggregates are more stable than the Ca-clay or the Mg-one, the combination of the two hydroxides could give better results in soil stabilization than each hydroxide alone.     

Water retention characteristics of swelling clays in different compaction states

The soil–water retention (SWR) characteristics of the clays play an important role in controlling their engineering behaviour, particularly, in the unsaturated state. Although, researchers have attempted to understand the water retention characteristics of the clays in their reconstituted or remoulded state, such studies are rare for the clays in their intact state. In this context, it becomes important to understand the influence of initial state of compaction, which would create different pore and fabric structure (viz., microstructure), on the water retention characteristics of the clays. With this in view, SWR behaviour was experimentally determined for the swelling clays (dried from different compaction states, viz., intact, reconstituted and remoulded) by employing Dewpoint PotentiaMeter (WP4C®). The changes in the pore size distribution of the clays at different stages of drying cycle were also studied by employing the Mercury Intrusion Porosimetry. The study reveals that the SWR curves for the intact and reconstituted specimens of the clays converge beyond a certain stage of drying. Also, a critical analysis of changes in the pore structure of the swelling clay specimens, during drying, indicates that the progressively deforming pore structure plays an important role in controlling its water retention characteristics to a great extent.     

The structure and dynamics of 2-dimensional fluids in swelling clays

The interlayer pores of swelling 2:1 clays provide an ideal 2-dimensional environment in which to study confined fluids. In this paper we discuss our understanding of the structure and dynamics of interlayer fluid species in expanded clays, based primarily on the outcome of recent molecular modelling and neutron scattering studies. Counterion solvation is compared with that measured in bulk solutions, and at a local level the cation-oxygen coordination is found to be remarkably similar in these two environments. However, for the monovalent ions the contribution to the first coordination shell from the clay surfaces increases with counterion radius. This gives rise to inner-sphere (surface) complexes in the case of potassium and caesium. In this context, the location of the negative clay surface charge (i.e. arising from octahedral or tetrahedral substitution) is also found to be of major importance. Divalent cations, such as calcium, eagerly solvate to form outer-sphere complexes. These complexes are able to pin adjacent clay layers together, and thereby prevent colloidal swelling. Confined water molecules form hydrogen bonds to each other and to the clays' surfaces. In this way their local environment relaxes to close to the bulk water structure within two molecular layers of the clay surface. Finally, we discuss the way in which the simple organic molecules methane, methanol and ethylene glycol behave in the interlayer region of hydrated clays. Quasi-elastic neutron scattering of isotopically labelled interlayer CH₃OD and (CH₂OD)₂ in deuterated clay allows us to measure the diffusion of the CH₃- and CH₂-groups in both clay and liquid environments. We find that in both the one-layer methanol solvates and the two-layer glycol solvates the diffusion of the most mobile organic molecules is close to that in the bulk solution.     

Modified Darcy''s law, Terzaghi''s effective stress principle and Fick''s law for swelling clay soils

Governing equations often used in soil mechanics and hydrology include the classical Darcy's law, Terzaghi's effective stress principle, and the classical Fick's first law. It is known that the classical forms of these relations apply only to non-swelling, granular materials. In this paper, we summarize recent generalizations of these results for swelling porous media obtained using hybrid mixture theory (HMT) by the authors. HMT is a methodical procedure for obtaining macroscopic constitutive restrictions which are thermodynamically admissible by exploiting the entropy inequality for spatially-averaged properties. HMT applied to the modeling of swelling clay particles, viewed as clusters of adsorbed water and clay minerals, produces additional terms necessary to account for the physico-chemical forces between the adsorbed water and clay minerals or, more generally, for swelling colloids. New directions for modeling consolidation of swelling clays are proposed based on our view of clay particles as a two-phase system.     

Rare earth elements in Quaternary clays of the Numedal area, southern Norway

Rare earth elements (REE) in the clay fraction (< 2μ) of the Quaternary deposits in the Numedal area, southern Norway, have been determined by a spark source mass spectrometric method. The REE content was studied in relation to weathering and sedimentological factors.

The total REE content varies from 100 to 1300 ppm. An average of the similar fraction of 16 non-marine clays, mostly tillitic, gave 527 ppm REE. An average of 38 glacial and postglacial marine clays from the lower part of the Numedal valley gave 335 ppm REE (max. 781 ppm). After removal of adsorbed ions the average total REE content of morainian and marine clays decreased to 186 ppm.

The content and distribution of the REE in the Numedal clays are strongly influenced by environmental factors. Under neutral and alkaline conditions the REE are accumulated by adsorption on clay minerals, and by increasing the hydrogen ion concentration the adsorbed ions are readily removed.     

An XPEEM study of structural cation distribution in swelling clays. I. Synthetic trioctahedral smectites

X-PEEM images and XPS were collected on isolated layers of three synthetic swelling clays, one hectorite and two saponites with various charge, recording the Si(2p), Al(2p) and Mg(2p) core level spectra from the clay sheets. Spectra were fitted to determine the different components of the core levels. Due to their large full width at half maximum, Si XPS spectra were fitted using two to three doublets. It appears that, for a given clay mineral, Si, Al and Mg binding energies (BE) were constant, for all the observed layers. However, variations of the Si BE were observed depending on the nature of the mineral investigated. The various components obtained from the fit of Si spectra could be assigned to different substitution rates; binding energy shifting to lower values with substitution increase in the layer. Furthermore, variations in Si BE according to charge location were assigned to the influence of exchangeable cation.     

Thermomechanical model of hydration swelling in smectitic clays: I two-scale mixture-theory approach

A thermomechanical theory of hydration swelling in smectitic clays is proposed. The clay is treated as a three-scale swelling system wherein macroscopic governing equations are derived by upscaling the microstructure. At the microscale the model has two phases, the disjoint clay platelets and adsorbed water (water between the platelets). At the intermediate (meso) scale (the homogenized microscale) the model consists of clay particles (adsorbed water plus clay platelets) and bulk water. At the macroscale the medium is treated as an homogenized swelling mixture of clay particles and bulk-phase water with thermodynamic properties defined everywhere within the macroscopic body. In Part I, the mesoscopic model governing the swelling of the clay particles is derived using a mixture-theoretic approach and the Coleman and Noll method of exploitation of the entropy inequality. Application of this procedure leads to two-scale governing equations which generalize the classical thermoelastic consolidation model of non-swelling media, as they exhibit additional physico-chemical and viscous-type terms accounting for hydration stresses between the adsorbed fluid and the clay minerals. In Part II the two-scale model is applied to a bentonitic clay used for engineered barrier of nuclear waste repository. The clay buffer is assumed to have monomodal character with most of the water essentially adsorbed. Further, partial results toward a three-scale thermomechanical macroscopic model including the bulk phase next to the swelling particles are derived by homogenizing the two-scale model with the bulk water. A notable consequence of this three-scale approach is that it provides a rational basis for the appearance of a generalized inter-phase mass transfer between adsorbed and bulk water. Copyright © 1999 John Wiley & Sons, Ltd.     

Investigating the influence of total electrolyte concentration and sodium–calcium ion competition on controlled dispersion of swelling clays

The influence of clay dispersion method on dewatering behaviour of a run-of-mine bentonite was examined to better understand the roles of calcium–sodium ion exchange and overall electrolyte concentration on the suppression of swelling and subsequent stabilisation of the clay. As with previous work, controlled dispersion of the clay directly into a swelling suppressing environment was observed to yield order of magnitude improvements in dewatering behaviour [de Kretser, R.G., Scales, P.J. and Boger, D.V., 1997. Improving clay-based tailings disposal: a case study on coal tailings. AIChE Journal. 43 (7), 1894–1903.]. The calcium ion, even after normalisation for its valence, yielded significantly better clay stabilisation performance than the sodium ion indicating the greater benefit afforded via divalent ion-exchange driven controlled dispersion. However the results also highlighted a synergistic effect of the double layer suppression effect on the efficacy of ion-exchange mediated controlled dispersion through simultaneous swelling suppression and structure preservation during the transient process of ion exchange on hydration. Studies of controlled dispersion in dual ion, Na⁺ and Ca²⁺, systems illustrated that although the efficacy of controlled dispersion deteriorated with an increase in the Na⁺ to Ca²⁺ ratio, even small amounts of calcium character could generate significant improvements in dewaterability over the pure sodium case. This result was relevant in terms of defining an operational window for the commonly used, but sparingly soluble calcium source, gypsum where the low deliverable calcium level could be more than offset by the controlled dispersion benefits of maintaining a higher overall salinity level. Based on the results presented, the potential impact of practical implementation of a controlled dispersion framework within a mineral processing operation was illustrated via numerical modelling of the operation of a steady state thickener.     

Weathering of Valle Ricca stiff and jointed clay

The study proposes a weathering model of Pliocene–Pleistocene stiff and jointed blue-grey clay transforming into yellow clay. Physical, mineralogical, chemical and textural changes, as well as the weathering profile were investigated in a quarry of central Italy. Based on geological records and inferences, these changes are likely to have occurred within a time-span of about 50,000 years BP, upon overburden stress unloading and in a stress regime that is locally controlled by suction. Weathering propagated into the clay at a rate of about 0.3 mm/year and was enhanced by the enlargement of the pre-existing tectonic discontinuities and by the formation of new joints. A mass loss of about 22–25 wt.% was calculated. Considering Fe and P as immobile elements, the individual oxides contribute to mass loss in the following order: SiO₂ > CaO = CO₂ > Al₂O₃ > MgO > K₂O > S > Na₂O > TiO₂ > MnO. The Fe₂O₃ / (Fe₂O₃ + FeO) ratio varies from 9–29% in the blue-grey clay to 75–82% in the yellow one. Oxidation and/or dissolution of 7 Å-Fe²⁺-bearing clay minerals, mica-like minerals and calcite and parallel increase of smectite and Fe-hydroxides play a critical role in the chemical changes and explain the higher plasticity of the yellow clay with respect to the blue-grey one. The role of water during the weathering process was inferred to occur in cyclical steps: 1) seepage of meteoric water; 2) dissemination of highly oxidizing meteoric water; 3) triggering of oxidation and dissolution of minerals; 4) water evaporation; 5) partial migration of the elements contained in the aqueous solution and consequent deposition of minerals in the joints.     

Evidences of felsic volcanism and hydrothermal activities from clays associated with the Palaeoproterozoic Porcellanite Formation of the Vindhyan Supergroup,Central India

Chemico-mineralogical attributes of authigenic clays associated with the altered volcanic tuffs that occur in the Palaeoproterozoic Porcellanite Formation contain evidences of hydrothermal alteration and diagenetic processes in a marine environment. Previous sedimentological and geochemical studies on Porcellanite Formation were restricted to the Chopan area, but, the details related to provenance, nature and source of volcanism archived in these clays have not been ascertained. In order to understand these aspects, present study on these authigenic clays were carried out. Clay minerals represent dominance of illite with subordinate amount of montmorillonite. Moreover, low abundance of kaolinite is also noticed. The illite fibers and plates associated with the kaolinite indicate illitization. The kaolinite to illite transformation is favoured by incorporation of K⁺ ions, derived from the K-feldspar dissolution and its overgrowth. Major oxide contents of these clays and their ratios when plotted over diagrams marked with standard illite, kaolinite, smectite and chlorite compositional fields show clustering within or close to the illite field. Thermodynamic components calculated for these clays when plotted over AR₂³⁺AlSi₃O₁₀(OH)₂ − R₂³⁺Si₄O₁₀(OH)₂ − AR²⁺R³⁺Si₄O₁₀(OH)₂ ternary diagram, data plots lie within the illite, mixed layer I/S and smectite fields. Binary major oxide data plots between bulk rock and authigenic clay compositions showed felsic affinity. Montmorillonite and illite predominated in the eastern and western marginal areas of the Vindhyan Basin, respectively. However, former resulted from the hydrothermal alteration of volcanic glass associated with the ferruginous breccia and altered tuffs and remnants of the volcanic vents, whereas, later is associated with the tuffaceous beds. Owing to the adsorption, Ba, Rb and Sr is enriched in clays comparing to the bulk rock composition. Low (< 15 ppm) Sc values suggested major contribution from the felsic component. Also, low Rb/Sr and Th/U values revealed moderate insitu weathering. The dominance of K-feldspar alteration and insitu weathering is also evident from clustering of clay data plots in the A-CN-K ternary diagram. Pronounced negative Eu anomaly together with higher LREE/HREE values associated with these clay minerals implied proximity to source and their possible derivation from the silicified felsic tuffs available in the provenance.     

Shear resistance of fissured Neogene clays

Two types of fissured Neogene clays (SM and WB) were tested in the laboratory using undisturbed and reconstituted specimens. Although of similar age, the clays differ in their geological history: SM clays were deposited in a marine environment, WB are lacustrine clays with a complex tectonic history.

The index properties of both clays are similar and, accordingly, their strength parameters are mutually close. Test results of the more compact and less wet clay (WB) are affected by the sampling and trimming procedures, especially for 38 mm diameter specimens.

Although the behaviour is similar, the origin of fissures is different. For the SM clays, weathering is the main cause and fissuring reaches a depth of about 20 m. WB clays are dissected by macro- and microfissures originating as the result of tectonic processes and volumetric changes (effect of the coal formation underneath the investigated massif).

Cementation of some samples was found and the transition from clays through cemented clays to claystones (soft rocks) is speculated.     

A constitutive thermomechanical model for saturated clays

The structural deformation in clays results from microscopic phenomena involving the mechanical contact-stress change, the physico-chemical variation of repulsive forces in expansive clays, and thermal dilatancy of macropores. These textural strains are associated to three plastic mechanisms represented by respectively the yield surfacesf_Tm, f_R-A andf_T. Under a thermal cycle, the sizes of interlamellar spaces between clay platelets are not modified, hence the temperature cycle is expected to have no effect on repulsive forces and thus the second mechanism is not affected by temperature changes.

This paper suggests a formulation of a model of thermo-elasto-plastic behaviour of non-expansive saturated clays characterised by two plastic mechanisms. The mechanical yield surfacef_Tm of the contact-stress mechanism is based on a modified cam-clay model; the thermal softening yield surfacef_T is a plane separating two thermal domains. In normally consolidated conditions, the resulting response to an increase of temperature is compressive. However, in highly overconsolidated conditions, a small irreversible dilative volumetric strain is observed when the temperature is above a threshold value. In intermediate conditions, the material starts with an expansion and tends to a compression.

The constitutive model combines thermo-mechanical hardening, predominant in normally consolidated states (NCS) and absent in overconsolidated states (OCS) where the thermal softening occurs. The characterisation of the model requires information about rheological parameters obtained from oedometric and triaxial paths. Lastly, some numerical simulations of thermo-mechanical tests onremoulded Boom, ‘Bassin Parisien’ andPontida clays are presented, which show satisfactory agreement between experiments and model predictions.     

Particle orientation and its influence on the mechanical behaviour of isotropically consolidated reconstituted clay

The behaviour of naturally occurring geological materials such as clay and sand depends on many factors. For example, stresses, strains, previous stress history, mineralogy and the depositional environment all contribute in some degree to a characteristic that all natural soils share, namely “structure”. The structure of clay, or more generally, the microstructure of microscopically sized clay mineral particles, is just as important as the many other parameters that are used to quantify the performance of clays. This paper examines the microstructure that results from the particle arrangement brought about during reconstitution in the laboratory and considers its relevance to the resulting stress–strain behaviour.

Samples of reconstituted kaolin clay were produced using two different procedures. In the first series of tests, kaolin slurry was simply isotropically compressed in one increment. In the second series, the slurry was first isotropically compressed to a low pressure and then completely remoulded. This was followed by isotropic compression to the same pressure as the other series. Specimens were taken from the two series of samples, reconsolidated at various isotropic pressures, and sheared under undrained conditions.

Scanning Electron Microscope (SEM) images indicated that the monotonically compressed samples (Series 1) exhibited an anisotropic microstructure that was distinct from the remoulded (Series 2) samples. Significant differences were also found in the consolidation and stress–strain characteristics of the samples produced in the two series.     

Study on the swelling behaviour of blended clay–sand soils

Soils containing expansive clays undergo swelling that can be both detrimental and beneficial in various applications. In the Arabian Gulf coastal region, natural heterogeneous soils containing clay and sand (tills, shales, and clayey sands) support most of the civil infrastructure systems. Likewise, mixes of clay and sand are used for local earthwork construction such as roads and landfills. A clear understanding of the swelling behaviour of such soils is pivotal at the outset of all construction projects. The main objective of this paper was to understand the evolution of swelling with increasing clay content in local soils. A theoretical framework for clay–sand soils was developed using phase relationships. Laboratory investigations comprised of mineralogical composition and geotechnical index properties of the clay and sand and consistency limits, swelling potential, and morphology of clay–sand mixes. Results indicated that soil consistency of mixes of a local expansive clay and an engineered sand depends on the weighted average of the constituents. Mixes with 10% clay through 40% clay capture the transition from a sand-like behaviour to a clay-like behaviour. Influenced by the initial conditions and soil matrix, the swelling potential of the investigated mixes correlated well with soil plasticity (SP(%) = 0.16 (I _p)^1.188). The parameters sand void ratio and clay–water ratio were found to better explain the behaviour of blended clay–sand soils.     

Reversible flocculation and deflocculation of ball clays

One of the main usages of ball clays is in the pottery industry. However, in order to transport the clay suspensions from the mine site, some distance away from the consumer, dewatering of the clay suspension must be performed. The main restriction is that any dewatering treatment must not interfere in obtaining deflocculated, free flowing suspensions required by the pottery manufacturer.Investigations in the flocculation/deflocculation of these clay suspensions, resulted in finding a technique capable of achieving both requirements. The technique employs flocculation by an anionic flocculant in the presence of 10 mM of magnesium sulfate, thus achieving the dewatering step. When the magnesium sulfate was removed from the flocculated suspensions by simply washing the filter cake, good deflocculation of the clay suspension was achieved at alkaline pH. The role of MgSO₄ in the flocculant adsorption/flocculation, and subsequently in the flocculant desorption/deflocculation, was discussed.     

Engineering characteristics and environmental impacts of the expansive Ankara Clay,and swelling maps for SW and central parts of the Ankara (Turkey) metropolitan area

Volume-changing clay soils constitute the most costly natural hazard to buildings on shallow foundations. With the existing expansive clays in Ankara, low-rise buildings at the southwest part of the city have shown damage resulting in considerable maintenance costs. This paper reports the findings of an experimental investigation emphasizing the swelling behavior of Ankara Clay and correlations between the swelling parameters and other soil properties, and present a synthesis of observed damage details. The poor performance of the affected light-weight structures is assessed in the light of environmental conditions. In addition, swelling maps for SW and central parts of the Ankara metropolitan area, based on measured and predicted swelling parameters, are constructed for the purposes of land-use planning and general assessment of environmental problems. The experimental results suggest that the clay has high-to-very high activity, depth of active zone generally ranges between 1–2 m, the use of remolded and desiccated specimens seems to be a better approach in swelling tests, and the empirical equations based on two or more index or physical properties are good predictors for the estimation of the swelling potential of the clay. High swelling pressures exerted by the soil, flat topography and poor drainage, climatic conditions and poor construction methods are the main reasons of the structural damage observed at the study site.     

The potentials of Nigerian coal-reject as a construction material

Coal production and utilization is associated with the production of waste materials. One of such wastes is coal-reject which is composed of coal fragments, shale, sandstone, siltstone and a host of other rock types. This waste has been studied in Nigeria to determine its engineering properties and potentials for use in engineering construction.

Chemical analysis shows that the waste material contains, as its major oxides, silica, alumina, titanium oxide and ferric oxide whereas proximate analysis shows that quartz and clay are the major constituents. The average specific gravity is 1.85. Atterberg limit tests indicate that the clayey fines are of low liquid limit (average 37) and of low-medium plasticity (average PI= 11). Linear shrinkage is as low as 3.9% and suggests the absence of expansive clays in the fines. The maximum dry density (M.D.D.) ranges from 1.35 to 1.59 Mg/m³ while the unsoaked and soaked CBR values range from 11 to 45% and 12–29%, respectively. Shear strength tests gave an angle of shearing resistance of 13–14° with cohesion values of 55–58 kN/m² while the Los Angeles Abrasion and Aggregate Crushing tests, gave values of 55% and 48%, respectively.

Although the material degrades slightly under impact compaction and soaking, the test results suggest that it can be successfully used for a variety of engineering purposes. With careful placement, proper moisture conditioning and compaction, the material would be suitable for highway fills/embankments and sub-bases, unimproved. It cannot, however, be successfully used as base course and structural fills unless improved.     

Clay swelling mechanism in clay-bearing sandstones

Swelling clays in stone can generate damaging stresses during a wetting or a drying cycle, which lead to deterioration of building stones such as Portland Brownstone. There are two primary types of swelling identified for clays: short-range, ordered intracrystalline swelling, and long-range, continuous osmotic swelling. Identification of the swelling mode is important for understanding and ultimately preventing swelling damage. Through comparison of XRD and swelling experiments with cationic pretreatments and organic solvents, we demonstrate that intracrystalline swelling is the primary mode of swelling present in three different stones, including Portland Brownstone. The results highlight the importance of the counterbalancing cation to the swelling process, and a method for characterizing the intracrystalline swelling in sandstones is developed. Finally, the implications of long-term swelling behavior for stones are discussed.     

Effect of heavy metal and alkali contamination on the swelling properties of kaolinite

One of the most important factors that determine engineering properties of soils are the type and the amount of clay present in soil. Kaolinite being a very common and non-swelling clay mineral in soil was chosen as the medium, and significance of the change in swelling property of kaolinite due to contaminant-clay interaction was investigated. The amount of change in swelling percentages of the kaolinite due to contamination with 10,000 ppm solutions of Pb(NO₃)₂ and Zn(NO₃)₂ was determined using oedometers. For uncontaminated kaolinite, the amount of swell was determined as 2.2%. For Pb-contaminated and Zn-contaminated kaolinite, these values reached to 5.8 and 5.3%, respectively. Besides heavy metals, kaolinite was also contaminated with 4 N NaOH. The biggest change in the amount of swelling was obtained from NaOH-contaminated kaolinite which is 13.9%. In addition to swelling percentages, swelling pressures were also determined. The swelling pressure of the uncontaminated kaolinite was found as 1.06 N/cm². For Zn and Pb-contaminated kaolinite, this value reached up to 2.0 and 2.6 N/cm². The NaOH-contaminated kaolinite has the greatest swelling pressure which was 230 N/cm².