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 Boardman, D. I., Glendinning, S. & Rogers, C. D. F. (2001). Geotechnique 50, No.

6, 533±543

Development of stabilisation and solidi®cation in lime±clay mixes
D. I . B OA R D M A N, à S . G L E N D I N N I N G { A N D C . D. F. RO G E R S à Two re®ned clay minerals, English China Clay (predominantly kaolinite) and Wyoming Bentonite (predominantly sodium-montmorillonite), were used to assess the timedependent effects of mineral structural chemistry on the lime±clay reaction. The two clays, representing the extremes of structural negative charge development, were treated with two lime contents. Changes in the physico-chemistry of the samples were monitored after three curing periods by performing batch leaching tests and monitoring changes in undrained shear strength and Atterberg limits. The effects of changing the batch test operating parameters and increasing the curing period were assessed by measuring changes in solution pH and conductivity, and by analysis of eight elements in solution. The solidi®cation mechanisms due to lime addition were found to be different for the two minerals. Pozzolanic reactions involving English China Clay and Wyoming Bentonite were found to occur owing to the dissolution of aluminium and silicon from the respective mineral. Development of the batch leaching test showed that changing the operational parameters had no effect on the observed trends associated with the time-dependent modi®cation and solidi®cation reactions. It was also shown that successful solidi®cation could be monitored using simple conductivity measurements without the need for extensive and complex elemental analysis.    Nous avons utilise deux mineraux argileux raf®nes, de la china-clay d'Angleterre (principalement de la kaolinite) et de la bentonite du Wyoming (principalement de la montmor  illonite de sodium) pour determiner les effets lies au temps   de la chimie structurale minerale sur la reaction chaux à argile. Les deux argiles, representant les deux extremes d'un     developpement de charge negative structurale, ont ete trai  tees avec deux contenus de chaux. Nous avons observe les  Á changements physico-chimiques des echantillons apres trois   periodes de sechage en faisant des essais de lixiviation   discontinue et en etudiant les changements de resistance au  cisaillement non draine et les limites de Atterberg. Nous    avons evalue les effets resultant de la modi®cation des Á parametres d'exploitation des essais ainsi que les effets   d'une augmentation de la periode de sechage en mesurant les changements survenant dans la solution pH et dans la    conductivite et en analysant huit elements dans la solution.   Á Nous avons trouve que les mecanismes de solidi®cation dus a    l'adjonction de chaux etaient differents pour les deux miner  aux. On a constate que les reactions pouzzolaniques sur la china-clay d'Angleterre et la bentonite de Wyoming se Á produisaient a cause de la dissolution d'aluminium et de   silicium presents respectivement dans ces deux mineraux. Le   developpement des essais de lixiviation discontinue a montre Á que la modi®cation des parametres d'exploitation n'avait    aucun effet sur les tendances observees associees aux reac tions de modi®cation et de solidi®cation liees au temps. Nous   avons constate aussi qu'il etait possible d'observer une bonne solidi®cation en utilisant de simples mesures de con Á  ductivite sans avoir recours a des analyses d'elements pous sees et complexes.

KEYWORDS: chemical properties; contaminated land; environmental engineering; ground improvement; plasticity; soil stabilisation

INTRODUCTION

Lime either in the form of quicklime (CaO(s) ) or as hydrated lime (Ca(OH)2(s) ) has been added to clay soils to improve physical properties for centuries. This process, generally known as lime stabilisation, has been bene®cial in improving the strength and stiffness characteristics of road foundations (Biczysko, 1996; Chaddock, 1996; Holt & Freer-Hewish, 1998; Snedker, 1996). The treatment requires intimate surface mixing of lime with the soil and subsequent compaction to produce a ®nal product that is as physically and chemically homogeneous and as dense as possible. A minimum percentage lime addition is required to bring about the full cementing reactions. If the cemented strength is not required, a smaller percentage lime addition can be used to reduce the plasticity of the clay soil and thereby render unsuitable materials workable for bulk ®ll and other earthworks applications. The procedures for these highways applications are contained in Highways Agency (2000). More recently lime has become established as a deep solidi®cation technique via deep mixing to create lime columns (Broms & Boman, 1976), using a powder or slurry placed into pre-formed holes to create lime piles (Rogers & Glendinning, 1997) or via lime slurry pressure injection into intact soils. A general description of these deep solidi®cation techniques is
Manuscript received 23 December 1999; revised manuscript accepted 17 October 2000. Discussion on this paper closes 1 February 2002, for further details see inside back cover. Ã School of Civil Engineering, University of Birmingham, UK. { Department of Civil Engineering, University of Newcastle upon Tyne, UK.

given by Glendinning & Rogers (1996). Lime has also been used to treat chemically contaminated sites as the development of brown®eld sites has become more prevalent. There are two aspects of this treatment that are of interest: the in¯uence of the contaminants on the lime modi®cation and solidi®cation reactions, and the ability of lime stabilisation and solidi®cation to reduce the availability of the contaminants to the surrounding environment. This is discussed in more detail by Glendinning et al. (1998) and Boardman (1999). In all cases, it is both the short-term and the long-term reaction mechanisms that are important in determining the success of the techniques.
THE LIME±CLAY REACTION MECHANISMS

The addition of lime (CaO(s) or Ca(OH)2(s) ) to a soil system containing water results in several different chemical reactions that cause a profound alteration of the physico-chemical properties of clay soils. The reactions that occur bring about both immediate and long-term changes to the soil, and have been described variously in the literature. They will be discussed brie¯y herein. If lime is added to a soil±water system in the form of CaO(s), a highly exothermic hydration reaction occurs forming Ca(OH)2(s) and releasing approximately 17 3 109 J of heat energy per kilogram of CaO(s) added. The water utilised in this hydration reaction (as well as that removed from the soil system via evaporation caused by the increased temperature) can result in signi®cant improvements in soil workability purely as a result of dewatering. More importantly, the hydration reaction results in high

533

Several reported results are of interest in the context of reaction mechanisms. In physical terms. Conversely. mineralogy. The extent of cation exchange on permanent charge sites is primarily governed by the ionic potential (charge/radius) and ion concentration of the replacing ion relative to the ions on the exchange sites. For example. who studied the properties of lime-treated clay subgrades in the ®eld. Bell (1988) discusses the ability of the OH À ion to modify the clay surface. This is important not only for ensuring the reliability of lime-treated materials. the cation exchange capacity developed on kaolinite (% 2±15 cmolakg) is small compared with that of the permanently high cation exchange capacity of WB EXPERIMENTAL INVESTIGATION The research reported herein aimed to investigate the mechanisms of the lime±clay reaction and the longevity of lime±clay reaction products. there is a dearth of literature on the changes in soil properties wrought by very low percentage lime additions (i. 1990a) derives from a test developed by Eades & Grim (1966). This has been demonstrated by Anson & Hawkins (1998). and the potential for different reaction mechanisms to occur in different minerals. A further reason for understanding the reaction mechanisms is to determine whether a simple test may be developed to monitor in situ the progress of lime treatment. and conclude that plasticity changes should be used to con®rm the lime requirement for solidi®cation. It is based on the philosophy that the pH of the pore ¯uid will reach the value of a saturated solution of Ca(OH)2 only once ion exchange is complete. Rogers et al. hydroxyl groups on the mineral. permitting the formation of calcium silicate hydrate (CSH) and calcium aluminate hydrate (CAH) compounds. The mechanisms of modi®cation and solidi®cation require a greater level of understanding for several reasons. 1993). However. as reported by Sparks (1995). This lack of agreement may. if these changes can be attributed to cation exchange alone. Eades & Grim (1966) discuss the potential for a high pH to dissolve silicates and aluminates in the clay in order to allow the pozzolanic reaction. The mechanisms that bring about the observed changes are not fully understood. more friable material. A second reason for understanding the reaction mechanisms is to appreciate the potential longevity of lime-solidi®ed materials. (Soaking prior to testing could change the chemical nature of the material profoundly and yield equally erroneous observations. the result is an apparently drier. It may be economical on very dif®cult sites to add these small quantities to allow working in wet conditions. 1993). Currently. if solidi®cation has occurred it is less likely that the reactions could be reversed.534 BOARDMAN. However. the changes in the WB physico-chemical properties are likely to be more apparent. predominantly kaolinite) and Wyoming Bentonite (WB. English China Clay (ECC. but many issues remain unresolved. predominantly montmorillonite) have markedly different mineral structures with cation exchange sites in different positions within the clay lattice (Fig. GLENDINNING AND ROGERS (% 80±150 cmolakg). Consequently. and often a reduction in permeability (El-Rawi & Awad. and that strength determinations should be used for design. The addition of CaCl2 instead of Ca(OH)2 will give rise to markedly different immediate changes in clay properties. The result of cation exchange is increased ¯occulation of mineral particles and changes in the plasticity properties of the soil. are pH sensitive. The timescale over which the reactions take place and. For example. Limited research into the long-term properties of limesolidi®ed clays has been reported by McCallister & Petry (1992). those below the requirement for solidi®cation calculated using the method outlined in Rogers et al. In addition. 1997). hence affecting the measurements by making them appear more acidic. the anion is also more signi®cant. (1997) suggest an alternative interpretation of the test data. Where surface pH-dependent charge is developed on a clay mineral and conditions are acidic. whether the reactions occur sequentially. predominantly. as determined by XOH ‡ H ‡ D XOH2 ‡ XOH D H ‡ XO ‡ À (1) (2) where X is the mineral structure. and pore water chemistry. This is particularly relevant for ECC. which is often very strong and brittle. where there are no permanent charge sites. Many researchers disagree on these issues. Current methodology (BSI. but also for the potential for lime-treated materials to leach contaminated pore water into the surrounding environment. The basic reactions described above are widely reported. then it is possible that any subsequent change in pore water chemistry due to leaching could reverse the reactions and thus return the soil to its original properties. signi®cant increases in shear strength. and therefore it is the development of this permanent positive charge de®cit that dictates many aspects of physico-chemical behaviour. either positive or negative. thereby promoting the dissolution of silicon and aluminium from the clay (Sherwood.. and the in¯uence of pore suctions on the strength of the (generally) partially saturated material. These compounds crystallise with time. resulting in further changes in clay plasticity (Sherwood. be attributed to the complex nature and wide variety of combinations of the minerals that constitute a clay soil. the pH electrode becomes sensitive to the Na‡ ions along with the H ‡ ion. The majority of variable charge. The dissolved components from the dissolved clay minerals react with the Ca2‡ ions present in the pore water. including the dif®culty of taking intact samples of lime-solidi®ed material. The number of these charge sites is further enhanced in some clay minerals by the increase in pH caused by the presence of the OH À ions. 1). This phenomenon is reported by Eades & Grim (1966) for soils that are holding univalent ions such as Na‡ in the exchange position. is also less well established. Although still signi®cant. 1994). the exchange is affected by the disorder of the system. more particularly. Particular objectives of the study were: . Solidi®cation occurs as a result of pozzolanic reactions. Very small additions of lime may be suf®cient to change the apparent nature of the soil profoundly. As the ions are replaced by the Ca2‡ ions in such soils. immediate. This dissociation of ions results in a sequence of reactions that vary with soil composition. the mechanisms by which cation exchange occurs are different for the two minerals. The longer-term physico-chemical changes are brought about by a process termed solidi®cation. who have carried out programmes of leach testing in the laboratory. and by Biczysko (1996). These sites. Consequently. 1981). Diamond & Kinter (1965) talk of lime adsorption and reaction at the clay surfaces giving rise to immediate local pozzolanic reactions at the clay surface. Some soils are observed never to reach the pH of a saturated lime solution. The ®rst is associated with deciding how much lime to add to a clay soil in order to bring about the pozzolanic reactions. no adequate chemical explanation of the long-term changes in physical properties has been put forward. which are responsible for inter-particle hydrogen bonding. This is initiated at the edge sites of the clay plates. in terms of both the modi®cation and solidi®cation reactions. Alternatively. which are facilitated by the lime creating a highly alkaline soil pore chemistry. which is governed in part by the orientation of clay plates (McBride. Furthermore. This has several drawbacks. The majority of exchange sites on WB are the result of isomorphous substitution brought about by natural weathering processes.) concentrations of Ca2‡ (aq) and OH À (aq) ions in the pore water of the soil.e. The initial. modi®cation reaction occurs as a result of cation exchange of calcium (Ca2‡ ) ions for the existing cations at negative charge sites on the clay mineral lattice. on kaolinite is located on edge sites of the mineral and. and for expansive clays to react more quickly owing to greater cation exchange capacity. progress may be measured only by sampling and measuring strength changes. or occur concurrently. in part.

1976) (a) to monitor time-dependent chemical changes brought about by the addition of CaO(s) to kaolinite and montmorillonite (b) to compare the results of elemental analyses and measurements of pH and conductivity changes (c) to measure the concomitant changes in Atterberg limits and shear vane strengths (d ) to investigate the effect of lime addition above and below that required for solidi®cation. The ICL values for ECC and WB were found to be 1´5% lime and 7´0% lime (by dry mass of the clay) respectively (Fig. while sodium montmorillonite (in the form of WB) was chosen because it has a very high permanent charge de®cit as well as pH-variable surface charge. One series of experiments ex- .. and 2´5% and 7´0% lime (at and below the ICL value) was added to WB. Chemical and physical tests The aim of the chemical testing was to investigate the development of the lime±clay reaction with time. 1´5% and 2´5% lime (at and above the ICL value) was added to ECC. Samples were prepared by mixing the dry clay with water. This material was sealed in plastic bags for 24 h to prevent evaporation. It was therefore divided into two sections. iron. The minimum quantity of lime required for solidi®cation of ECC was found using the initial consumption of lime (ICL) test (BSI. Naturally this had an effect on the values of pH measured. 1. The samples were sealed in the moulds with paraf®n wax to prevent water loss and stored at 11´58C Æ 0´58C until required. the addition of 2´5% to both clays allowing additional comparisons to be made.STABILISATION AND SOLIDIFICATION IN LIME±CLAY MIXTURES 535 OH Oxygens OH Hydroxyl group OH OH OH OH OH Aluminiums Silicons Kaolinite chemical structure OH OH OH Exchangeable cations n H2O Hydroxyl Aluminium. 1997). Consequently larger quantities (300 ml. Kaolinite (in the form of ECC Grade 50) was investigated because it has predominantly pH-variable surface charge. Based upon these ICL values. 520 ml and 1000 ml) of deionised water were used. A further modi®cation was necessary for WB since the speci®ed addition of 100 ml of water to 20 g of soil resulted in a thick sludge. The lime was then added to ensure an even distribution. owing to the inherent swelling characteristics of the mineral. magnesium Oxygens OH group and Silicon. 1990a) with revised interpretation of the results (Rogers et al. but not signi®cantly on the quantity of lime required to bring about no further rise in pH. occasionally aluminium Montmorillonite chemical structure Fig. Samples were compacted into plastic moulds at water contents 2% wet of optimum. 2). Typical structure of English China Clay and Wyoming Bentonite (after Mitchell.

This acid digestion process was repeated twice. usually within 2 or 3 days. This process was continued until a consistently smooth mixture was created. This difference between the two minerals is also apparent in the higher ®nal conductivity of the WB relative to the ECC. After 7. and therefore changes in water content. Initial consumption of lime of ECC and WB amined the nature and quantity of ions not bound to the lime± clay matrix. silicon. and another examined those that were inherently part of the solidi®ed material. The containers were then placed in a reciprocating mixer and mixed at either 30 revamin or 60 revamin for 6 h or 24 h. ¯uorinated. If it is assumed that the solutions in the batch test are saturated with . crushed with a pestle and mortar. Atterberg limits were measured in accordance with BS 1377 (BSI. Owing to the sensitivity of some of the reaction products to pH. made up to a standard volume using BS 3696 Grade 1 deionised water and analysed for the eight chosen elements: calcium. primarily because of the differences in the development and magnitude of charge sites between the clays and the ions associated with these sites. In order to study the nature of the permanently reacted material. the parallel physical changes were measured by means of Atterberg limits and shear vane strength in order to determine the relative effect of permanent and non-permanent change on soil properties. The effects of altering the operating parameters on element concentrations. This consisted of cutting cubes of solidi®ed material of known dimensions and adding them to 2 l wide-necked. the same trends in behaviour were observed. aluminium. the solid-to-liquid ratio and the speed and duration of rotation. in solution. pH is a measure of H3 O‡ (aq) ion concentration and indirectly OH À (aq) ion concentration since the product of the concentrations (moladm3 ) of the H3 O‡ (aq) and OH À (aq) ions is always equal to 1 3 10À14 mol2 adm6 . Additionally. high-density polyethylene containers with Grade 1 deionised water to achieve mixtures of known solid-to-liquid ratio. RESULTS Batch tests The data presented will illustrate the changes in pH and conductivity at varying curing times for different lime contents and the results of elemental analysis immediately following the batch tests. Note that the results presented below represent a small selection from 1300 tests. Additionally. GLENDINNING AND ROGERS English China Clay CaO(s) content: % 2 3 4 5 12·8 ICL ECC = 1·5% 12·6 12·6 Wyoming Bentonite: pH English China Clay: pH 12·4 12·4 Wyoming Bentonite + lime + 300 ml deionised water Wyoming Bentonite + lime + 520 ml deionised water Wyoming Bentonite + lime + 1000 ml deionised water English China Clay + lime + 100 ml deionised water 12·2 12·2 12·0 ICL WB ≈ 7·0% 11·8 12·0 11·8 11·6 11·6 11·4 0 5 10 15 Wyoming Bentonite CaO(s) content: % 20 11·4 Fig. In contrast. A chemical batch test was performed on the lime±clay samples after the same curing periods. a comparison between the relatively simple tests to measure conductivity and pH was made with the elemental pro®le of the ions present in solution. iron. 1987) and precisely 2´7 ml of Aristar concentrated hydrochloric acid and 1´3 ml of Aristar concentrated nitric acid. either cations or anions. Hence conductivity re¯ects the quantity of dissolved solids. The process involved re¯uxing 1 g of dry material measured to within Æ0. Additionally.1 mg with 46 ml of BS 3978 Grade 1 deionised water (BSI. Periodically the pH and conductivity of the solutions were measured. and acid-digested twice. manganese and lead. changes in water content and temperature could affect the crystallisation of hydrated reaction products and their physical behaviour. and after cooling the samples were ®ltered through Whatman 542 hardened ashless ®lter papers. However. 175 and 301 days' curing the undrained shear strength was assessed using the shear vane apparatus. 1990b) with the exception of sample preparation. while the WB is naturally alkaline. ECC is slightly acidic. for all batch test parameter variations.536 12·8 0 1 BOARDMAN. Figures 3 and 4 illustrate the changes in pH and conductivity for ECC and WB samples respectively. For the purposes of this discussion the results from 24 h tests at 30 revamin with 20 mm initial cube sizes and a solid to liquid ratio of 1:40 will be presented. and hence the data are interpreted on the basis of consistent trends as well as on the measurements presented. and in the case of solid-toliquid ratio the ®nal equilibrium of ions in solution is completely changed. after 301 days' curing each lime±clay mix was dried at 105 Æ 0X58C for 24 h. and illustrated clearly the time-dependent chemical changes as a result of lime addition. pH and conductivity were investigated by altering the size of the cubes of material cut from the monolithic mass. Samples were crushed at their extracted water content using a pestle and mortar. Samples were ®ltered through Whatman 542 hardened ashless ®lter papers and the solution acidi®ed to below pH 4´0 and stored below 48C until analysis by inductively coupled argon plasma atomic emission spectroscopy. conductivity is a measure of the solution electrical conductivity that is directly related to the quantity of ions. magnesium. sodium. These changes alter the development of chemical equilibrium during the batch test. the samples were not dried in the oven. 2. This was required to see whether pH or conductivity could be used in situ to monitor the progress of the lime reactions. Once particles appeared to be approximately 1 mm in diameter further water was added to the mixture and further particle crushing was carried out. for speci®c ions present in the solution.

Conductivity 10 Clay + 2·5% lime. Figures 6 and 7 illustrate the changing elemental concentrations in solution with curing time and consequently the signi®cant differences in behaviour between ECC mixes and WB mixes. large increases in soluble silicon concentration and very small increases in soluble aluminium con- . for WB at 7 days a signi®cant proportion of the Ca2‡ ion concentration is evidently removed from solution and Na‡ ions are deposited into solution as a result of exchange processes. pH and conductivity Ca2‡ and OH À ions then a similar pH environment is likely in the pore water during curing. suggesting limited effects due to mineral dissolution. pH Clay + 7·0% lime. Conductivity 3000 Conductivity: µS/cm 2500 8 2000 6 1500 4 1000 2 Clay + 2·5% lime.STABILISATION AND SOLIDIFICATION IN LIME±CLAY MIXTURES 4000 14 537 3500 12 Clay only. Clearly ECC would not be expected to exhibit this behaviour because of its limited ion exchange potential. However. which shows the pH-dependent solubility of Al2 O3 and SiO2. Conductivity 10 Clay + 1·5% lime. pH and conductivity 4000 14 3500 12 Clay only. At 7 days very small concentrations of soluble silicon or aluminium are measured in solution. Time-dependent behaviour in both mineral mixes is also illustrated. 6 shows that the large reduction in conductivity of ECC±lime mixes is due to signi®cant reductions in the soluble calcium concentration. WB: end of batch test. as might be expected. as illustrated in Fig. This is signi®cant as the pH is maintained to a suf®cient level to allow mineral dissolution. pH pH Clay + 7·0% lime. increased curing periods signi®cantly reduce conductivity. ECC: end of batch test. 3. Conductivity Clay only. pH Clay + 2·5% lime. for WB±lime mixes (Fig. pH 500 0 0 50 100 150 200 Curing time: days 250 300 0 350 Fig. After 175 days' curing there is a large increase in soluble aluminium concentration and no signi®cant amount of soluble silicon for ECC mixes. pH pH Clay + 2·5% lime. Conversely. Conductivity Clay only. 7) the reduction in conductivity is evidently due to a reduction in soluble calcium and sodium. Conductivity 3000 Conductivity: µS/cm 2500 8 2000 6 1500 4 1000 2 Clay + 1·5% lime. Fig. 5. Equally. pH 500 0 0 50 100 150 200 Curing time: days 250 300 0 350 Fig. 4. However. the pH and conductivity observed after 7 days' curing are markedly increased. while pH remains relatively unchanged. After the addition of lime.

However. Therefore it may be argued that more Ca2‡ ions are removed from solution by curing at the higher lime content. whereas the lower lime addition (2´5%) resulted in little apparent change. approximately similar plastic limits being achieved after 7 days for the 1´5% and 2´5% lime additions. It should also be noted that pH affects the solubility of some of the compounds likely to be present. 11). Solubility of some soil mineral species in relation to pH (after Loughnan. Wyoming Bentonite. At 7 days there were negligible water-soluble aluminium and silicon concentrations with 1´5% lime. 5. Greater increases in undrained shear strength were observed for the 7´0% lime addition after 7 days. Similar large aluminium concentrations and small silicon concentrations were observed after 175 and 300 days for both lime contents. Both lime±clay mixes showed only a small increase in undrained shear strength after 7 days. The concentration of Ca2‡ ions and conductivity. In contrast. What was apparent. and (as acknowledged by the suppliers) will vary from approximately 350% to 600%. As the lime content of the ECC samples increased the soluble fractions of calcium. the 2´5% lime sample increased in strength by at least 80% between 7 and 175 days (again the absolute value for the sample with 2´5% lime was above the operating limits of the measuring apparatus). the liquid limit of the untreated WB is notoriously dif®cult to measure. The addition of 2´5% lime to WB had little effect on the plastic limit. 5. and consistent readings at the lowermost boundary of the untreated readings were obtained. The addition of lime signi®cantly increased the liquid limit. silicon and (to a much smaller degree) aluminium increased. was that upon addition of 2´5% lime these problems disappeared. The acid-soluble fractions due to clay alone have been subtracted so that the effects of the lime±clay reaction can be seen more clearly. 1969) centration were measured in WB mixes at the same curing period. Shear strength variations Figure 9 illustrates the development in undrained shear strength of ECC and WB mixes. although this was very small in the context of the overall reduction from the untreated state. However. However. plastic limit and plasticity index of ECC after varying curing times. as illustrated in Fig. Atterberg limits English China Clay. while very much greater for the higher lime content after 7 days. A 7´0% lime addition to WB resulted in a considerable decrease in liquid limit (Fig. however. the plasticity index reduced substantially. Figure 10 illustrates the effects of varying lime content on the liquid limit. The material. however. GLENDINNING AND ROGERS Extreme range of soil pH values Natural range of soil pH values Mg(OH)2 Al2O3 SiO2 Ca(OH)2 Fe(OH)3 Fe2O3 Al2O3 FeO only 4%. whereas the effect of increasing curing time was to reduce the plasticity index of the samples containing 2´5% lime. The effect of increasing curing time was to reduce the liquid limit. while soluble fractions of sodium decreased. aluminium and (to a somewhat smaller degree) silicon. some of the behavioural characteristics associated with the exchange reactions were lost owing to the high H ‡ (aq) ion concentration altering the number of pH-dependent charge sites on the mineral lattice and forcing substitution of ions on the exchange sites. whereas with 7´0% lime the plastic limit increased signi®cantly (Fig. Curing time had little effect on the liquid limits. although not fully modi®ed. These effects combined resulted in an increased plasticity index after 7 days due to the addition of lime. Thereafter the plastic limit of the samples containing 2´5% lime was signi®cantly greater as the values for 1´5% lime tended towards the value for clay only. This trend was also apparent after 175 and 301 days owing to the addition of 1´5% lime. while between 175 and 301 days there was an additional increase of English China Clay The batch tests demonstrated that it was the reduction in Ca2‡ ion concentration that was largely responsible for the reduction in conductivity measured in mixes with increasing curing period. it is important to note that after increased curing periods the sample with no lime also showed a reduction in liquid limit. and it was generally apparent that there was no signi®cant further increase in the liquid limit achieved by increasing the lime content beyond the ICL value (to 2´5% lime addition). Figure 8 illustrates the variations in the acid (a mixture of concentrated nitric and hydrochloric acids) soluble fractions of the four mineral mixtures due to increasing lime content. The sample containing 1´5% lime (the ICL value) showed a signi®cant increase of 28% between 7 and 175 days. The addition of lime also increased the plastic limit of ECC (Fig. the plastic limit reducing markedly with increased curing time. DISCUSSION 9 8 Solubility: mmol/l 7 6 5 4 3 2 1 0 0 1 2 3 4 5 CaCO3 6 7 Fe(OH)2 8 9 10 10 11 12 13 14 Range of pH values in natural waters and rain Fig. The undrained shear strength of WB with 2´5% lime increased by 20% immediately after 7 days. For fully modi®ed WB (7´0% lime addition). The combined effect of these changes for WB ‡ 2X5% lime is a reduction in plasticity index to the lower boundary of values for the untreated WB. increases in strength were perceived during the process of performing the test. converged to similar values for the two different lime contents with increasing curing period. 6). and although it was not possible to measure an increase in strength after longer curing periods since the readings exceeded the maximum value that could be measured by the shear vane. Acid-soluble element fractions The acid-soluble element fractions also revealed substantial information about the behaviour of the clay minerals. but thereafter there was no appreciable change in the undrained shear strength. whereas there was a signi®cant concentration of aluminium with 2´5% lime (Fig. the reduction being approximately half that of the lime-treated samples. 11). The WB samples exhibited increased soluble fractions of calcium. 10). The shear strength development of the ECC mixes was substantially different from that of WB. The two lime contents produced mixes with similar undrained shear strengths .538 BOARDMAN. had an evidently changed character at this lime addition. There was a marginal increase in plasticity index with curing period for the fully modi®ed WB as a result of the fall in plastic limit. thus indicating a potential method of in situ monitoring.

Al concentration (ppm) Clay + 2·5% lime. Al concentration (ppm) Clay + 7·0% lime. 20 mm cubes). Si concentration (ppm) Clay + 7·0% lime. End of batch test: element analysis of ECC samples with (a) 1´5% and (b) 2´5% lime (24 h. 1:40 S/L. Si concentration (ppm) Clay + 2·5% lime. Ca concentration (ppm) 8 6 100 4 50 2 0 (a) 14 Si and Al concentration in batch test solution: mg/kg 0 250 200 10 150 Ca concentration in batch test solution: mg/kg 12 Clay + 2·5% lime. 30 revamin. 1:40 S/L. Ca concentration (ppm) 8 6 100 4 50 2 0 0 50 100 150 200 Curing time: days (b) 250 300 0 350 Fig. Na concentration (ppm) 50 0 0 50 100 150 200 Curing time: days 250 300 0 350 Fig. 20 mm cubes) 30 Ca. Elemental analysis of WB samples with 2´5% lime was not available because the material from these batch tests could not be ®ltered . Al concentration (ppm) Clay + 1·5% lime. 7. Ca concentration (ppm) Clay + 7·0% lime. 6. Si concentration (ppm) Clay + 1·5% lime.STABILISATION AND SOLIDIFICATION IN LIME±CLAY MIXTURES 14 Si and Al concentration in batch test solution: mg/kg 250 539 200 10 150 Ca concentration in batch test solution: mg/kg 12 Clay + 1·5% lime. Si and Al concentration in batch test solution: mg/kg 350 25 300 250 20 200 15 150 10 100 5 Na concentration in batch test solution: mg/kg Clay + 7·0% lime. End of batch test: element analysis of WB samples with 7´0% lime (24 h. 30 revamin.

Mg concentration in solid: mg/kg 16 000 14 000 12 000 400 10 000 8000 200 6000 4000 0 –200 (a) 10 000 60 000 1 2 3 2000 0 Ca. whereas in the long term an additional bene®t of the pozzolanic reaction is observed. Similarly. Mg concentration in solid: mg/kg 8000 50 000 Ca concentration in solid: mg/kg Na concentration Al concentration Fe concentration Si concentration Mg concentration Ca concentration 6000 40 000 4000 30 000 2000 20 000 0 0 –2000 (b) 1 2 3 4 5 CaO(s) content: % 6 7 8 10 000 0 Fig. The presence of pozzolanic material is evidenced by the presence of acid-soluble aluminium and silicon after 301 days (Fig. By observation of the lattice structure of kaolinite it would suggest that dissolution occurs at the edges of the mineral where aluminium is more prevalent (i. Fig. but for increased curing periods they showed signi®cant differences in plastic limit and therefore plasticity index. The addition of lime above the ICL value has substantial bene®t for long-term strength gain. GLENDINNING AND ROGERS 20 000 18 000 800 Fe. Si. soluble calcium is `consumed' by the reaction with aluminium to produce cementitious material and concomitantly reduce conductivity. near the pH-dependent negative charge sites. while at 175 and 301 days the higher lime content produced mixtures of signi®cantly higher strength. The sample with a higher lime content has a higher proportion of acid-soluble calcium but a similar water-soluble content. Changes in strength and plasticity may be attributed to ion exchange in the short term. this alludes to greater pozzolanic activity with higher percentage lime additions. Corrected acid-soluble fractions of (a) ECC and (b) WB samples with increasing lime content after 301 days' curing after 7 days. The presence of increased silicon in the sample with 2´5% lime suggests that there is more mineral breakdown induced by the higher lime content. It is apparent therefore that a greater quantity of CAH is being formed than CSH. Al concentration in solid: mg/kg 600 Fe concentration Si concentration Mg concentration Ca concentration Al concentration 0 Na. 8). The ICL test gives a good indication of the amount of lime required to satisfy ion exchange. At 7 days the reaction for 1´5% lime may be attributed to ion exchange effects alone. . Si. Fe.540 1000 BOARDMAN. but was shown to be slowing down between 175 and 301 days. because no soluble silicon or aluminium was observed in batch test solutions. 8. As the mineral lattice is dissolved. An important observation relating to the development of the solidi®cation reactions is the relatively small amount of watersoluble and acid-soluble silicon compared with aluminium. The reduction in soluble calcium content and increase in soluble aluminium content at increased curing times point towards considerable pozzolanic activity. The observations made allude to potential reaction mechanisms and differences between the two lime additions. 1). producing soluble aluminium. addition of lime above this amount having little short-term bene®t since early dissolution of the clay minerals yields no physical gain. This pozzolanic activity took place largely after 7 days. Al. both mixes exhibited very similar plasticity changes at 7 days. whereas with 2´5% lime some clay mineral dissolution at the exposed edges (and hence aluminium concentration) had begun.e. Again.

Shear strength values illustrated as 145 kNam2 are at the measurement limit for the shear vane apparatus. is observed. Again. and the physical effects of ¯occulation are not fully achieved. unlike the ECC case. and thus the presence of less sodium in solution may also be an indication of incomplete cation exchange. However. Similarly the pattern of high initial conductivity and Ca2‡ ion concentration. The strength increases and plasticity changes were considerably greater in WB than in ECC. The strength increase and plasticity changes wrought by 2´5% lime are similarly far less pronounced at 7 days. The strength increases for WB with increased curing period were very much greater with the higher lime content. there is a marked increase in conductivity (to a value similar to that of ECC at the ICL lime content) when 7´0% lime is added. the reduction in soluble sodium possibly being due to its incorporation into the pozzolanic reaction products or to the formation of a separate product that is less soluble at high pH. Ca2‡ ions exchange for Na‡ ions. there is very little soluble silicon or aluminium present at 7 days.STABILISATION AND SOLIDIFICATION IN LIME±CLAY MIXTURES 160 140 541 Undrained shear strength: kN/m2 120 100 Clay only 80 Clay + 1·5% CaO(s) Clay + 2·5% CaO(s) 60 40 20 0 (a) 160 140 Undrained shear strength: kN/m2 120 100 Clay only 80 Clay + 2·5% CaO(s) Clay + 7·0% CaO(s) 60 40 20 0 0 50 100 150 200 Curing time: days (b) 250 300 350 Fig. which reduce with curing time owing to solidi®cation. Unlike ECC the reduced conductivity is caused by both a reduction in soluble calcium and sodium. The explanation for this has been attributed to the difference in cation exchange capacity discussed earlier. which undoubtedly . Variation of undrained shear strength of (a) ECC and (b) WB samples with increasing lime content and curing time. This is mirrored by the plasticity changes that were much greater with the higher lime content. However. and the actual strength may be signi®cantly higher Wyoming Bentonite Despite the initial difference in pH between the two minerals. Reduction in conductivity at increased curing periods once more suggests increased pozzolanic reaction products that improve strength and plasticity characteristics. As ion exchange occurs at the permanent charge sites. After 7 days the conductivity of the ECC mixture with 2´5% lime is higher than that of the same mixture with WB. the initial large difference between the conductivity and Ca2‡ ion concentration between the two lime contents reduces with time as the Ca2‡ ions with 7´0% lime addition are used up by the pozzolanic reactions. This indicates that 2´5% lime is not suf®cient to complete ion exchange. indicating that the strength increases and plasticity changes observed are due primarily to cation exchange rather than pozzolanic activity. there remains a signi®cant difference in conductivity since the lower lime addition is much less than the ICL value. the pH achieved after lime addition is very similar throughout to that achieved by ECC. Similarly to ECC. 9.

when these changes can largely be attributed to ¯occulation. The amount of soluble silicon was approximately twice as great as the dominant aluminium concentration in the ECC samples. Again. GLENDINNING AND ROGERS 80 70 70 Liquid limit (LL) and plasticity index (Pl): % 60 60 Clay only (LL) Clay + 1·5% CaO(s) (LL) Plastic limit (PL): % 50 50 Clay + 2·5% CaO(s) (LL) Clay only (PI) Clay + 1·5% CaO(s) (PI) Clay + 2·5% CaO(s) (PI) Clay only (PL) Clay + 1·5% CaO(s) (PL) 40 40 30 30 20 20 Clay + 2·5% CaO(s) (PL) 10 10 0 0 50 100 150 200 Curing time: days 250 300 0 350 Fig. In contrast to ECC. plastic limit and plasticity index of WB with increasing lime content and curing time accounts for the differences at 7 days. Variation of the liquid limit. and that more pozzolanic product is formed than for ECC. plastic limit and plasticity index of ECC with increasing lime content and curing time 600 180 160 500 Liquid limit (LL) and plasticity index (Pl): % 140 Clay only (LL) 400 120 Plastic limit (PL): % Clay + 2·5% CaO(s) (LL) Clay + 7·0% CaO(s) (LL) Clay only (PI) Clay + 2·5% CaO(s) (PI) Clay + 7·0% CaO(s) (PI) Clay only (PL) Clay + 2·5% CaO(s) (PL) Clay + 7·0% CaO(s) (PL) 40 100 20 Boundary of LL determinations for clay only 100 300 80 200 60 0 0 50 100 150 200 250 Curing time: days 300 0 350 Boundary of PI determinations for clay only Fig. an examination of the mineral structure (Fig. 10. silicon is the dominant element in this case. 11. This indicates that WB preferentially forms CSH rather than CAH. the amount of water-soluble aluminium present during batch tests was relatively low throughout. . the increase in soluble silicon being the indicator of mineral dissolution in this case.542 80 BOARDMAN. Variation of the liquid limit. 1) shows that if dissolution occurs at the edges of the crystal lattice. further differences were noted in the pozzolanic activity in the two clays. However.

Methods of test for soils for civil engineering purposes. It seems probable that a small amount of pozzolanic reaction occurs despite the low lime content. Found. E. Soil Mech. Leach tests on lime-treated clays. 47. Geotech. Glendinning and N. Whether to add additional lime above that determined by the ICL test is dependent upon what is required of the product. (1969). In Lime stabilisation (eds C. M. Glendinning. Little strength gain is achieved after 7 days with 2´5% lime addition and. Mitchell.. London: HMSO. The development of pozzolanic reactions in WB can be monitored similarly by measuring increases in the concentration of leachable silicon. (1998). Glendinning. 228±239. pp. no signi®cant increase occurs thereafter. 127±138. 106±114. F. 14. B. probably because of its greater surface area. 1. No signi®cant pozzolanic activity (and certainly no crystallisation of reaction products) appears to take place until after 7 days' curing. importantly. D. B. PhD thesis. 6. A. Fundamentals of soil behaviour. S. F. In Lime stabilisation (eds C. 75±94. Mineral dissolution takes place initially at the edges of the crystalline structure. & Roff. The pH remained suf®ciently high to dissolve the mineral structure. & Kinter. S. (1992). W. C. Rogers. Highways Agency (2000). New York: Oxford University Press. Geotechnique 48. Eades. London: Geological Society. Holt. Dixon). (1996). Proc. In Contaminated land and groundwater: future directions. L. Highway Research Record. 4. S. Vienna. However. Broms. A. F. The precise solid-to-liquid ratio is not necessarily vital so long as it remains consistent with time. M. This implies that kaolinite is far more sensitive to the effects of the nature of the anion(s) in solution than montmorillonite at low pH. if long-term strength is required a greater quantity of lime gives a better product. S. Dixon). If an immediate reduction in plastic limit is required there is little point in adding greater quantities of lime. S. J. Glendinning. 2. Cation exchange takes place on pHdependent charge sites in kaolinite and additionally at permanent charge sites in montmorillonite. Ground Engng 21. In Lime stabilisation (eds C. The development of pozzolanic reactions with time for ECC can be measured by monitoring increases in concentration of leachable aluminium and reductions in concentration in leachable calcium (and hence conductivity). Lime stabilisation of inorganic contaminants in clays. (1996). D. S. A. C. Permeability of lime stabilized soils. F. Therefore. Stabilization and treatment of clay soils with lime. W. & Boman. A quick test to determine lime requirements of lime stabilisation. BS 1377. Environmental chemistry of soils. J. (1996). Rogers. F. London: Thomas Telford. 207±210. London: HMSO. S. In: Lime stabilisation (eds C. Bell. & Hawkins. (1965). D. F. 62±74. Engrs Transport 129. C. 139. D. Diamond. London: BSI. New York: Elsevier. M. McCallister. Transportation Engng J. The use of lime-treated British clays in pavement construction. Vol. (1998). (1999). (1976). 15. January. Dixon). British Standards Institution (1990b). McBride. 10±15.STABILISATION AND SOLIDIFICATION IN LIME±CLAY MIXTURES It is dif®cult to conclude that no pozzolanic reactions had occurred at the lower lime content. London: Thomas Telford. No. J. S. leading to a difference in the reaction products between kaolinite and montmorillonite owing to the relative positions of silicon and aluminium in the crystal lattices. London: Thomas Telford. Civ. BS 3696. Loughnan. 19±28. despite the recorded reductions in conductivity after this time. (1995). but that this has little (if any) practical bene®t. & Grim. 243±257. Proc. B. Rogers. I. Engng. 61±72. P. J. . Inst. thereby monitoring the development of solidi®cation in a non-destructive way. K. but cheap and simple. (1997). Mechanisms of soil-lime stabilization. Stabilized materials for civil engineering purposes. Water for laboratory use. & Petry. 142±158. & Rogers. Biczysko. Test. the strength data are likely to provide the most conclusive evidence of no practical bene®t from solidi®cation. pp. Civ. Conf. Modi®cation of clay soils for construction expediency. E.. S. Proc. Snedker. F. Engrs Geotech. an ideal. Indeed. & Freer-Hewish. Montmorillonite produces more reaction product. P. The effect of calcium ions in pore water on the residual shear strength of kaolinite and sodium  montmorillonite. T. D. the bene®t of a lower addition of lime is more questionable and less signi®cant in terms of the cost of the reagent. Highway Research Record. Improvement of clay soils using lime piles. Rogers. There is also potential for a difference between the fabrics of the two lime±clay products owing to the relative position at which dissolution takes place and therefore the position of subsequently crystallised reaction products. (1996). B. Methods of test for cement-stabilized and lime-stabilized materials. London: BSI. C. British Standards Institution (1990a). & Glendinning. Chemical weathering of silicate minerals. T. It has been shown that lime addition above the ICL value has little bene®t in the short term but substantial value in the longer term in terms of strength. G. Long-term performance of lime stabilised road subgrade. the dif®culty with mixing such very small quantities of lime in practice would probably counteract any cost saving for reduced lime consumption. No. London: Academic Press. EL-Rawi. BS 1924: Part 2. D. November. Glendinning and N. I. C. 25±35. J. L. (1993). Treatment of ®ll and capping materials using either lime or cement or both. Inst. (1998). D. CONCLUSIONS 543 ments. Elemental concentrations could not be made owing to the dif®culty of ®ltering the samples at the lower lime content. A. No. M40-Lime stabilisation experiences. Stabilisation of deep cuts with lime columns. (1966). F. & Awad. In addition. D. N. (1988). J. The slight changes in plasticity also indicate some chemical alteration of the mineral. UK. 1±8. D. 6th Eur. Rogers. London: BSI. Glendinning and N. Dixon). E. Loughborough University. The mechanism of strength gain is attributable to ¯occulation in the short term and additionally to pozzolanic reaction in the longer term. C. conductivity of the pore water could be measured in situ. Sparks. The structural performance of stabilised soil in road foundations. D. Rogers. Part 1: The effect of mellowing on the modi®cation process. & Boardman. London: Thomas Telford. in situ test to monitor the progress of lime treatment reactions in the long term is by conductivity measure- REFERENCES Anson. R. S. Section 1. Boardman. L. Soil stabilisation with cement and lime. In Design manual for roads and bridges. pp. C. New York: John Wiley & Sons. Chaddock. No. C. Environmental soil chemistry. 787±800. B. Glendinning and N. (1997). Vol. pp. Engng 125. Sherwood. E.. For clays with high cation exchange capacity. Lime stabilisation: clay±metal±lime interactions. and reductions in the concentration of leachable calcium and sodium (and hence again conductivity). T. pp. D. Deep stabilisation using lime. R. British Standards Institution (1987). No. and the acid-soluble calcium and aluminium increases indicate the development of pozzolanic material. 92. For clays with low cation exchange capacity. considerable bene®t can be gained by lime addition below the ICL value. Engineering Geology Special Publications. The ICL addition of lime provides an indication of the amount of lime required to satisfy ion exchange. J. (1981). Engng Geol. F. (1994). Rogers. R. B. (1976). 83±102. D. F.