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

6, 533543

Development of stabilisation and solidication in limeclay mixes

D. I . B OA R D M A N, S . G L E N D I N N I N G { A N D C . D. F. RO G E R S Two rened 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 limeclay 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 solidication 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 modication and solidication reactions. It was also shown that successful solidication could be monitored using simple conductivity measurements without the need for extensive and complex elemental analysis. Nous avons utilise deux mineraux argileux rafnes, 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 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 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 modication des 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. Nous avons trouve que les mecanismes de solidication 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 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 que la modication des parametres d'exploitation n'avait aucun effet sur les tendances observees associees aux reac tions de modication et de solidication liees au temps. Nous avons constate aussi qu'il etait possible d'observer une bonne solidication en utilisant de simples mesures de con 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 benecial 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 solidication 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 solidication 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. 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 browneld sites has become more prevalent. There are two aspects of this treatment that are of interest: the inuence of the contaminants on the lime modication and solidication reactions, and the ability of lime stabilisation and solidication 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 LIMECLAY 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 briey herein. If lime is added to a soilwater 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 signicant improvements in soil workability purely as a result of dewatering. More importantly, the hydration reaction results in high

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BOARDMAN, GLENDINNING AND ROGERS (% 80150 cmolakg), as reported by Sparks (1995). Consequently, the changes in the WB physico-chemical properties are likely to be more apparent. Where surface pH-dependent charge is developed on a clay mineral and conditions are acidic, the anion is also more signicant. This is particularly relevant for ECC, where there are no permanent charge sites. The addition of CaCl2 instead of Ca(OH)2 will give rise to markedly different immediate changes in clay properties. This has been demonstrated by Anson & Hawkins (1998). The mechanisms of modication and solidication require a greater level of understanding for several reasons. The rst is associated with deciding how much lime to add to a clay soil in order to bring about the pozzolanic reactions. Current methodology (BSI, 1990a) derives from a test developed by Eades & Grim (1966). 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. (1997) suggest an alternative interpretation of the test data, and conclude that plasticity changes should be used to conrm the lime requirement for solidication, and that strength determinations should be used for design. Several reported results are of interest in the context of reaction mechanisms. Some soils are observed never to reach the pH of a saturated lime solution. This phenomenon is reported by Eades & Grim (1966) for soils that are holding univalent ions such as Na in the exchange position. As the ions are replaced by the Ca2 ions in such soils, the pH electrode becomes sensitive to the Na ions along with the H ion, hence affecting the measurements by making them appear more acidic. A second reason for understanding the reaction mechanisms is to appreciate the potential longevity of lime-solidied materials. Limited research into the long-term properties of limesolidied clays has been reported by McCallister & Petry (1992), who have carried out programmes of leach testing in the laboratory, and by Biczysko (1996), who studied the properties of lime-treated clay subgrades in the eld. However, no adequate chemical explanation of the long-term changes in physical properties has been put forward. This is important not only for ensuring the reliability of lime-treated materials, but also for the potential for lime-treated materials to leach contaminated pore water into the surrounding environment. In addition, there is a dearth of literature on the changes in soil properties wrought by very low percentage lime additions (i.e. those below the requirement for solidication calculated using the method outlined in Rogers et al., 1997). Very small additions of lime may be sufcient to change the apparent nature of the soil profoundly. It may be economical on very difcult sites to add these small quantities to allow working in wet conditions. However, if these changes can be attributed to cation exchange alone, 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. Conversely, if solidication has occurred it is less likely that the reactions could be reversed. 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, in terms of both the modication and solidication reactions. Currently, progress may be measured only by sampling and measuring strength changes. This has several drawbacks, including the difculty of taking intact samples of lime-solidied material, which is often very strong and brittle, and the inuence of pore suctions on the strength of the (generally) partially saturated material. (Soaking prior to testing could change the chemical nature of the material profoundly and yield equally erroneous observations.)

concentrations of Ca2 (aq) and OH (aq) ions in the pore water of the soil. This dissociation of ions results in a sequence of reactions that vary with soil composition, mineralogy, and pore water chemistry. The initial, immediate, modication 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. 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 ions. The result of cation exchange is increased occulation of mineral particles and changes in the plasticity properties of the soil. In physical terms, the result is an apparently drier, more friable material. The longer-term physico-chemical changes are brought about by a process termed solidication. Solidication occurs as a result of pozzolanic reactions, which are facilitated by the lime creating a highly alkaline soil pore chemistry, thereby promoting the dissolution of silicon and aluminium from the clay (Sherwood, 1993). This is initiated at the edge sites of the clay plates. The dissolved components from the dissolved clay minerals react with the Ca2 ions present in the pore water, permitting the formation of calcium silicate hydrate (CSH) and calcium aluminate hydrate (CAH) compounds. These compounds crystallise with time, resulting in further changes in clay plasticity (Sherwood, 1993), signicant increases in shear strength, and often a reduction in permeability (El-Rawi & Awad, 1981). The basic reactions described above are widely reported, but many issues remain unresolved. The mechanisms that bring about the observed changes are not fully understood. The timescale over which the reactions take place and, more particularly, whether the reactions occur sequentially, or occur concurrently, is also less well established. Many researchers disagree on these issues. For example, 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. Alternatively, Diamond & Kinter (1965) talk of lime adsorption and reaction at the clay surfaces giving rise to immediate local pozzolanic reactions at the clay surface. Bell (1988) discusses the ability of the OH ion to modify the clay surface, and for expansive clays to react more quickly owing to greater cation exchange capacity. This lack of agreement may, in part, be attributed to the complex nature and wide variety of combinations of the minerals that constitute a clay soil, and the potential for different reaction mechanisms to occur in different minerals. For example, English China Clay (ECC, predominantly kaolinite) and Wyoming Bentonite (WB, predominantly montmorillonite) have markedly different mineral structures with cation exchange sites in different positions within the clay lattice (Fig. 1). Consequently, the mechanisms by which cation exchange occurs are different for the two minerals. The majority of exchange sites on WB are the result of isomorphous substitution brought about by natural weathering processes, and therefore it is the development of this permanent positive charge decit that dictates many aspects of physico-chemical behaviour. 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. Furthermore, the exchange is affected by the disorder of the system, which is governed in part by the orientation of clay plates (McBride, 1994). The majority of variable charge, either positive or negative, on kaolinite is located on edge sites of the mineral and, predominantly, hydroxyl groups on the mineral. These sites, which are responsible for inter-particle hydrogen bonding, are pH sensitive, as determined by XOH H D XOH2 XOH D H XO

(1) (2)

where X is the mineral structure. Although still signicant, the cation exchange capacity developed on kaolinite (% 215 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 limeclay reaction and the longevity of limeclay reaction products. Particular objectives of the study were:

STABILISATION AND SOLIDIFICATION IN LIMECLAY 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, iron, magnesium Oxygens OH group and Silicon, occasionally aluminium Montmorillonite chemical structure

Fig. 1. Typical structure of English China Clay and Wyoming Bentonite (after Mitchell, 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 solidication. Kaolinite (in the form of ECC Grade 50) was investigated because it has predominantly pH-variable surface charge, while sodium montmorillonite (in the form of WB) was chosen because it has a very high permanent charge decit as well as pH-variable surface charge. The minimum quantity of lime required for solidication of ECC was found using the initial consumption of lime (ICL) test (BSI, 1990a) with revised interpretation of the results (Rogers et al., 1997). A further modication was necessary for WB since the specied addition of 100 ml of water to 20 g of soil resulted in a thick sludge, owing to the inherent swelling characteristics of the mineral. Consequently larger quantities (300 ml, 520 ml and 1000 ml) of deionised water were used.

Naturally this had an effect on the values of pH measured, but not signicantly on the quantity of lime required to bring about no further rise in pH. The ICL values for ECC and WB were found to be 15% lime and 70% lime (by dry mass of the clay) respectively (Fig. 2). Based upon these ICL values, 15% and 25% lime (at and above the ICL value) was added to ECC, and 25% and 70% lime (at and below the ICL value) was added to WB, the addition of 25% to both clays allowing additional comparisons to be made. Samples were prepared by mixing the dry clay with water. This material was sealed in plastic bags for 24 h to prevent evaporation. The lime was then added to ensure an even distribution. Samples were compacted into plastic moulds at water contents 2% wet of optimum. The samples were sealed in the moulds with parafn wax to prevent water loss and stored at 1158C 058C until required. Chemical and physical tests The aim of the chemical testing was to investigate the development of the limeclay reaction with time. It was therefore divided into two sections. One series of experiments ex-

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128 0 1

BOARDMAN, GLENDINNING AND ROGERS

English China Clay CaO(s) content: % 2 3 4 5 128 ICL ECC = 15% 126 126

Wyoming Bentonite: pH

English China Clay: pH

124

124

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

122

122

120 ICL WB 70% 118

120

118

116

116

114 0 5 10 15 Wyoming Bentonite CaO(s) content: % 20

114

Fig. 2. Initial consumption of lime of ECC and WB

amined the nature and quantity of ions not bound to the lime clay matrix, and another examined those that were inherently part of the solidied material. Additionally, 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. Additionally, a comparison between the relatively simple tests to measure conductivity and pH was made with the elemental prole of the ions present in solution. This was required to see whether pH or conductivity could be used in situ to monitor the progress of the lime reactions. After 7, 175 and 301 days' curing the undrained shear strength was assessed using the shear vane apparatus. Atterberg limits were measured in accordance with BS 1377 (BSI, 1990b) with the exception of sample preparation. Owing to the sensitivity of some of the reaction products to pH, and therefore changes in water content, the samples were not dried in the oven. Additionally, changes in water content and temperature could affect the crystallisation of hydrated reaction products and their physical behaviour. Samples were crushed at their extracted water content using a pestle and mortar. Once particles appeared to be approximately 1 mm in diameter further water was added to the mixture and further particle crushing was carried out. This process was continued until a consistently smooth mixture was created. A chemical batch test was performed on the limeclay samples after the same curing periods. This consisted of cutting cubes of solidied material of known dimensions and adding them to 2 l wide-necked, uorinated, high-density polyethylene containers with Grade 1 deionised water to achieve mixtures of known solid-to-liquid ratio. The containers were then placed in a reciprocating mixer and mixed at either 30 revamin or 60 revamin for 6 h or 24 h. Periodically the pH and conductivity of the solutions were measured. pH is a measure of H3 O (aq) ion concentration and indirectly OH (aq) ion concentration since the product of the concentrations (moladm3 ) of the H3 O (aq) and OH (aq) ions is always equal to 1 3 1014 mol2 adm6 . In contrast, conductivity is a measure of the solution electrical conductivity that is directly related to the quantity of ions, either cations or anions, in solution. Hence conductivity reects the quantity of dissolved solids. Samples were ltered through Whatman 542 hardened ashless lter papers and the solution acidied to below pH 40 and stored below 48C until analysis by inductively coupled argon plasma atomic emission spectroscopy, usually within 2 or 3 days, for specic ions present in the solution.

The effects of altering the operating parameters on element concentrations, pH and conductivity were investigated by altering the size of the cubes of material cut from the monolithic mass, the solid-to-liquid ratio and the speed and duration of rotation. These changes alter the development of chemical equilibrium during the batch test, and in the case of solid-toliquid ratio the nal equilibrium of ions in solution is completely changed. However, for all batch test parameter variations, the same trends in behaviour were observed, and illustrated clearly the time-dependent chemical changes as a result of lime addition. 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. In order to study the nature of the permanently reacted material, after 301 days' curing each limeclay mix was dried at 105 0X58C for 24 h, crushed with a pestle and mortar, and acid-digested twice. The process involved reuxing 1 g of dry material measured to within 0.1 mg with 46 ml of BS 3978 Grade 1 deionised water (BSI, 1987) and precisely 27 ml of Aristar concentrated hydrochloric acid and 13 ml of Aristar concentrated nitric acid. This acid digestion process was repeated twice, and after cooling the samples were ltered through Whatman 542 hardened ashless lter papers, made up to a standard volume using BS 3696 Grade 1 deionised water and analysed for the eight chosen elements: calcium, silicon, aluminium, iron, sodium, magnesium, manganese and lead. Note that the results presented below represent a small selection from 1300 tests, and hence the data are interpreted on the basis of consistent trends as well as on the measurements presented.
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. Figures 3 and 4 illustrate the changes in pH and conductivity for ECC and WB samples respectively. ECC is slightly acidic, while the WB is naturally alkaline, primarily because of the differences in the development and magnitude of charge sites between the clays and the ions associated with these sites. This difference between the two minerals is also apparent in the higher nal conductivity of the WB relative to the ECC. If it is assumed that the solutions in the batch test are saturated with

STABILISATION AND SOLIDIFICATION IN LIMECLAY MIXTURES

4000 14

537

3500

12 Clay only. Conductivity 10 Clay + 15% lime. Conductivity

3000

Conductivity: S/cm

2500 8 2000 6 1500 4 1000 2 Clay + 15% lime. pH Clay + 25% lime. pH pH Clay + 25% lime. Conductivity Clay only. pH

500

0 0 50 100 150 200 Curing time: days 250 300

0 350

Fig. 3. ECC: end of batch test, pH and conductivity

4000

14

3500

12 Clay only. Conductivity 10 Clay + 25% lime. Conductivity

3000

Conductivity: S/cm

2500 8 2000 6 1500 4 1000 2 Clay + 25% lime. pH Clay + 70% lime. pH pH Clay + 70% lime. Conductivity Clay only. pH

500

0 0 50 100 150 200 Curing time: days 250 300

0 350

Fig. 4. WB: end of batch test, pH and conductivity

Ca2 and OH ions then a similar pH environment is likely in the pore water during curing. After the addition of lime, the pH and conductivity observed after 7 days' curing are markedly increased, as might be expected. However, increased curing periods signicantly reduce conductivity, while pH remains relatively unchanged. This is signicant as the pH is maintained to a sufcient level to allow mineral dissolution, as illustrated in Fig. 5, which shows the pH-dependent solubility of Al2 O3 and SiO2. Figures 6 and 7 illustrate the changing elemental concentrations in solution with curing time and consequently the signicant differences in behaviour between ECC mixes and WB mixes. Fig. 6 shows that the large reduction in conductivity of ECClime mixes is due to signicant reductions in the soluble calcium concentration. However, for WBlime mixes (Fig. 7)

the reduction in conductivity is evidently due to a reduction in soluble calcium and sodium. Equally, for WB at 7 days a signicant proportion of the Ca2 ion concentration is evidently removed from solution and Na ions are deposited into solution as a result of exchange processes. Clearly ECC would not be expected to exhibit this behaviour because of its limited ion exchange potential. Time-dependent behaviour in both mineral mixes is also illustrated. At 7 days very small concentrations of soluble silicon or aluminium are measured in solution, suggesting limited effects due to mineral dissolution. After 175 days' curing there is a large increase in soluble aluminium concentration and no signicant amount of soluble silicon for ECC mixes. Conversely, large increases in soluble silicon concentration and very small increases in soluble aluminium con-

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BOARDMAN, 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%. In contrast, the 25% lime sample increased in strength by at least 80% between 7 and 175 days (again the absolute value for the sample with 25% lime was above the operating limits of the measuring apparatus). Atterberg limits English China Clay. Figure 10 illustrates the effects of varying lime content on the liquid limit, plastic limit and plasticity index of ECC after varying curing times. The addition of lime signicantly increased the liquid limit, and it was generally apparent that there was no signicant further increase in the liquid limit achieved by increasing the lime content beyond the ICL value (to 25% lime addition). The effect of increasing curing time was to reduce the liquid limit. However, it is important to note that after increased curing periods the sample with no lime also showed a reduction in liquid limit, the reduction being approximately half that of the lime-treated samples. The addition of lime also increased the plastic limit of ECC (Fig. 10), approximately similar plastic limits being achieved after 7 days for the 15% and 25% lime additions. Thereafter the plastic limit of the samples containing 25% lime was signicantly greater as the values for 15% lime tended towards the value for clay only. These effects combined resulted in an increased plasticity index after 7 days due to the addition of lime. This trend was also apparent after 175 and 301 days owing to the addition of 15% lime, whereas the effect of increasing curing time was to reduce the plasticity index of the samples containing 25% lime. Wyoming Bentonite. A 70% lime addition to WB resulted in a considerable decrease in liquid limit (Fig. 11), whereas the lower lime addition (25%) resulted in little apparent change. However, the liquid limit of the untreated WB is notoriously difcult to measure, and (as acknowledged by the suppliers) will vary from approximately 350% to 600%. What was apparent, however, was that upon addition of 25% lime these problems disappeared, and consistent readings at the lowermost boundary of the untreated readings were obtained. The material, although not fully modied, had an evidently changed character at this lime addition. Curing time had little effect on the liquid limits. The addition of 25% lime to WB had little effect on the plastic limit, whereas with 70% lime the plastic limit increased signicantly (Fig. 11), the plastic limit reducing markedly with increased curing time. 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. For fully modied WB (70% lime addition), however, the plasticity index reduced substantially. There was a marginal increase in plasticity index with curing period for the fully modied WB as a result of the fall in plastic limit, although this was very small in the context of the overall reduction from the untreated state.
DISCUSSION

9 8 Solubility: mmol/l 7 6 5 4 3 2 1 0 0 1 2 3 4 5

CaCO3

Fe(OH)2 8 9

10

10 11

12

13

14

Range of pH values in natural waters and rain

Fig. 5. Solubility of some soil mineral species in relation to pH (after Loughnan, 1969)

centration were measured in WB mixes at the same curing period. Acid-soluble element fractions The acid-soluble element fractions also revealed substantial information about the behaviour of the clay minerals. However, 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. It should also be noted that pH affects the solubility of some of the compounds likely to be present, as illustrated in Fig. 5. 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 acid-soluble fractions due to clay alone have been subtracted so that the effects of the limeclay reaction can be seen more clearly. As the lime content of the ECC samples increased the soluble fractions of calcium, silicon and (to a much smaller degree) aluminium increased. The WB samples exhibited increased soluble fractions of calcium, aluminium and (to a somewhat smaller degree) silicon, while soluble fractions of sodium decreased. Shear strength variations Figure 9 illustrates the development in undrained shear strength of ECC and WB mixes. The undrained shear strength of WB with 25% lime increased by 20% immediately after 7 days, but thereafter there was no appreciable change in the undrained shear strength. Greater increases in undrained shear strength were observed for the 70% lime addition after 7 days, 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, increases in strength were perceived during the process of performing the test. The shear strength development of the ECC mixes was substantially different from that of WB. Both limeclay mixes showed only a small increase in undrained shear strength after 7 days. The sample containing 15% lime (the ICL value) showed a signicant increase of 28% between 7 and 175 days, 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, thus indicating a potential method of in situ monitoring. The concentration of Ca2 ions and conductivity, while very much greater for the higher lime content after 7 days, converged to similar values for the two different lime contents with increasing curing period. Therefore it may be argued that more Ca2 ions are removed from solution by curing at the higher lime content. At 7 days there were negligible water-soluble aluminium and silicon concentrations with 15% lime, whereas there was a signicant concentration of aluminium with 25% lime (Fig. 6). Similar large aluminium concentrations and small silicon concentrations were observed after 175 and 300 days for both lime contents. The two lime contents produced mixes with similar undrained shear strengths

STABILISATION AND SOLIDIFICATION IN LIMECLAY 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 + 15% lime. Si concentration (ppm) Clay + 15% lime. Al concentration (ppm) Clay + 15% lime. Ca concentration (ppm)

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 + 25% lime. Si concentration (ppm) Clay + 25% lime. Al concentration (ppm) Clay + 25% lime. Ca concentration (ppm)

100

4 50 2

0 0 50 100 150 200 Curing time: days (b) 250 300

0 350

Fig. 6. End of batch test: element analysis of ECC samples with (a) 15% and (b) 25% lime (24 h, 30 revamin, 1:40 S/L, 20 mm cubes)
30 Ca, 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 + 70% lime. Ca concentration (ppm) Clay + 70% lime. Si concentration (ppm) Clay + 70% lime. Al concentration (ppm) Clay + 70% lime. Na concentration (ppm)

50

0 0 50 100 150 200 Curing time: days 250 300

0 350

Fig. 7. End of batch test: element analysis of WB samples with 70% lime (24 h, 30 revamin, 1:40 S/L, 20 mm cubes). Elemental analysis of WB samples with 25% lime was not available because the material from these batch tests could not be ltered

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1000

BOARDMAN, GLENDINNING AND ROGERS

20 000 18 000 800 Fe, Si, 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, Al concentration in solid: mg/kg

600

Fe concentration Si concentration Mg concentration Ca concentration Al concentration

Na, Al, Fe, Si, 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

Fig. 8. Corrected acid-soluble fractions of (a) ECC and (b) WB samples with increasing lime content after 301 days' curing

after 7 days, while at 175 and 301 days the higher lime content produced mixtures of signicantly higher strength. Similarly, both mixes exhibited very similar plasticity changes at 7 days, but for increased curing periods they showed signicant differences in plastic limit and therefore plasticity index. The observations made allude to potential reaction mechanisms and differences between the two lime additions. At 7 days the reaction for 15% lime may be attributed to ion exchange effects alone, because no soluble silicon or aluminium was observed in batch test solutions, whereas with 25% lime some clay mineral dissolution at the exposed edges (and hence aluminium concentration) had begun. The ICL test gives a good indication of the amount of lime required to satisfy ion exchange, addition of lime above this amount having little short-term benet since early dissolution of the clay minerals yields no physical gain. The reduction in soluble calcium content and increase in soluble aluminium content at increased curing times point towards considerable pozzolanic activity. As the mineral lattice is dissolved, producing soluble aluminium, soluble calcium is `consumed' by the reaction with aluminium to produce cementitious material and concomitantly reduce conductivity. This pozzolanic activity took place largely after 7 days, but was shown to be slowing

down between 175 and 301 days. The addition of lime above the ICL value has substantial benet for long-term strength gain. Changes in strength and plasticity may be attributed to ion exchange in the short term, whereas in the long term an additional benet of the pozzolanic reaction is observed. The presence of pozzolanic material is evidenced by the presence of acid-soluble aluminium and silicon after 301 days (Fig. 8). The sample with a higher lime content has a higher proportion of acid-soluble calcium but a similar water-soluble content. Again, this alludes to greater pozzolanic activity with higher percentage lime additions. An important observation relating to the development of the solidication reactions is the relatively small amount of watersoluble and acid-soluble silicon compared with aluminium. It is apparent therefore that a greater quantity of CAH is being formed than CSH. 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.e. near the pH-dependent negative charge sites; Fig. 1). The presence of increased silicon in the sample with 25% lime suggests that there is more mineral breakdown induced by the higher lime content.

STABILISATION AND SOLIDIFICATION IN LIMECLAY MIXTURES

160 140

541

Undrained shear strength: kN/m2

120

100 Clay only 80 Clay + 15% CaO(s) Clay + 25% CaO(s)

60 40

20 0 (a) 160 140

Undrained shear strength: kN/m2

120

100 Clay only 80 Clay + 25% CaO(s) Clay + 70% CaO(s)

60 40

20 0 0 50 100 150 200 Curing time: days (b) 250 300 350

Fig. 9. Variation of undrained shear strength of (a) ECC and (b) WB samples with increasing lime content and curing time. Shear strength values illustrated as 145 kNam2 are at the measurement limit for the shear vane apparatus, and the actual strength may be signicantly higher

Wyoming Bentonite Despite the initial difference in pH between the two minerals, the pH achieved after lime addition is very similar throughout to that achieved by ECC. Similarly the pattern of high initial conductivity and Ca2 ion concentration, which reduce with curing time owing to solidication, is observed. Again, the initial large difference between the conductivity and Ca2 ion concentration between the two lime contents reduces with time as the Ca2 ions with 70% lime addition are used up by the pozzolanic reactions. However, unlike the ECC case, there remains a signicant difference in conductivity since the lower lime addition is much less than the ICL value. After 7 days the conductivity of the ECC mixture with 25% lime is higher than that of the same mixture with WB. However, there is a marked increase in conductivity (to a value similar to that of ECC at the ICL lime content) when 70% lime is added. The strength increase and plasticity changes wrought by 25% lime are similarly far less pronounced at 7 days. This indicates that 25% lime is not sufcient to complete ion exchange, and the physical effects of occulation are not fully achieved. As ion exchange occurs at the permanent charge sites, Ca2 ions

exchange for Na ions, and thus the presence of less sodium in solution may also be an indication of incomplete cation exchange. Similarly to ECC, there is very little soluble silicon or aluminium present at 7 days, indicating that the strength increases and plasticity changes observed are due primarily to cation exchange rather than pozzolanic activity. Reduction in conductivity at increased curing periods once more suggests increased pozzolanic reaction products that improve strength and plasticity characteristics. Unlike ECC the reduced conductivity is caused by both a reduction in soluble calcium and sodium, 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. The strength increases for WB with increased curing period were very much greater with the higher lime content. This is mirrored by the plasticity changes that were much greater with the higher lime content. The strength increases and plasticity changes were considerably greater in WB than in ECC. The explanation for this has been attributed to the difference in cation exchange capacity discussed earlier, which undoubtedly

542
80

BOARDMAN, GLENDINNING AND ROGERS

80

70

70

Liquid limit (LL) and plasticity index (Pl): %

60

60

Clay only (LL) Clay + 15% CaO(s) (LL) Plastic limit (PL): %

50

50

Clay + 25% CaO(s) (LL) Clay only (PI) Clay + 15% CaO(s) (PI) Clay + 25% CaO(s) (PI) Clay only (PL) Clay + 15% CaO(s) (PL)

40

40

30

30

20

20

Clay + 25% CaO(s) (PL)

10

10

0 0 50 100 150 200 Curing time: days 250 300

0 350

Fig. 10. Variation of the liquid limit, 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 + 25% CaO(s) (LL) Clay + 70% CaO(s) (LL) Clay only (PI) Clay + 25% CaO(s) (PI) Clay + 70% CaO(s) (PI) Clay only (PL) Clay + 25% CaO(s) (PL) Clay + 70% 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. 11. Variation of the liquid limit, plastic limit and plasticity index of WB with increasing lime content and curing time

accounts for the differences at 7 days, when these changes can largely be attributed to occulation. However, further differences were noted in the pozzolanic activity in the two clays. In contrast to ECC, 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. The amount of soluble silicon was

approximately twice as great as the dominant aluminium concentration in the ECC samples. This indicates that WB preferentially forms CSH rather than CAH, and that more pozzolanic product is formed than for ECC. Again, an examination of the mineral structure (Fig. 1) shows that if dissolution occurs at the edges of the crystal lattice, silicon is the dominant element in this case.

STABILISATION AND SOLIDIFICATION IN LIMECLAY MIXTURES It is difcult to conclude that no pozzolanic reactions had occurred at the lower lime content. Little strength gain is achieved after 7 days with 25% lime addition and, importantly, no signicant increase occurs thereafter, despite the recorded reductions in conductivity after this time. Elemental concentrations could not be made owing to the difculty of ltering the samples at the lower lime content. The pH remained sufciently high to dissolve the mineral structure, and the acid-soluble calcium and aluminium increases indicate the development of pozzolanic material. The slight changes in plasticity also indicate some chemical alteration of the mineral. However, the strength data are likely to provide the most conclusive evidence of no practical benet from solidication.
CONCLUSIONS

543

ments. The precise solid-to-liquid ratio is not necessarily vital so long as it remains consistent with time. Indeed, conductivity of the pore water could be measured in situ, thereby monitoring the development of solidication in a non-destructive way.

The ICL addition of lime provides an indication of the amount of lime required to satisfy ion exchange. For clays with high cation exchange capacity, considerable benet can be gained by lime addition below the ICL value. It seems probable that a small amount of pozzolanic reaction occurs despite the low lime content, but that this has little (if any) practical benet. For clays with low cation exchange capacity, the benet of a lower addition of lime is more questionable and less signicant in terms of the cost of the reagent. In addition, the difculty with mixing such very small quantities of lime in practice would probably counteract any cost saving for reduced lime consumption. Whether to add additional lime above that determined by the ICL test is dependent upon what is required of the product. It has been shown that lime addition above the ICL value has little benet in the short term but substantial value in the longer term in terms of strength. If an immediate reduction in plastic limit is required there is little point in adding greater quantities of lime; if long-term strength is required a greater quantity of lime gives a better product. The mechanism of strength gain is attributable to occulation in the short term and additionally to pozzolanic reaction in the longer term. No signicant pozzolanic activity (and certainly no crystallisation of reaction products) appears to take place until after 7 days' curing. Cation exchange takes place on pHdependent charge sites in kaolinite and additionally at permanent charge sites in montmorillonite. 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. Mineral dissolution takes place initially at the edges of the crystalline structure, 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. Montmorillonite produces more reaction product, probably because of its greater surface area. There is also potential for a difference between the fabrics of the two limeclay products owing to the relative position at which dissolution takes place and therefore the position of subsequently crystallised reaction products. 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). The development of pozzolanic reactions in WB can be monitored similarly by measuring increases in the concentration of leachable silicon, and reductions in the concentration of leachable calcium and sodium (and hence again conductivity). Therefore, an ideal, but cheap and simple, in situ test to monitor the progress of lime treatment reactions in the long term is by conductivity measure-

REFERENCES Anson, R. W. W. & Hawkins, A. B. (1998). The effect of calcium ions in pore water on the residual shear strength of kaolinite and sodium montmorillonite. Geotechnique 48, No. 6, 787800. Bell, F. G. (1988). Stabilization and treatment of clay soils with lime. Ground Engng 21, No. 1, 1015. Biczysko, S. J. (1996). Long-term performance of lime stabilised road subgrade. In: Lime stabilisation (eds C. D. F. Rogers, S. Glendinning and N. Dixon), pp. 6274. London: Thomas Telford. Boardman, D. I. (1999). Lime stabilisation: claymetallime interactions. PhD thesis, Loughborough University, UK. British Standards Institution (1987). Water for laboratory use, BS 3696. London: BSI. British Standards Institution (1990a). Stabilized materials for civil engineering purposes. Methods of test for cement-stabilized and lime-stabilized materials, BS 1924: Part 2. London: BSI. British Standards Institution (1990b). Methods of test for soils for civil engineering purposes, BS 1377. London: BSI. Broms, B. B. & Boman, P. (1976). Stabilisation of deep cuts with lime columns. Proc. 6th Eur. Conf. Soil Mech. Found. Engng, Vienna, 207210. Chaddock, B. C. J. (1996). The structural performance of stabilised soil in road foundations. In Lime stabilisation (eds C. D. F. Rogers, S. Glendinning and N. Dixon), pp. 7594. London: Thomas Telford. Highways Agency (2000). Treatment of ll and capping materials using either lime or cement or both. In Design manual for roads and bridges, Vol. 4, Section 1. London: HMSO. Diamond, S. & Kinter, E. B. (1965). Mechanisms of soil-lime stabilization. Highway Research Record, No. 92, 83102. Eades, J. L. & Grim, R. E. (1966). A quick test to determine lime requirements of lime stabilisation. Highway Research Record, No. 139, 6172. EL-Rawi, N. M. & Awad, A. A. (1981). Permeability of lime stabilized soils. Transportation Engng J., January, 2535. Glendinning, S. & Rogers, C. D. F. (1996). Deep stabilisation using lime. In Lime stabilisation (eds C. D. F. Rogers, S. Glendinning and N. Dixon), pp. 127138. London: Thomas Telford. Glendinning, S., Rogers, C. D. F. & Boardman, D. I. (1998). Lime stabilisation of inorganic contaminants in clays. In Contaminated land and groundwater: future directions, Engineering Geology Special Publications, Vol. 14, pp. 1928. London: Geological Society. Holt, C. C. & Freer-Hewish, R. J. (1998). The use of lime-treated British clays in pavement construction. Part 1: The effect of mellowing on the modication process. Proc. Inst. Civ. Engrs Transport 129, November, 228239. Loughnan, F. C. (1969). Chemical weathering of silicate minerals. New York: Elsevier. McBride, M. B. (1994). Environmental chemistry of soils. New York: Oxford University Press. McCallister, L. D. & Petry, T. M. (1992). Leach tests on lime-treated clays. Geotech. Test. J. 15, No. 2, 106114. Mitchell, J. K. (1976). Fundamentals of soil behaviour. New York: John Wiley & Sons. Rogers, C. D. F. & Glendinning, S. (1997). Improvement of clay soils using lime piles. Engng Geol. 47, 243257. Rogers, C. D. F., Glendinning, S. & Roff, T. E. J. (1997). Modication of clay soils for construction expediency. Proc. Inst. Civ. Engrs Geotech. Engng 125, 18. Sherwood, P. T. (1993). Soil stabilisation with cement and lime. London: HMSO. Snedker, E. A. (1996). M40-Lime stabilisation experiences. In Lime stabilisation (eds C. D. F. Rogers, S. Glendinning and N. Dixon), pp. 142158. London: Thomas Telford. Sparks, D. L. (1995). Environmental soil chemistry. London: Academic Press.