Applied Clay Science 141 (2017) 36–45

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Applied Clay Science

journal homepage: www.elsevier.com/locate/clay

Research paper

Multi-scale analysis and time evolution of pozzolanic activity of lime

treated clays
E. Vitale ⁎,a, D. Deneele b,c, M. Paris b, G. Russo a
a
Department of Civil and Mechanical Engineering, University of Cassino and Southern Lazio, G. Di Biasio, 43, 03043 Cassino, FR, Italy
b
Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS, 2 rue de la Houssiniere, BP 32229, 44322 Nantes, Cedex 3, France
c
IFSTTAR, Institut Français des Sciences et des Technologies des Transports, de l'Aménagement et des Réseaux, CS4, route de Bouaye, 44344 Bouguenais Cedex, Nantes, France

a r t i c l e i n f o a b s t r a c t

Article history: A multi-scale investigation on the influence of clay mineralogy on the pozzolanic activity of lime treated clays has
Received 4 December 2016 been presented. Two clays of different mineralogy have been considered for this study, namely kaolin and ben-
Received in revised form 26 January 2017 tonite. The time dependent mineralogical and microstructural changes induced by lime addition have been mon-
Accepted 11 February 2017
itored at increasing curing time by means of X-ray diffraction (XRD), thermogravimetric analysis, 29Si NMR
Available online xxxx
spectroscopy, Scanning electron microscopy (SEM) and nitrogen adsorption/desorption measurements. Differ-
Keywords:
ent lime contents of the treated samples have been considered in order to highlight the ongoing of pozzolanic
Lime treatment reactions. The time scale of chemical reactions taking place after the addition of lime depends on clay mineralogy.
Kaolinite In the short term, flocculation phenomena due to the cation exchange reactions control the microstructural fea-
Bentonite tures of lime treated kaolin. The low reactivity of kaolinite clay minerals to pozzolanic reactions was detected as a
Pozzolanic reactions delay in precipitation of new hydrated phases. The chemo-physical evolution of lime treated bentonite depends
Multi-scale analysis on the combined effect of cation exchange and pozzolanic reactions which develop with a comparable time scale.
The results of micro-scale investigations were directly linked to the experimental evidences at volume scale of
the samples, allowing an interpretation of the mechanical improvement of the treated clays in the short and
long term as a function of the chemo-physical evolution of the system.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
The addition of lime to a clay has a strong impact on its physical and
mechanical properties through the time (Glenn and Handy, 1963;
Brandl, 1981; Bell, 1996, Rogers and Glendinning, 1996; Locat et al.,
1996; Sivapullaiah et al., 2000a; Tremblay et al., 2001; Sudhakar Rao
and Shivananda, 2005).
Several studies on the basic lime-clay-reaction mechanisms have
been widely reported in literature (Eades and Grim, 1960; Diamond
and Kinter, 1965; Boardman et al., 2001; Maubec, 2010; Delavernhe,
2011; Pomakhina et al., 2012; Dewindt et al., 2014; Chemeda et al.,
2015), allowing a better understanding of the chemo-physical evolution
of the system and microstructural features induced after the addition of
lime (Russo et al., 2007; Metelkova et al., 2012, Russo and Modoni,
2013; Vitale et al., 2016a,b,c,d).
The reactions kinetic controlling the chemo-physical evolution of
clay-lime-water system depend on clay mineralogy (Al-Mukhtar et al.,
2014). The time scale of chemical reactions taking place after lime
⁎ Corresponding author at: Department of Civil and Mechanical Engineering, University
of Cassino and Southern Lazio, Via G. Di Biasio, 43, 03043 Cassino, FR, Italy.
E-mail address: e.vitale@unicas.it (E. Vitale).
addition plays a key role in the interpretation of the macroscopic evolu-
tion of clay properties, and it has not been thoroughly investigated in
literature.
When lime is added to the clay water system, either in the form of
quicklime (CaO(s)) or as hydrated lime (Ca(OH)2), a change in the
pore water chemistry occurs. For quicklime the first reaction taking
place is hydration reaction, highly exothermic, leading to the formation
of hydrated lime (portlandite) in the clay water system. The dissociation
reaction of the hydrated lime formed due to the quicklime hydration
leads to an increase of the pH and to a high concentration of calcium
ions in the pore water. The increase of pH alters the distribution of
charge on the clay platelets whereas the calcium ions released from
lime replace the exchangeable cations from clay, leading to a reduction
of the thickness of double layer surrounding clay particles (Rogers and
Glendinning, 1996). This process, referred to as cation exchange reac-
tion, makes clay minerals flocculate and agglomerate leading to quick
changes in plasticity, workability and particle size distribution.
In addition to cation exchange, the high pH environment induced by
lime enables the dissolution of the alumino-silicate constituents of clay
minerals promoting the development of the pozzolanic reactions. The
silica and alumina released from clay minerals react with lime leading
to the precipitation of calcium silicate hydrate (CSH), calcium aluminate

http://dx.doi.org/10.1016/j.clay.2017.02.013
0169-1317/© 2017 Elsevier B.V. All rights reserved.
 E. Vitale et al. / Applied Clay Science 141 (2017) 36–45
hydrate (CAH) or calcium aluminate silicate hydrate (CASH). These
amorphous phases crystallise with time forming cementitious com-
pounds bonding clay particles together (Ingles and Metcalf, 1972; Bell,
1996; Little, 1996; James et al., 2008).
The presence of a high pH environment, namely pH value of 12.4–
12.6 (the pH of a saturated lime solution) or higher, is essential to guar-
antee the effectiveness of lime (CaO or Ca(OH)2) stabilisation of clays by
means of pozzolanic reactions. At these high pH levels, the solubility of
silica and alumina is largely increased. Thus, as long as the lime is avail-
able in the system and the pH remains high enough to maintain the sol-
ubility, pozzolanic reactions continue over time to form bonding
compounds that cause long-term strength increase (Al-Mukhtar et al.,
2014; Locat et al., 1996; Sivapullaiah et al., 2000b; Tremblay et al.,
2001; Rao and Shivananda, 2005). The pozzolanic reaction is therefore
a time-dependent reaction, whose kinetic depends on the soil mineral-
ogy, the amount of unconsumed of portlandite (Ca(OH)2) in the system
and on the curing time temperature (Little, 1996; Rao and Shivananda,
2005; Rojas and Cabrera, 2002; Al-Mukhtar et al., 2010).
A multi scale analysis on the short and long term effects of lime
treatment have been performed in this study to highlight the link be-
tween the ongoing reactions and the macroscopic evolution of clay
properties. The influence of clay mineralogy on the chemo-physical evo-
lution of lime treated clays have been investigated by comparing two
different clays, namely kaolin and bentonite. At particle level, both the
mineralogical and microstructural changes have been monitored at in-
creasing curing time by means of X-ray Diffraction (XRD), Thermo-
Gravimetric Analysis (TGA), 29Si NMR spectroscopy, Scanning Electron
Microscopy (SEM) and Nitrogen adsorption/desorption measurements.
At macroscopic level, the mechanical behaviour of lime treated clays
have been analysed by one dimensional compression tests on samples
cured for short and long time intervals, highlighting the mechanisms re-
sponsible for the improvement of the mechanical properties of the
treated clays.
2. Materials and experimental methods
2.1. Materials
A highly refined kaolin (Speswhite kaolinite, Imerys Minerals) from
deposits in the South West of England has been used. The specific grav-
ity is Gs = 2.6, and surface area determined by nitrogen adsorption
(BET) is 14 m2/g. The pH value of the clay is about 4.6. The liquid and
plastic limits are 70% and 32% respectively, with a plastic index IP of
38%. The sample is mainly formed by kaolinite clay minerals with a
small amount of quartz (SiO2) and muscovite (KAl3Si3O10(OH)2). No
swelling clay phases were detected after the ethylene glycol treatment.
The element composition of kaolin has been reported in Table 1.
Natural bentonite has been supplied by SSB Srl (Italy). The specific
gravity is Gs = 2.54, and surface area determined by nitrogen adsorp-
tion (BET) is 99.38 m2/g. The pH value of the clay is about 7.55. The liq-
uid and plastic limits are 143% and 69% respectively, with a plastic index
IP of 74%. The clay is formed by Ca-montmorillonite as a major phase.
The minor phases identified in bentonite sample include quartz and cal-
cite. The element composition of bentonite is reported in Table 2.
The quicklime used for treatment of the studied clays contained
more than 90% of free calcium oxide, 1% Ca(OH)2 and 4% calcite.
Table 1
Micro XRF chemical composition of kaolin.
Constituent Percentage (%)
SiO2 53.80
Al2O3 43.75
CaO 0.02
K2O 1.45
TiO2 0.05
37
2.2. Methods
2.2.1. X-ray diffraction analysis
The mineralogical composition of clays and the time dependent
mineralogical changes induced by lime addition were investigated by
X-ray analysis performed on randomly oriented powder using a Brucker
AXS D8 Advance Diffractometer with CuKα (λ = 0.154 nm) radiation
and a step size of 0.021°. Samples have been freeze-dried before testing
(Delage and Pellerin, 1984).
2.2.2. Micro-XRF analysis
The element analysis of clays has been carried out by using micro-
XRF M4 Tornado spectrometer (Bruker AXS microanalysis) equipped
with energy dispersive detector (SDD) and rhodium X-ray source. The
X-ray tube was operated at a voltage of 50 kV and a current of 300 μA
and X-ray focal spot size of 25 μm. All the experiments were performed
on pressed powder pellets.
2.2.3. Thermo-gravimetric analysis
Thermo-gravimetric analysis has been performed with a Netzsch
STA 449F3 Jupiter, equipped with a mass spectrometer to monitor
evolved molecule of water and carbon dioxide with elevated tempera-
ture. Finely ground clay was heated at a rate of 10 °C min− 1, under
argon atmosphere, from ambient temperature to 1000 °C. The Netzsch
Proteus software has been used to process the results. The first deriva-
tive of the TG curves (DTG) leads to better reading of the peak data.
2.2.4. NMR
29
Si solid state NMR were performed on a 300 MHz Bruker Avance III
by using a 7 mm MAS probe. The 29Si MAS NMR spectra were acquired
with single π/2 excitation of 5.5 μs and 1H decoupling. The MAS frequen-
cy was set to 5 kHz and the recycle delay between scans to 5 s. Chemical
shifts were referenced to TMS using tetrakis (trimethylsilyl) silane as a
secondary reference (δ = −9.85 ppm from TMS).
2.2.5. SEM
The surface state modifications and fabric changes of clay particles
due to the lime treatment have been examined through Scanning Elec-
tron Microscopy (SEM) by using XL Philips microscope. Not treated and
lime treated samples have been dehydrated by freeze-drying technique
(Delage and Pellerin, 1984). A gold coating pre-treatment has been per-
formed for SEM observations.
2.2.6. N2 adsorption
The microstructure evolution of lime treated clays has been moni-
tored by nitrogen adsorption/desorption measurements, by comparing
the specific surface area of the treated clays with the not treated ones
as a function of lime content and curing time. The adsorption isotherms
at 77 K of N2 gas have been carried out using ASAP 2010 physisorption
Analyzer (Micromeritics, Georgia, USA).
2.2.7. Oedometer tests
Oedometer tests have been performed on not treated and lime treat-
ed samples cured for increasing time intervals. The tests have been per-
formed in standard oedometer cells, where vertical stress was
conventionally applied in successive steps (Δsv/sv = 1) within the stress
Table 2
Microchemical composition of Ca-montmorillonite bentonite.
Constituent Percentage (%)
SiO2 64.85
Al2O3 24.33
CaO 2.14
K2O 0.21
MgO 3.18
FeO 4.21
38 E. Vitale et al. / Applied Clay Science 141 (2017) 36–45

Fig. 1. X-ray diffraction patterns of untreated and lime treated kaolin as a function of curing time: a) 1% CaO, b) 5% CaO.

interval 10 ÷ 6400 kPa. Micrometer dial gauges with an accuracy of
0.001 mm have been used to measure vertical displacements.
2.2.8. Samples preparation
Samples of not treated and lime treated clays were prepared in order
to monitor the chemo-physical evolution of the systems as function of
treatment parameters (lime content and curing time). 1%, 3% and 5%
of lime by dry weight of clay were selected for kaolin, whereas 3%, 5%,
10% and 20% of lime were selected for bentonite. The initial water con-
tent of samples for microstructure analyses was equal to w = 100%. The
curing time selected for microstructure analyses ranged between 0 and
270 days in order to highlight the ongoing of the reactions over the
short and long term.
Remoulded samples were prepared for oedometer tests by hand
mixing the clay with distilled water to slurry at approximately its liquid
limit (i.e. wL = 70% for kaolin, wL = 143% for bentonite). The same pro-
cedure was also used for lime treated samples, starting from slurry at an
initial water content corresponding to the liquid limit of the treated
samples (wL = 101% for treated kaolin with 3% and 5% CaO; wL =
124% and wL = 115% for 3% CaO and 5% CaO treated bentonite respec-
tively). The samples were poured in the mould and placed in oedometer
without compaction. The treated samples were then sealed in plastic
bags and cured at increasing curing times of 0, 7, 14, 28, 60, 120, 210
and 300 days before performing the mechanical tests.

Fig. 2. Time quantitative interpretation of TGA analysis on 3% and 5% CaO treated samples Fig. 3. 29Si NMR spectra of raw and treated kaolin at increasing lime contents and 270 days
due to hydrates formation. of curing time.
 E. Vitale et al. / Applied Clay Science 141 (2017) 36–45 39

3. Results
3.1. Kaolinite
X-ray diffraction patterns of kaolinite samples treated with 1% and
5% of lime at increasing curing time have been compared with the
not treated sample as shown in Fig. 1. New reflections attributed to
the presence of unconsumed portlandite were detected in the
samples treated with 5% CaO since the very short term (24 h of curing)
(Fig. 1b). The intensities of these peaks decrease with increasing
curing time, until their disappearance after 60 days of curing. New
peaks corresponding to calcium aluminate hydrate (CAH) and
monocarboaluminate hydrate (C4-A-C-H11) (Bakolas et al., 2006) were
detected after 28 days of curing. The peak intensities of new hydrates in-
crease with curing time. No new reflections were observed for kaolinite
samples treated with 1% CaO (Fig. 1a), proving the complete consump-
tion of the added lime since the very short term.
Thermal analyses of the not treated and lime treated kaolinite (3%
and 5% CaO) after 24 h, 3, 7, 28, 60, 210 and 270 days of curing time
showed the loss of water of calcium hydrates in the range of 110–
350 °C (Maubec et al., 2017). The mass loss in the temperature range
of 390 °C–460 °C evidences the decomposition of portlandite, whereas
the relevant weight loss between 500 °C and 600 °C is due to the loss
of structural water (dehydroxylation) (Manju et al., 2001). A quantita-
tive interpretation for determining the mass loss attributed to uncon-
sumed portlandite (hydrated lime) and cementitious compounds
formed after the treatment has been performed (Fig. 2). A significant
consumption of portlandite and the formation of new cementitious
phases have been detected starting from 28 days of curing. In the
short term the addition of lime leads to the precipitation of portlandite,
whose amount increases with lime content and influences the forma-
tion of secondary cementitious phases.
The 29Si NMR spectra of raw and treated kaolin with 3% CaO and 5%
CaO at 270 days of curing time is shown in Fig. 3. The spectrum of kaolin

Fig. 4. SEM images: a) and b) not treated kaolin; c) and d) 5% CaO treated kaolin cured for 24 h; e) and f) 5% CaO treated kaolin cured for 270 days.
40 E. Vitale et al. / Applied Clay Science 141 (2017) 36–45

is characterized by two main signals located at −91.5 and −90.1 ppm.

These resonance peaks correspond to silicon atom in the tetrahedral
layer of kaolinite particles (Q3) (Lippmaa et al., 1980). The two signals
are associated with two crystallographic sites of the kaolinite structure
(Barron et al., 1983; Thompson and Barron, 1987). No significant mod-
ifications of the spectra were detected after the addition of lime at
270 days of curing time, especially in the range between − 78 and
−88 ppm, which is characteristic of signals attributed to calcium silicate
hydrates (CSH) and calcium aluminate silicate hydrates (CASH). No
spectra modification were observed at shorter curing time as well.
SEM observations of not treated and 5% CaO treated samples at 24 h
and 270 days of curing have been reported in Fig. 4. In the short term, a
modification of the clay particles arrangement was observed with for-
mation of larger aggregates compared to not treated kaolin (Fig. 4a)
without any evidence of new hydrated phases. After longer curing
time (i.e. 270 days) the presence of CAH at the surface of clay particles
and filling the intra-aggregate porosity have been evidenced (Fig. 4e
and f).
Table 3 shows the evolution of specific surface area over curing time
of 3% CaO and 5% CaO treated kaolinite samples, evaluated from BET
theory (Brunauer et al., 1938). In the short term, a significant decrease
of specific surface (As) was detected as a result of particles aggregation
due to flocculation, mostly occurring immediately after the addition of
lime. A following increasing trend was detected for the tested samples
after 7 days of curing (3% CaO sample) and 28 days (5% CaO sample),
mainly depending on the ongoing formation of secondary hydrated
phases over curing time.
1D compressibility curves of not treated and 5% CaO treated kaolin at
increasing curing times, namely 24 h, 7, 14, 210 and 270 days are report-
ed in Fig. 5a). Addition of lime induces a compressive strength increase
of the treated samples, with reduced volume strains for reference verti-
cal stress, the reduction being more relevant for increasing curing times.
Yield stress is also affected by lime addition. A slight increase is detected
for short curing times, while it is relevant for samples after longer curing
times. At increasing stress levels, an increase of the compressibility
characterizes the post-yield phase until the reaching of the compress-
ibility curve of the not treated sample. At short term, the behaviour of
treated samples does not significantly depend on lime content, as
shown in Fig. 5b) for samples prepared at 3% and 5% of CaO after 24 h
of curing. Conversely, at long term (Fig. 5c) compressibility curves of
3% and 5% CaO samples show different behaviours, with a marked struc-
ture-induced behaviour for sample prepared at 5% CaO.

Table 3
Time evolution of specific surface (As) of not treated and lime treated kaolin and Ca-mont-
morillonite bentonite samples.

Samples % CaO Curing time As (m2/g)

Kaolin 0 – 14.13
24 h 8.72
7d 7.63
3 28 d 8.72
60 d 10.30
270 d 11.60
24 h 6.74 Fig. 5. One dimensional compression tests on raw and lime treated kaolin: a) 5% CaO
5 28 d 15.98 treated kaolin at increasing curing times; b) 3% CaO and 5% CaO at 24 h of curing time;
270 d 20.66 c) 3% CaO and 5% CaO at 210 days of curing time.
Bentonite 0 – 99.38
24 h 31.03
3 28 d 19.93
60 d 34.59 3.2. Bentonite
24 h 7.07
5 28 d 34.70
60 d 57.86
Fig. 6 shows the X-ray diffraction patterns of raw and lime treated
120 d 65.76 bentonite at different lime contents (5% and 20% CaO) and increasing
24 h 4.10 curing times. The addition of high amount of lime (up to 20% CaO)
10 28 d 47.81 was considered in order to highlight the reactivity of the system to poz-
60 d 63.01
zolanic reactions. As shown in Fig. 6a) no peak of portlandite was
 E. Vitale et al. / Applied Clay Science 141 (2017) 36–45 41

Fig. 6. X-ray diffraction patterns of raw and lime treated bentonite at increasing curing times: a) 5% CaO, b) 20% CaO.

detected in the diffractograms after the addition of 5% of quicklime since previously discussed. For 5% CaO treated sample, a fast and complete
the very short term (24 h of curing). The presence of unconsumed consumption of added lime in the range of temperature of 390 °C and
portlandite was detected only after the addition of 20% CaO, whose re- 460 °C as well as a fast formation of new hydrated phases between
flections progressively reduce over time (Fig. 6b). A broad reflection 110° and 400 °C have been observed. A mass loss attributed to
possibly corresponding to poorly crystalline compounds of CSH was ob- portlandite was detected only after the addition of 20% CaO.
served in all the treated samples starting from 24 h of curing time. Con-
versely, the presence of CAH was detected only after 14 days of curing in
samples treated with 20% CaO.
The thermal analyses of raw, 5% CaO and 20% CaO treated bentonite
after 0, 7, 28 and 60 days of curing showed a weight loss between 500 °C
and 700 °C attributed to the dehydroxylation of montmorillonite parti-
cles. The weight loss between 80 °C and 130 °C is primarily due to loss of
adsorbed water (i.e. interlamellar water not linked to the exchangeable
cation and water between the clay particles). No additional peaks be-
tween 390 °C and 460 °C due to dehydration of portlandite were ob-
served since 24 h for samples treated with 5% of lime. The presence of
unconsumed portlandite was detected only for the 20% CaO treated
sample. Differences between the raw and treated samples were detect-
ed between 110 °C and 400 °C, mainly due to dehydration of new
formed calcium hydrates as products of pozzolanic reactions
(Al-Mukhtar et al., 2014; Pomakhina et al., 2012; Dewindt et al.,
2014). These results are relevantly consistent with the XRD results. Fig. 7. Time quantitative interpretation of TGA analysis on 5% and 20% CaO treated samples
Fig. 7 shows the quantitative interpretation of thermal analyses due to hydrates formation.
42 E. Vitale et al. / Applied Clay Science 141 (2017) 36–45
The evolution of the NMR spectra of raw and treated bentonite with
5% CaO at 28, 60 and 120 days of curing is shown in Fig. 8a. The main sig-
nal at −93.3 ppm for raw sample is attributed to silicon in montmoril-
lonite (Q3) (Kinsey et al., 1985; Weiss et al., 1987; Lippmaa et al., 1980).
Slight changes corresponding to the formation of CSH are detectable in
the −78 to − 88 ppm region evolving with curing time. The effect of
lime content on the evolution of the silicon environment of treated ben-
tonite at 28 days of curing time is shown in Fig. 8b. Signals correspond-
ing to CSH were not clearly detected after the addition of 3% CaO and 5%
CaO, whereas they can be observed by increasing lime content. After
28 days of curing, the 29NMR spectrum of the 10% CaO treated bentonite
showed different peaks, namely Q1, Q2 and Q2(1Al) in the − 78 to
− 88 ppm range attributed to the evolution of the CSH formation
(Pomakhina et al., 2012).
The formation of new mineralogical phases and a significant modifi-
cation of the surface state of clay particles were clearly detected in lime
treated bentonite since the very short term, as shown by SEM images in
Fig. 9. The presence of cementitious compounds coating the surface of
clay particles of lime treated samples at increasing curing times is clear-
ly shown.
An abrupt reduction of the specific surface is detected immediately
after the addition of lime (24 h) and is particularly relevant for higher
lime contents; an increasing trend is observed for longer curing times
(Table 3).
1D compression curves of raw and 5% CaO treated bentonite at in-
creasing curing times, namely 24 h, 7, 28, 60 and 120 days, are reported
in Fig. 10a. The addition of lime increases the compressive strength of
Fig. 8. 29Si NMR spectra of raw and treated bentonite: a) 5% CaO samples cured for
increasing curing times; b) samples at increasing lime contents (3% CaO, 5% CaO and
10% CaO) at 28 days of curing.
the treated samples since the short term, inducing a reduction of volu-
metric strains. An increase of yield stress is also detected, whose extent
depends on the curing time. For stress levels higher than yield stress,
treated samples show a high compressibility depending on the
destructuration induced by loads. The stress levels achieved during
the test were not high enough to induce the complete destructuration
of the treated clay. Fig. 10b and c show the relevant role of lime content
in the short (24 h of curing) and long term (120 day of curing) on the
mechanical behaviour of the treated samples.
4. Discussion
The microstructural investigations highlighted a different reactivity
of kaolin and bentonite treated with lime. The low reactivity of kaolinite
clay is consistent with the delay of the portlandite consumption and
new hydrated phases formation (Zhou and Gunter, 1992; Boardman
et al., 2001), as confirmed by XRD and TGA analyses. According to
Chemeda (2015), the coating of kaolinite surface by a layer of adsorbed
calcium or Ca(OH)2 on kaolinite surface inhibits the dissolution reac-
tions favoured by the high pH environment, lowering the release of sil-
icon and aluminium to the system and therefore delaying the kinetic of
pozzolanic reactions. Chemeda (2015) also proposed the preferential
release of aluminium over silicon since the relative easy breaking of
Al\\O bonds of octahedral layer compared to Si\\O bonds of tetrahedral
layer. This can be attributed to the higher strength of Si\\O bonds in the
silicate sheets compared to the Al\\O bonds (Mantovani et al., 2009). As
a consequence of high aluminium concentration, the formation of alu-
minate-hydrated phases (CAH, CACH) is favoured as confirmed by
XRD analyses, whereas 29Si NMR spectra showed no evidence of CSH.
The high reactivity of bentonite is evidenced by the fast and total
consumption of portlandite since the very short term, which can be at-
tributed to the higher cation exchange capacity of montmorillonite, and
its high specific surface area (Boardman et al., 2001). As confirmed by
XRD analyses, portlandite is detected in the system for high lime con-
tents (e.g. 20% CaO). The precipitation of CAH was detected by XRD
only after 14 days for 20% CaO treated samples. 29Si NMR spectra clearly
revealed the presence of CSH.
The development of pozzolanic reactions affects the microstructural
features of the treated soil (Wild et al., 1986; Choquette et al., 1987; Le
Runigo et al., 2011; Metelkova et al., 2012; Cecconi and Russo, 2013).
The strong impact of lime addition on the evolution of specific surface
area As of lime treated samples can be mainly associated with the floc-
culation of particles into larger aggregates (Vitale et al., 2016a). The fol-
lowing increasing trend is mainly due to precipitation of secondary
compounds, whose amount increases over time. The formation of new
mineralogical phases in lime treated samples was also confirmed by
SEM observations. These products are associated with the reaction of
the hydrated lime with the silicon and aluminium released from clay
minerals lattice.
The chemo–physical evolution of the system can be directly linked
to the hydro-mechanical behaviour of the treated samples. For lime
treated kaolin samples, the slight increase of compressive strength
and the yield stress in the very short term (24 h) is mainly due to the re-
organization of clay particles with the formation of larger aggregates
(Vitale et al., 2016a; Vitale et al., 2016b). The microstructural reorgani-
zation is a consequence of flocculation induced by calcium adsorption at
particles surface, and this is consistent with the low reactivity of the clay
in terms of pozzolanic compounds formation with the evidence of new
phases only after long curing times. The precipitation of cementitious
compounds, clearly detected for time intervals longer than 60 days, is
responsible for the mechanical improvement shown by one-dimension-
al tests. The bonding induced by secondary phases promotes an increase
of the yield stress and compressive strength of treated clay towards a
structure-induced behaviour (Leroueil and Vaughan, 1990). The initial
lime content influences the amount of unconsumed portlandite in the
system, playing a key role in the long term development of hydrated
 E. Vitale et al. / Applied Clay Science 141 (2017) 36–45 43

Fig. 9. SEM images: a) and b) raw bentonite; c) and d) 5% CaO treated bentonite cured for 24 h; e) and f) 5% CaO treated bentonite cured for 120 days.

phases formed and hence in the mechanical improvement of the treated
clay. Conversely, the effects of lime addition on the compressibility of
bentonite are relevant since the very short term. The mechanical behav-
iour of the bentonite depends on the combined effect of cation exchange
reaction, flocculation and pozzolanic reactions, which simultaneously
affect its microstructural features. Nevertheless, the rapid development
of pozzolanic reactions with the formation of not well crystallized
cementing compounds prevail on the effect of the microstructural
reorganization of clay aggregates, evidenced by the initial reduction of
the specific surface area of the samples after the addition of lime. The
mechanical response, typical of a structured soil, is not relevantly
affected by curing time, whereas the modification of this behaviour
is proportional to the amount of secondary hydrates phases and there-
fore depending on the lime content of the samples. A relevant
destructuration is indicative of high level of structure induced by the on-
going pozzolanic reactions.
5. Conclusions
In the paper a multi-scale analysis on the influence of clay miner-
alogy on the pozzolanic activity of lime treated clays has been devel-
oped. Chemo-physical evolution and microstructural changes
induced by lime addition have been investigated and interpreted
by means of different investigation techniques. The results of
micro-scale investigations have been directly linked to the experi-
mental evidences at the volume scale of the sample, allowing an in-
terpretation of the mechanical improvement of the treated clays in
the short and long term as a function of the chemo-physical evolu-
tion of the system.
The main findings allow the following conclusions to be drawn:
• pozzolanic activity of lime treated clays strongly depends on clay min-
eralogy
44 E. Vitale et al. / Applied Clay Science 141 (2017) 36–45

• for treated bentonite samples a fast consumption of portlandite has

been detected for lime contents up to 20%; the high reactivity of clay
minerals promotes the formation of CSH compounds since the very
short term
• microstructural reorganization of the clay-lime system and formation
of cementitious compounds affect the macroscopic behaviour of lime
treated samples
• the structured behaviour observed after the addition of lime (increase
of compressive strength and increase of yielding stress) is directly
linked to the chemo-physical evolution of the system
• for lime treated kaolin samples the microstructural reorganization has
a role in mechanical improvement in the short term, whereas the de-
layed formation of secondary phases highlights the structure-induced
mechanical behaviour in the long term.
• due to the high reactivity of the system, the formation of cementitious
compounds is the predominant factor affecting the mechanical behav-
iour of treated bentonite samples

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