Engineering Geology 135136 (2012) 4851

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Engineering Geology
journal homepage: www.elsevier.com/locate/enggeo

The matrix potential of ne-grained soils at the liquid limit

Bojana Dolinar , Stanislav krabl
University of Maribor, Faculty of Civil Engineering, Smetanova ul. 17, 2000 Maribor, Slovenia

a r t i c l e

i n f o

Article history:
Received 14 March 2011
Accepted 10 March 2012
Available online 21 March 2012
Keywords:
Unsaturated soils
Matrix potential
Soil suction
Liquid limit

a b s t r a c t
The liquid and plastic limits (Atterberg limits) are of key importance in soil mechanics because they determine, in
a simple way, the interaction between the solid and liquid phases in soils, and thus provide the possibility of
classifying soils into groups with similar mechanical properties. It has been observed that all ne-grained soils
have an almost equal undrained shear strength and hydraulic conductivity at the liquid limit as well as for the
matrix suction. The results of the experimental tests of several researches have shown the values of the matrix
suction at the liquid limit to be between 0.5 kPa and 7 kPa. The aim of the present study was to determine the
matrix potential of ne-grained soils at the liquid limit by using the experimentally obtained thickness of the
adsorbed water lm on the external surfaces of clay minerals. The double-porosity model for the pore space
geometry was considered as well as the assumption that, at equilibrium, the water in the clay mineral aggregates
and macropores of ne-grained soils is in the same energy state. The obtained values of the matrix potential ranged from 2.2 kPa to 8.6 kPa, depending on the adopted value of the Hamaker constant for the soilwater
system.
2012 Elsevier B.V. All rights reserved.

1. Introduction
As the water content is increased, the consistency of a ne-grained
soil changes from the semi-solid state, to the plastic state, and eventually to the liquid state. The plastic limit is the soil's water-content boundary between the semi-solid and the plastic consistency. The liquid limit
is the soil's water content where further increases in the amount of
water change the consistency from the plastic to the liquid state. The
plastic limit and liquid limit are often collectively referred to as the
Atterberg Limits. These limits are of key importance in soil mechanics
because they determine, in a simple way, the interaction between the
solid and liquid phases in soils, and thus provide the possibility of
classifying soils into groups with similar mechanical properties. The
results of these investigations, in most cases, provide a good basis for
predicting other soil properties, such as deformability, expansion,
hydraulic conductivity, and strength.
In the earlier studies of several researchers it was found that negrained soils have an equal undrained shear strength and hydraulic
conductivity at the liquid limit as well as for the matrix suction. A
review of the accessible literature has shown that the experimentally
determined values of the matrix suction range from 0.5 to 7 kPa.
This paper presents a determination of the matrix potential of negrained soils at their liquid limit based on the experimentally determined thickness of the adsorbed water lm on the external surfaces
of clay minerals. The recent nding that the matrix potential consists
Corresponding author. Tel.: + 386 2 2294325; fax: + 386 22524179.
E-mail addresses: bojana.dolinar@uni-mb.si (B. Dolinar),
stanislav.skrabl@uni-mb.si (S. krabl).
0013-7952/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.enggeo.2012.03.003

of adsorptive and capillary components was also considered as well as

the assumption that ne-grained soils have a double porosity, consisting of micropores within the clay mineral aggregates and macropores
between them.
2. Theoretical consideration
Casagrande (1932) deduced that the liquid limit approximately
corresponds to the water content at which a soil has a shear strength
of about su = 2.5 kPa. Subsequent studies have indicated that the liquid
limit for all ne-grained soils corresponds to a shearing resistance of
about 1.72.8 kPa (Wroth and Wood 1978, Koumoto and Houlsby,
2001). It was also found that although the water contents and void
ratios at the liquid limit for the different ne-grained soils vary over a
very wide range, the hydraulic conductivity is very nearly the same
for all of them (Nagaraj et al., 1991). This means that the effective
pore sizes controlling the uid ow must be about the same for all
ne-grained soils at the liquid limit (Mitchell, 1993). Such a fabric is
consistent with the double-porosity model, i.e., the individual clay minerals associate into aggregates, where the pores between the aggregates
(inter-aggregate) are macropores and the pores within the individual
aggregates (intra-aggregate) form micropores. For the formation of
such an identical pattern of fabric at the liquid limit, the forces of the interaction between the stable units of the clay mineral aggregates need
to be of the same order. If this is true, the amount of water held by the
micropores per unit volume has to be of the same order. For the equilibrium requirement, the same order of matrix suction should prevail in all
the zones of the soilwater system at their liquid-limit state (Nagaraj
and Miura, 2001). Wroth (1979), on the basis of earlier investigations

B. Dolinar, S. krabl / Engineering Geology 135136 (2012) 4851

2.1. Adsorbed and free pore water at the liquid limit

On the basis of previous ndings and experimental tests, Dolinar and
Trauner (2004) determined the portion of adsorbed and free pore water
at the liquid limit of ne-grained soils. They gave the following explanation. Fine-grained soils contain both clay minerals and associated minerals, and the interactions between the clay minerals and the water
affect the soil's water-holding capacity. The water is strongly adsorbed
onto the external surfaces wea of the hydrophilic, non-expanding clay
minerals, whereas the water adsorbs onto both the external wea and
internal surfaces wia of the expanding clay minerals. The soils contain
free pore water (interparticle and inter-aggregate pore water wp) in
addition to strongly adsorbed water (Fripiat et al., 1984). The water
content is usually measured by the mass loss after drying at 100 to
110 C. The total water content w measured by oven drying equals the
pore water plus the external and internal surface water (w = wp + wea
+ wia). The amount of pore water and the external surface water is
mostly dependent on the content of the clay mineral particles (Seed
et al., 1964) and their specic surface area (Farrar and Coleman, 1967;
Grismer, 1987; Muhunthan, 1991), whereas the interlayer water wia is
mostly dependent on the type of the clay mineral and the exchangeable
cations (Grim, 1962; Bergaya et al., 2006). The interlayer water is
strongly adsorbed between the layers; therefore, it cannot inuence
the strength and the compressibility of the ne-grained soils. This
explains why a general criterion cannot be found relating the water
content to the other mechanical properties for soils with and without
expandable clay minerals.
Considering that the quantity of adsorbed water on the external surfaces is directly proportional to the specic surface area of the soils and
that the quantity of pore water depends on the portion of clay minerals
in the soil composition, the total water content at the liquid limit of the
soils wLL (g/g) can be expressed by Eq. (1) for non-swelling soils and by
Eq. (2) for swelling soils.
wLL pwpjLL weajLL pwpjLL hajLLASe w

wLL pwpjLL weajLL wiajLL pwpjLL hajLL ASe w wiajLL

where p is the content (%) of clay minerals in the soil divided by 100
(0b p 1), w (g/m3) is the density of water, wp|LL (g/g) is the quantity
of free pore water at the liquid limit and wea|LL (g/g) is the quantity of
rmly adsorbed water on the clay mineral's external surfaces. The
adsorbed water quantity wea|LL (g/g) depends on the size of the external
surfaces of the clay minerals in soils ASe (m2/g) because the thickness
ha|LL (m) of the rmly adsorbed water on the external surfaces is, for
all clay minerals, constant at the liquid limit (Nagaraj and Miura, 2001).
On the basis of experimental tests on articial mono-mineral soils
(samples 1, 2, 3), their mixtures (samples 4, 5, 6, 7) and composites
containing 10% and 50% non-clay additives (samples 8, 9, 10, 11),
Dolinar and Trauner (2004) conrmed that the quantity of pore water
plus the external surface water at the liquid limit we|LL (%) is linearly
dependent on the external specic surface area ASe and the clay mineral
content p in soils (Eq. (3)).

method). Eqs. (1) and (3) have the same structure; therefore, the rst
and the second terms in both of them have to be equal. Consequently,
the quantity of free pore water at the liquid limit wp|LL = LL (%), the
average thickness of the rmly adsorbed water around the clay grains
hLL = LL (10 8 m) and the quantity of the rmly adsorbed water
around the clay grains wae|LL = hLL ASe = LL ASe (%). If the non-clay
minerals are present, the value of the parameter LL decreases in
proportion to the weight portion of the clay minerals in the soils, but
the slope of the function remains the same (Figure 1).
The samples used in the study of Dolinar and Trauner (2004) also
contained a swelling clay mineral montmorillonite with the calcium
exchangeable cation (samples 3, 5, 6, 7, 8, 9). To determine the relationship between the quantity of pore water plus the external surface water
at the liquid limit and the external specic surface area of the soils it was
necessary to decrease the total water content at the liquid limit for the
interlayer water portion in the expanding soils. The interlayer water
quantity wia was calculated in accordance with Eq. (4), (Fink and
Nakayama, 1972).
wia

ASi d2 d1
pm %
2103

2.2. Soilwater potentials

The total soilwater potential T is dened as the amount of work
per unit quantity of pure water that must be done by external forces
to transfer reversibly and isothermally an innitesimal amount of
water from the standard state to the soil at the point under consideration. If the unit quantity of water in the above denition is taken as
the unit mass, T is the chemical potential T, which has units of
[J/kg]. Considering the energy per unit weight of water, the results in
T are expressed as the total head, hT, which has units of length [m].
The reference to energy per unit volume of water yields a measure T,
which has units of pressure [Pa]. The relationship between the three
different forms of T is T = W T, T = g w hT, where w is the mass
density of water, and g is the acceleration due to gravity. The total
120
3-Ca-montmorillonite

The parameters LL = 31.90 and LL = 0.81 were determined from

the values of ASe (m2/g) and we|LL (%) by approximation (least-squares

7-43,5%(1)+56,5(3)

100

6-51,9%(1)+48,1(3)

p=1

5-62,3%(1)+37,7%(3)

80

2-kaolinite
4-kaolinite

60

p=0,9

1-kaolinite

8-90%(3)+
10%(Q)

9-50%(3)+50%(Q)

p=0,5

40

10-90%(1)+10%(Q)

20
0

wejLL p LL LL ASe

The basal spacing in the c direction, which is d1 =0.96 nm for

dry calcium montmorillonite (dried at 105C), increases to d2 =1.90 nm
in water (Brindley and Brown, 1984). In the case of a calciumexchangeable cation in montmorillonite, the adsorption of water between
the layers is then completed and the basal spacing is practically constant.
When calculating the interlayer water quantity with Eq. (4), the internal
specic surface area ASi =626.80 m2/g and the appropriate mass portions
of montmorillonite pm in the individual soils were used. The assumed basal
spacing (d2) of montmorillonite at the liquid limit was 1.90 nm.

we / LL (%)

and critical state concepts (Russell and Mickle, 1970; Wroth and Wood,
1978), has indicated that all ne-grained soils tend to equilibrate from
the same high initial water-content state to their respective liquidlimit water contents at an applied suction of the order of 6 kPa. According to Nelson and Miller (1992), the matrix suction at the liquid limit is
0.51.0 kPa, while Biarez and Favre (1975) and Fleureau et al. (2002)
obtained a suction of about 7 kPa.

49

100 % clay minerals

90 % clay minerals
50 % clay minerals

11-50%(1)+50%(Q)

10

20

30

40

50

60

70

80

90

100

ASe m2/g
Fig. 1. Quantity of pore water plus the external surface water at the liquid limit we|LL (%) as
a function of the specic surface area ASe. (Q = quartz sand of grain size 0.080.40 mm).

B. Dolinar, S. krabl / Engineering Geology 135136 (2012) 4851

50

soilwater potential T can be separated into a number of components,

but only the matrix potential m and the osmotic potential are
associated with sources that are internal to the soil element.
T m

In Eq. (5) m represents the interaction of the soil water with both
the mineral soil skeleton and the gas phase, while depends on the
salt concentration in the bulk water. It should be noted that the energy
state of the water in the soil is always lower than the energy state of free
water. Consequently, all the potentials are negative quantities, and
their positive values are equal to the suction when the gravitational
and air-pressure potentials are neglected. Some devices for measuring
water potential (e.g., tensiometers) measure the matrix potential only,
while others (e.g., psychrometers) measure both the matrix and osmotic
potentials. The osmotic potential is often small in absolute terms compared to the matrix potential, particularly in non-saline soils.
The basic work concerning liquid adsorption on solid surfaces was
summarised in the fundamental study of Derjaguin et al. (1987). It
can be shown (Philip, 1977; Tuller et al., 1999), that Derjaguin et al.'s
work implies that the matrix potential m results from the combined
effects of the capillary cp and adsorptive ad potentials within the soil
matrix, and it can be expressed as the following, i.e., the augmented
YoungLaplace equation:
m ad h cp

where h is the thickness of the adsorbed water lm and is the mean

curvature of the liquidvapour interface. It should be noted that the
capillary potential is always equal to
cp ua uw b 0

where ua and uw are the pore air pressure and the pore-water pressure.
Note that when ua =0 (ambient air pressure), cp =uw b 0. The adsorptive potential, based on van der Waal's interaction, was studied by
Iwamatsu and Horii (1996). Tuller et al. (1999) used this work in order
to establish the following approximate theoretical form for this potential
ad

6 h3

where h is the thickness of the adsorbed liquid layers and A (J) is the
Hamaker constant. It represents the average interactions between
macro-objects, such as mineral surfaces, and the liquid due to the shortrange van der Waals forces (Ackler et al., 1996; Bergstrm, 1997). For a
soilwater system A=10 20 to 10 19 J. Or and Tuller (1999)
recommended adopting a value of A=6.010 20 J, Mitchell and
Soga (2005) quoted values of A=3.110 20 J for kaolinite, A=
2.510 20 J for illite and A=2.210 20 J for montmorillonite.
Medout-Marere (2000) found values of A=6.810 20 J for kaolinite,
A=8.610 20 J for illite, and A=7.810 20 J for montmorillonite.
In Eq. (8), when h is expressed in metres and A in joules, then the resulting
potential ad is given in pascals.
3. Matrix potential at the liquid limit of ne-grained soils
The matrix potential of ne-grained soils at the liquid limit can be
determined on the basis of the following ndings:
1. The thickness of the adsorbed water lm on the external clay mineral
surfaces is 8.1 nm for the quantity of water that corresponds to the
liquid limit (Dolinar and Trauner, 2004).
2. The adsorption of the interlayer water in swelling clay minerals is
fully complete at the liquid limit (Brindley and Brown, 1984).
3. The fabric of ne-grained soils is of the same pattern at their liquid
limit, consisting of clay mineral aggregates, associated minerals and

angular macropores (Mitchell, 1993; Nagaraj and Miura, 2001). The

angular macropores allow the simultaneous occupation of water
and air in each cross-section, with the water occupying the corners
of the macropores while the air is located in their interior. The curvature of the airwater interface produces a capillary potential, which
implies tensile stresses in the capillary water. The voids inside the
aggregates represent the microporosity. These pores are assumed
to be saturated at the liquid limit, and the interaction between the
water and the clay minerals is governed by adsorption mechanisms.
In such conditions the capillary potential of the water in the aggregates is equal to zero, cp(aggregate) = 0 and the matrix potential is
equal to the adsorbtive potential m(aggregate) = ad. The external
surfaces of the aggregates constitute the internal surface of the
macropores, and so it is convenient to consider the adsorbed water
in the macropores as part of the aggregates' water. Adopting this
convention ad(macropore) = 0 and m(macropore) = cp. At equilibrium,
the water in the aggregates and macropores must be at the same
energy state, i.e., m(aggregate) = m(macropore) or equivalently
m ad cp :

Failure to satisfy this requirement must result in the migration of

water from the macropores to the aggregates or vice versa, until the
potential equality is re-established. It should be noted that these relations
do not contradict the augmented YoungLaplace Eq. (6), since they are
relevant to different water phases, located in the aggregates and the
macropores, respectively. These relations are only valid if the macropores
are not empty of water (Baker and Frydman, 2009; Frydman and Baker,
2009).
Considering the above ndings, Eqs. (8) and (9) and the Hamaker
constant A=6.010 20 J (recommended by Or and Tuller, 1999),
the matrix potential at the liquid limit m|LL of ne-grained soils is equal
to:
m j LL ad

A
5:99 kPa:
6 h3

10

For the proposed limit values of the Hamaker constant A=

2.210 20 J and A=8.6 210 20 J, the matrix potential at the liquid
limit of ne-grained soils ranged from m|LL =2.2 kPa to m|LL =
8.6 kPa.
4. Conclusion
This paper focuses on an investigation of the matrix potential of negrained soils at their liquid limit. The previously obtained experimental
values for the suction ranged from 0.5 to 7 kPa. The calculated values of
the matrix potentials presented in this paper vary from 2.2 kPa
to 8.6 kPa depending on the adopted value of the Hamaker constant
for a soilwater system. For the recommended value of the Hamaker constant 6.010 20 J, the calculated matrix potential is equal to 6 kPa,
which is consistent with the several previously determined values
based on experiments. The procedure used for determining the matrix
potential was based on the experimentally obtained thickness of the
adsorbed water lm on the external surfaces of clay minerals at their
liquid limit. The double-porosity model consisting of saturated clay aggregates and angular macropores was considered as well as the assumption
that, at equilibrium, the water in the aggregates and macropores is in the
same energy state.
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