Applied Clay Science 54 (2011) 189–195

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Applied Clay Science

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The unusual behavior of a Milos bentonite in cement suspensions

K.-H. Ohrdorf a,⁎, S. Kaufhold b, F. Rüßmann c, K. Ufer d, H. Flachberger e
a
Ingenieurbüro für Bentonit-Technologie Dipl.-Ing. Ohrdorf, Wiesbaden, Germany
b
Bundesanstalt für Geowissenschaften und Rohstoffe, Hannover, Germany
c
Dyckerhoff AG, Wiesbaden, Germany
d
TU Bergakademie Freiberg, Institute of Mineralogy, Freiberg, Germany
e
Montanuniversität Leoben, Chair of Mineral Processing, Austria

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

Article history: Bentonites from different deposits worldwide often show unexplainable differences with respect to their per-
Received 27 October 2010 formance in different applications. Examples are the water uptake capacity and bleaching ability (Kaufhold,
Received in revised form 5 August 2011 2001; Kaufhold et al., 2010). The present study focused on the rheological parameters of bentonite-cement
Accepted 5 August 2011
slurries used in civil and underground engineering. By measuring the viscosity and yield point of several dif-
Available online 1 November 2011
ferent Na+-activated calcium bentonites mixed with blast furnace cement, behavior of a Milos bentonite was
Keywords:
detected characterized by an unusual increase of the viscosity after addition of the cement. A detailed miner-
Bentonite alogical characterization was conducted to identify the reason. The most striking difference of the samples
Rheological parameters was the content of soluble silica making up 27 mass% of the bentonite (soluble in hot sodium carbonate so-
Soluble silica lution). However, the addition of silica gel to bentonites free of soluble silica proved the effect on the rheo-
logical parameters viscosity and yield point.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction – there is no pre-swelling required,

Bentonite-cement suspensions are recently applied in some special
fields of civil and underground engineering. In retention walls the ben-
tonite of such a suspension acts as a supporting agent of the trench dur-
ing excavation and provides low permeability of water after the setting
of the cement. The process in which the bentonite-cement suspension
remains inside the trench is called the “One-Phase-Method” (Fig. 1)
and was inaugurated by the French civil engineering firms Soletanche
and Bachy in the 1970s. The bentonite was stirred with water, and a
pre-swelling time of up to 24 h was allowed to develop the best achiev-
able viscosity and yield point of the commercially available bentonite at
the site.
Then, the cement and additives (e.g. mineral filler) were added to
the aged bentonite suspension.
As an alternative to this method, dry premixes of bentonite, ce-
ment, and additives made in special mixing plants of cement factories
have become more and more popular. Based on the research of the
firms Anneliese Cement AG and Dyckerhoff AG in 1988, a patent
was granted to Anneliese (DE 3633736A1) which is exclusively used
by Dyckerhoff. In Germany and Austria most of the constructors of re-
tention walls use such premixes. The advantages of this method are:
– the premixes are easier to handle,
– they require less site equipment,
⁎ Corresponding author.
E-mail address: bentonit.technologie.ohrdorf@t-online.de (K.-H. Ohrdorf).
– there is better recipe and quality control of the mixture during
production.
However, the disadvantage is that the recipe cannot be easily
modified on site in the case of special site requirements (e.g. special
soil properties).
The one-phase-retention wall method requires increased perfor-
mance of activated calcium bentonites, particularly with respect to vis-
cosity and thixotropy during the time of trenching and excavation.
Therefore, bentonites with high swelling capacity are required. Activat-
ed bentonites are known to lose appreciable swelling capacity in the
presence of free Ca ++-ions. Therefore, a certain “cement-stability” is
required. This change of the rheological properties most probably can
be attributed to a cation exchange whereby the Na +/Ca ++ ratio deter-
mines the rheological properties. The reasons, however, for the rather
different performance of different bentonites with respect to the change
of rheological properties cannot be explained yet. Possibly, different
selectivity constants for the cation exchange of the different smectites
play a role. In addition, minor components such as carbonates are
known to affect cation exchange processes (e.g. Kaufhold and Dohrmann,
2009a,b). The carbonate anions react with the Ca++-ions of the cement.
Though the term “cement-stability” is not defined exactly, in in-
dustrial usage a bentonite is called “cement stable” if it does not sig-
nificantly change its rheological properties after being mixed with
cement and within the time of trenching until the cementation starts.
The three economically most important European regions for ben-
tonite production: Milos (GR), Bavaria (D) and Sardinia (I) have been

0169-1317/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2011.08.001
190 K.-H. Ohrdorf et al. / Applied Clay Science 54 (2011) 189–195
Fig. 1. Trenching using a bentonite-cement slurry.
selected in order to compare the rheological properties in cement
slurries. Each of the samples was composed of at least 50 individual
samples of different horizons and stocks of the deposits. Commercially
available hydrophobized precipitated silica “Vulkasil S”, hydrophilic
Fig. 2. Activation curve of three bentonites of high viscosity from the three European
economically most important mining regions.
fumed silica “Aerosil 90” and water glass solution were used as additives
to bentonites free of soluble silica.
The preparation for mineralogical and chemical analysis includ-
ed crushing to b2 mm, homogenizing, drying at 80 °C to a moisture
content of approx. 5 mass% and grinding (b63 μm) in an agate
mortar.
The mineralogical composition was determined by the XRD-Rietveld
technique as described by Ufer et al. (2008).
The chemical composition of the powdered samples was deter-
mined using a PANalytical Axios and a PW2400 spectrometer. The
samples were prepared by mixing with a flux material and melting
into glass beads. The beads were analyzed by wavelength dispersive
X-ray fluorescence spectrometry (WD-XRF). To determine loss on
ignition, (LOI) 1 g of the sample material was heated to 1030 °C for
10 min.
The CEC was determined by the so-called Cu-triene method
(Meier and Kahr, 1999).
The amount of soluble silica was determined by using 0.02, 0.04,
0.06, 0.08, 0.1 g (pre-dried at 105 °C for 24 h) samples and a
50.0 mL 2% sodium carbonate solution. The suspension was shaken
at 60 °C. The Si content in the supernatant was determined by ICP-
OES. The reproducibility was approximately ±0.1%.
The total carbon, sulfur and organic carbon contents of air-dried
samples (170–180 mg) were measured with the LECO CS-444-
Analysator. The carbonates were removed by reaction with HCl at
80 °C.
To determine the rheological properties, the samples were activated
at 30 mass% of moisture in laboratory scale with the I.B.O. activation
method. This method describes an industrial activation technique to
create new surfaces by destroying continuously the sediment structure
of a bentonite from a given deposit in such a way that no further mixing
time or shear forces can increase the efficiency of the cation exchange
under the conditions of a commercial production. The efficiency of the
cation exchange can be detected by the yield point of the bentonite
suspension.
The guidelines to determine the suspension properties for reten-
tion walls are a combination derived from the API Spec. 13 for drilling
fluids, the DIN 4126 and 4127 for retention walls and the DIN 18136
and 18310 for geotechnics.
Fig. 3. Activation curve of three different bentonites of low viscosity of the three European
economically most important mining regions.
 K.-H. Ohrdorf et al. / Applied Clay Science 54 (2011) 189–195 191

Fig. 4. Marsh viscosity of bentonite- and bentonite-cement slurries (arrow shows the lower limit of the desired value range).

The preparation of the suspension has to follow the specific in-
structions given by each of the cement manufacturers.
In the present paper the suspensions were prepared as follows:
80 g of activated bentonite was added to 2 L of deionized water
at 20± 2 °C and stirred for 10 min with a dissolver-type stirrer at
3,000 ± 200 rpm.
A 3 L cup of 150 mm inside diameter was used. After swelling for
1 h 400 g of a blast furnace cement type CEM III/C (Dyckerhoff SOLI-
DUR®) was added. The suspension was then stirred under the same
conditions for 10 min.
To determine the viscosity, a Marsh-funnel according to the API
Spec. 13, Sect. 2 (1982) with an outlet tube diameter of 4.76 mm
was filled with 1500 mL of the suspension, and the outflow of
1000 mL was measured after a relaxation time of 30 s. Known as the
“Marsh-time” or “Marsh-viscosity” this data allows the assessment
of the flow properties and processability of the suspension during
trenching and excavation. The value of water is approx. 28 s, whereas
the guidelines (desired value) for bentonite-cement-suspensions
require a Marsh-time of 35 to 40 s.
The yield point relates particularly well to the stability of the trench
and the processability of the suspension. The yield point was measured
with the “Kugelharfe” (would be “sphere harp” in English), a device
which can be easily handled on site (DIN 4126). Ten small spheres with
different diameters and densities were held by strings and numbered
according to increasing mass and diameter. The slurry was poured into
a cup, and after a relaxation time of 60 s all spheres were slowly dipped
into the slurry. The first number in row from the lightest (no. 1) to the
heaviest (no. 10) sphere which sinks into the slurry represents the yield
point of the slurry and is converted in N/cm2 by a specific scheme.
The guidelines (desired value) for a bentonite-cement-suspension
require a yield point of 14–50 N/cm 2 corresponding to sphere no.
4–8.

Fig. 5. Yield point of bentonite- and bentonite-cement suspensions.

192 K.-H. Ohrdorf et al. / Applied Clay Science 54 (2011) 189–195
2. Results and discussion
2.1. Rheological data
The rheological properties of industrially activated bentonites
directly correlate with the “chemical degree of activation” (CAG),
i.e. the amount of sodium carbonate needed for the cation exchange
according to the nature of the bentonite and the “technical degree
of activation” (TAG), i.e., the feasibility to activate lumpy raw mate-
rials of 30 ± 3 mass% of moisture in a production plant.
The maximum values of the rheological properties were reached
only if both degrees of activation approach 100%. Any under- or
over-activation inevitably leads to a loss of rheological properties, in-
dependent of the deposit-related bentonite characteristics. Typical
activation curves following the CAG of bentonite from different
deposits were obtained with a 5 mass%-suspension and a newly
developed method using the Rheometer RS 600 made by Thermo-
Fisher GmbH, Karlsruhe.
The suspensions were then screened at 0.075 mm to eliminate
particles above the measuring distance of the plate-cone combination
of the Rheometer (0.105 mm) resulting in differences of the solid
concentration. In order to eliminate these small differences and to
make the yield points comparable, a “specific yield point” (yield
point per gram bentonite) was calculated, and the optimum of the
CAG could be clearly defined (Ohrdorf, 2010) (Figs. 2 and 3).
In order to compare bentonite deposits of different origins the
identification of the optimum activation is necessary. The large con-
tent of Ca ++-ions in the suspension derived from the cement, causes
an aggregation of the montmorillonite platelets (Lagaly, 1993).
Therefore, mostly blast furnace slag cements are used in bentonite-
cement-slurries.
The data in Figs. 4 and 5 proved that
– the optimum activation can minimize but not completely avoid
the loss of rheological properties upon addition of cement,
– the assumption which was made up to now, that only Milos ben-
tonites can be used in bentonite-cement slurries is incorrect. At
CAG = 100% and at TAG = 100%, activated Bavarian and Sardinian
bentonites of high basic viscosities can be used as well,
– a Milos bentonite was identified which had a comparatively low
basic viscosity but obtained high viscosity after addition of the
cement.
This bentonite fulfilled all the required bentonite-cement slurry
properties including Marsh viscosity, “Kugelharfen” yield point, filtra-
tion and sedimentation behavior (Table 1).
The unusual behavior of this Milos bentonite was only observed
after activation, i.e. when Na +-ions were present (Fig. 6). At
CAG = 0%, i.e. calcium bentonite, the Marsh viscosity became similar
to water. Adding sodium carbonate until CAG = 100%, the Marsh vis-
cosity of the bentonite-cement suspension was significantly in-
creased exceeding the Marsh viscosity of the pure bentonite
suspension in spite of the presence of the Ca ++-ions of the cement.
Based on viscosity tests with a pure bentonite suspension, this
rheological anomaly could not be related to the type of the
Table 1
Properties of the Milos bentonite slurries with unusual rheological behavior.
Bentonite suspension Bentonite-cement suspension
Marsh Liquid limit Marsh Liquid limit Filtrate
viscosity “Kugelharfe” viscosity “Kugelharfe”
s N/m2 s N/m2 mL
32.8 8.1 47 56.8 38.2
Desired value 38–55 37–67 b55
(Dyckerhoff)
montmorillonite. It was assumed that accessory minerals could play
an important role.
2.2. Chemical and mineralogical investigation
The results of the mineralogical characterization are summarized
in Table 2.
ASP and V3 were two samples of the Milos bentonite, showing the
anomaly described, V2 was a Milos bentonite with good rheological
properties, V4, V5, were Bavarian bentonites with good and bad rhe-
ological properties, V6B, V6G were Bavarian and Sardinian bentonites
also with good and bad rheological properties.
As expected, all samples are mainly composed of smectites with
partially significant contents of illite/muscovite. However, the large
illite/muscovite content of samples V4 and V5 was attributed to a sys-
tematic error of the Rietveld refinement which depends on the qual-
ity of the structural models and particularly on the disorder models.
Hence considering the sum of 2:1 clay minerals is probably closer to
the true composition. The contents of the minerals not needing a dis-
order model in the Rietveld refinement (carbonates, quartz, feldspar)
are supposed to be close to the real contents. The contents of the min-
erals not needing a disorder model in the Rietveld refinement (car-
bonates, quartz, feldspar) are supposed to be close to the real
contents. This was confirmed by comparing the calcite content calcu-
lated with the LECO data.
Sample V4 contained ankerite, pyrite was found only in sample
V3, and dolomite only in sample V7. Furthermore, the kaolinite con-
tent of V5 is particularly large, which is properly reflected by the
Al2O3-content. Samples ASP and V3, from the same location, contain
appreciable amounts of low crystalline silica polymorphs (cristoba-
lite, opal-CT, and probably some opal-A) which results in the large
amount of soda-soluble silica (Fig. 7). The exchangeable cation popu-
lation before activation did not vary significantly. The significant dif-
ferences of the Ca ++-contents can be attributed to the different
content of carbonates which partially dissolve throughout during
the CEC determination (Dohrmann and Kaufhold, 2010).
The most striking property of the samples with unusual rheology
was the high content of soda-soluble silica of 27 mass% of the benton-
ite. The soda-soluble silica, which is also dissolved in contact with the
alkaline cement pore water, may react with the cement. One possible
reaction is a formation of CSH phases.
24 h
sedimentation
%
0.5
b3
Fig. 6. Marsh viscosity of a bentonite-cement suspension versus CAG; CAG = 0 refers to
calcium bentonite (arrow shows the lower limit of the desired value range).
 K.-H. Ohrdorf et al. / Applied Clay Science 54 (2011) 189–195 193

Table 2
Mineralogical and chemical characterization of the bentonites.

Sample ASP V2 V3 V4 V5 V6 B V6 G V7

Mineralogical composition (XRD-Rietveld according to Ufer et al., 2008)

Quartz [mass%] 3 3 3 11 9 4 10
Smectite [mass%] 54 77 53 51 46 90 78
Illite/muscovite [mass%] 24 19
Feldspar [mass%] 5 4 6 4 6 5 11
OpalCT [mass%] 13 13
Cristobalite [mass%] 19 10 20
Calcite [mass%] 2 9 1 2 1
Dolomite [mass%] 1
Ankerite [mass%] 2
Gypsum [mass%] 2 4 2
Kaol/halloysite [mass%] 4 4 20
Anatase [mass%] 1
Pyrite [mass%] 0
Sum [mass%] 100 100 100 100 100 100 0 100

C-/S-analysis (LECO)
Organic C [mass%] 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Inorg. C [mass%] 0.1 0.3 0.1 1.3 0.0 0.2 0.1 0.4
Calcite (modal) [mass%] 0.6 2.5 0.9 11.0 0.2 1.6 0.6 3.2
Total C [mass%] 0.1 0.3 0.2 1.4 0.1 0.2 0.1 0.4
Total S [mass%] 0.3 0.8 0.3 0.0 0.0 0.2 0.0 0.0

Soda soluble silica (ICP)

0.02 g/0 mL 27.0 9.3 27.3 4.1 4.7 5.9 5.8 4.6
0.04 g/50 mL 27.1 8.0 22.8 3.0 3.4 4.1 4.0 3.4
0.06 g/50 mL 22.3 7.6 18.0 2.4 2.8 3.3 3.0 2.6
0.08 g/50 mL 23.9 7.2 14.5 2.1 2.4 2.8 2.5 2.4
0.1 g/50 mL 22.2 7.0 12.8 1.8 2.0 2.4 2.1 1.9

Cation exchange capacity (Cu-triene-method)

Na+ [meq/100 g] 7 10 6 0 0 0 0 1
K+ [meq/100 g] 0 1 0 3 2 3 3 4
2+
Mg [meq/100 g] 28 31 30 18 20 54 50 38
2+
Ca [meq/100 g] 27 85 26 55 41 60 51 37
Sum cations [meq/100 g] 62 127 63 76 62 117 104 81
CEC [meq/100 g] 53 78 56 62 62 104 100 73
S-T [meq/100 g] 9.0 49.6 6.7 14.6 0.1 12.8 3.4 7.6

Chemical composition of main elements (XRF)

SiO2 [mass%] 65.0 52.8 66.3 48.8 52.2 50.1 51.4 52.2
TiO2 [mass%] 0.3 0.6 0.3 0.4 0.4 0.3 0.3 0.5
Al2O3 [mass%] 13.9 15.7 14.2 15.2 20.0 16.2 16.2 14.6
Fe2O3 [mass%] 2.0 4.5 2.1 4.9 5.6 3.7 4.2 5.5
MnO [mass%] 0.0 0.0 0.0 0.1 0.1 0.0 0.0 0.1
MgO [mass%] 2.1 2.8 2.2 3.2 2.7 5.6 5.5 5.3
CaO [mass%] 1.0 3.2 1.0 6.7 1.4 2.1 1.6 2.1
Na2O [mass%] 0.3 0.4 0.3 0.3 0.4 0.0 0.1 0.2
K2O [mass%] 0.5 0.7 0.5 1.7 1.4 1.1 1.3 2.4
P2O5 [mass%] 0.0 0.1 0.0 0.1 0.1 0.1 0.1 0.1
(SO3) [mass%] 0.4 1.6 0.3 0.0 b0.01 0.3 0.0 0.0
LOI [mass%] 14.4 17.2 12.6 18.3 15.6 20.0 19.2 16.8
Sum [mass%] 99.8 99.7 99.8 99.7 99.7 99.5 99.8 99.8

However, CSH phases were not detected by electron microscopy
(NanoSEM).
One open question is why the unusual rheology was not observed
in the case of calcium bentonites. On the one hand, the Na +-ions could
form water glass as an intermediate product. Alternatively, the pH
could be important because calcium bentonites are known to effec-
tively buffer the pH at around 6.5, which decreases the dissolution of
silica to finally prove the mechanism, additional tests are required.
2.3. Explanation of the unusual rheological behavior
The idea that soluble silica could be responsible for the unusual rhe-
ological behavior was tested by using a mixture of activated bentonite
free of soluble silica and different types of synthetic silica gels. However,
silica gels show strong differences in the rheological properties of the
mixtures. This can be easily explained by the different structures and
solubilities of the gels. Moreover, some silica gels were hydrophobized
which of course decreases the solubility in aqueous solutions. Hydro-
phobized silica gels such as “Vulkasil S” from Lanxess AG did not show
any increase of the viscosity and yield point. Two silica gels, the hydro-
phyllic “Aerosil 90” from Evonik AG and sodium water glass solution
were tested with positive results (Fig. 9).
Although the level of the Milos bentonite could not be reached, the
significant increase of the viscosity and yield point of the cement sus-
pensions with Bavarian and Sardinian bentonites after addition of sil-
ica was evident (Figs. 8, 9).
3. Summary and conclusions
By measuring the viscosity and yield point of several bentonites
mixed with standard blast furnace cement, an unusual increase of
the viscosity of one of these, a Milos bentonite, was observed. The
most striking property of this bentonite was the high content (up to
27 mass%) of soda-soluble silica. The presence of sodium ions was a
194 K.-H. Ohrdorf et al. / Applied Clay Science 54 (2011) 189–195

precondition but the effect of sodium ions on the unusual increase of

the rheological properties could not be evaluated. The influence of
soluble silica was verified with the addition of Aerosil 90 and sodium
water glass solution. The Milos bentonites contain variable amounts
of soluble silica due to the acid post formational alteration (Decher,
1997; Kaufhold, 2001; Kaufhold and Decher, 2003). Therefore, the
content of soda-soluble silica of bentonites might be an additional
quality-determining parameter of bentonites which are intended to
be used in combination with cement.

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